Resistor composition and method for forming inhibitor pattern

Abstract

This invention provides an inhibitor composition containing a polymer compound having a constituent unit (a01) derived from a compound represented by a general formula (a0-1), wherein W01 is a polymerizable group, Ct is a tertiary carbon atom, Xt is a hydrocarbon group that forms a monocyclic or polycyclic ring with Ct, and some or all of the hydrogen atoms in the monocyclic or polycyclic hydrocarbon group may be substituted by substituents, and some of the carbon atoms constituting the ring may be substituted by heteroatoms, and Ra01 is a linear, branched, or cyclic aliphatic hydrocarbon group.

Description

[Technical Field]

[0001] This invention relates to a resist composition and a method for forming a resist pattern. This invention claims priority based on Japanese Patent Application No. 2020-214127 filed on December 23, 2020 and Japanese Patent Application No. 2021-024651 filed on February 18, 2021, the contents of which are incorporated herein by reference. [Previous Technology]

[0002] In recent years, the miniaturization of patterns has rapidly evolved in the manufacturing of semiconductor devices or liquid crystal display devices due to advancements in lithography technology. As a method of miniaturization, one common approach is to shorten the wavelength (increase the energy) of the exposure light source.

[0003] Resistant materials are required to have photolithography properties such as sensitivity to such exposure light sources and resolution capable of reproducing finely sized patterns. As resist materials that meet such requirements, conventionally, chemically amplified resist compositions have been used, which contain a substrate component whose solubility in the developer changes due to the action of acid and an acid-generating agent component that generates acid due to exposure.

[0004] In chemically amplified inhibitor compositions, resins having multiple constituent units are generally used to improve lithography properties, etc. For example, Patent Document 1 describes a copolymer with a uniform molecular weight, which is used as an inhibitor material having specific constituent units containing triple bonds and specific constituent units containing lactone ring groups. [Prior Art Documents] [Patent Documents]

[0005] [Patent Document 1] Japanese Patent Application Publication No. 2009-84490 [Summary of the Invention]

[0006] [The problem this invention aims to solve]

[0007] Lithography technology is constantly evolving, with resist patterns becoming increasingly finer. For example, in EUV or EB lithography, the goal is to form patterns as fine as tens of nanometers. Thus, the smaller the resist pattern size, the higher the required sensitivity to the exposure light source, in-plane uniformity (CDU) of the pattern size, and good lithography characteristics such as resolution. However, in resist compositions containing conventional resins, as described above, it is difficult to obtain the desired resist pattern shape if high sensitivity to the exposure light source is desired; satisfying any of these characteristics is quite challenging.

[0008] In view of the above facts, the present invention aims to provide a resist composition capable of forming a resist pattern with higher sensitivity and good CDU and resolution, and a method for forming a resist pattern using the resist composition. [Means for Solving the Problem]

[0009] To solve the above-mentioned problems, the present invention adopts the following structure. That is, the first type of the present invention is a resist composition that generates acid due to exposure and whose solubility in the developing solution changes due to the action of the acid, wherein it contains a resin component (A1) whose solubility in the developing solution changes due to the action of the acid, and the aforementioned resin component (A1) has a constituent unit (a01) derived from a compound represented by the following general formula (a0-1).

[0010] [In the formula, W01 is a polymerizable group, Ct is a tertiary carbon atom, Xt is a hydrocarbon group that forms a monocyclic or polycyclic ring with Ct, and some or all of the hydrogen atoms in this monocyclic or polycyclic hydrocarbon group may be substituted by substituents, and some of the carbon atoms constituting the substituted ring may be substituted by heteroatoms, and Ra01 is a straight-chain, branched-chain or cyclic aliphatic hydrocarbon group].

[0011] The second aspect of the present invention is a method for forming a resist pattern, which includes the steps of forming a resist film by using a resist composition as described in the first aspect on a support, exposing the resist film, and developing the exposed resist film to form a resist pattern. [Effects of the Invention]

[0012] By means of the present invention, a resist composition capable of forming a resist pattern with higher sensitivity and good CDU and resolution can be provided, and a method for forming a resist pattern using the resist composition can be provided.

Implementation Method

[0013] In this specification and the scope of this application, "aliphatic" refers to a concept relative to aromatic and non-aromatic compounds. "Alkyl" unless otherwise specified includes monovalent saturated hydrocarbon groups in the form of straight chains, branched chains, and cycles. The same applies to alkyl groups in alkoxy groups. "Decanyl" unless otherwise specified includes divalent saturated hydrocarbon groups in the form of straight chains, branched chains, and cycles. "Halogen atom" includes 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 also have substituents," it includes cases where hydrogen atoms (-H) are replaced by monovalent groups and cases where methylene (-CH2-) is replaced by divalent groups. "Exposure" is a concept that includes irradiation by radiation.

[0014] An "acid-decomposable group" is an acid-decomposable group whose structure is capable of breaking at least a portion of its bonds due to the action of an acid. Examples of acid-decomposable groups that increase polarity due to the action of an acid include groups that decompose due to the action of an acid and generate polar groups. Examples of polar groups include carboxyl groups, hydroxyl groups, amino groups, and sulfonic acid groups (-SO3H). More 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 a polar group containing OH are protected by acid-dissociating groups).

[0015] "Acid-dissociable group" refers to (i) an acid-dissociable 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 due to the action of an acid, and which, through a decarbonation reaction, can further break the bonds with adjacent atoms. The acid-dissociable group constituting the acid-dissociable group must be a group with a lower polarity than the polar group generated by the dissociation of the acid-dissociable group. Therefore, when the acid-dissociable group dissociates due to the action of an acid, a polar group with a higher polarity than the acid-dissociable group will be generated, thus increasing the polarity. As a result, the overall polarity of component (A1) increases. By increasing polarity, the solubility of the developing solution will change accordingly. When the developing solution is alkaline, the solubility will increase, and when the developing solution is organic, the solubility will decrease.

[0016] "Substrate component" refers to an organic compound with film-forming energy. Organic compounds used as substrate components are broadly distinguished as non-polymers and polymers. As non-polymers, those with a molecular weight of 500 or more but less than 4000 are generally used. The term "low molecular weight compound" below refers to non-polymers with a molecular weight of 500 or more but less than 4000. As polymers, those with a molecular weight of 1000 or more are generally used. The term "resin," "high molecular weight compound," or "polymer" below refers to polymers with a molecular weight of 1000 or more. The molecular weight of polymers is the weight average molecular weight converted from polystyrene in GPC (gel permeation chromatography).

[0017] "Derived constituent units" refers to the multiple bonds between carbon atoms, such as the constituent units formed by the cleavage of vinyl double bonds. In "acrylates", the hydrogen atom bonded to the α-carbon atom can also be substituted by a substituent. The substituent (Rαx) that replaces the hydrogen atom bonded to the α-carbon atom is an atom or group other than hydrogen. It also includes itaconic acid diesters in which the substituent (Rαx) is substituted by a substituent including an ester bond, or α-hydroxyacrylates in which the substituent (Rαx) is substituted by a hydroxyalkyl group or a group that modifies its hydroxyl group. Furthermore, the α-carbon atom of an acrylate, unless otherwise specified, refers to the carbon atom bonded to the carbonyl group of acrylic acid. Hereinafter, acrylates in which the hydrogen atom bonded to the α-carbon atom is substituted by a substituent are sometimes referred to as α-substituted acrylates.

[0018] "Derivative" refers to the concept of derivatives of a compound in which the α-hydrogen atom is replaced by an alkyl group, a haloalkyl group, or other substituents. Examples of such derivatives include those in which the hydrogen atom of the hydroxyl group in a compound in which the α-hydrogen atom can also be replaced by a substituent is replaced by an organogroup; and those in a compound in which the α-hydrogen atom can also be replaced by a substituent is bonded to a substituent other than the 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 α-hydrogen atom of substituted hydroxystyrene include those identical to Rαx.

[0019] In this specification and the scope of this application, based on the structure represented by the chemical formula, there may be asymmetric carbon, and there may also be mirror-image isomers (enantiomers) or non-mirror-image isomers (diastereomers). In this case, one chemical formula represents such isomers. Such isomers may be used alone or as mixtures.

[0020] (Resistant Composition) The resist composition of this embodiment is acid generated by exposure, and its solubility in the developer changes due to the action of the acid. The relevant resist composition contains a substrate component (A) whose solubility in the developer changes due to the action of the acid (hereinafter also referred to as "(A) component").

[0021] When a resist film is formed using the resist composition of this embodiment and the resist film is selectively exposed, acid is generated in the exposed portion of the resist film. Due to the action of the acid, the solubility of component (A) in the developer solution changes. On the other hand, in the unexposed portion of the resist film, the solubility of component (A) in the developer solution does not change. Therefore, a difference in solubility in the developer solution will occur between the exposed and unexposed portions of the resist film.

[0022] The resist composition of this embodiment can be either a positive resist composition or a negative resist composition. Furthermore, the resist composition of this embodiment can be used in an alkaline developing process where an alkaline developing solution is used in the developing process during resist pattern formation, or in a solvent developing process where an organic solvent-based developing solution is used in the developing process. That is, the resist composition of this embodiment is a "positive resist composition for alkaline developing process" that forms a positive resist pattern in the alkaline developing process, and a "negative resist composition for solvent developing process" that forms a negative resist pattern in the solvent developing process.

[0023] <(A) Component> In the resist composition of this embodiment, the (A) component contains a resin component (A1) (hereinafter also referred to as "(A1) component") whose solubility in the developer changes due to the action of acid. The aforementioned resin component (A1) has a constituent unit (a01) derived from a compound represented by the general formula (a0-1). As the (A) component, at least the (A1) component is used, and the (A1) component may also be used in combination with at least one of other high molecular weight compounds and low molecular weight compounds.

[0024] In the inhibitor composition of this embodiment, component (A) may be used alone or in combination with two or more components.

[0025] • Regarding component (A1), component (A1) has a constituent unit (a01).

[0026] ≪Constituted Unit (a01)≫ The constituent unit (a01) is a constituent unit derived from a compound represented by the following general formula (a0-1).

[0027] [In the formula, W01 is a polymerizable group, Ct is a tertiary carbon atom, Xt is a hydrocarbon group that forms a monocyclic or polycyclic ring with Ct, and some or all of the hydrogen atoms in this monocyclic or polycyclic hydrocarbon group may be substituted by substituents, and some of the carbon atoms constituting the substituted ring may be substituted by heteroatoms, and Ra01 is a straight-chain, branched-chain or cyclic aliphatic hydrocarbon group].

[0028] In the above general formula (a0-1), WO1 is a base containing a polymerizable group. In WO1, "polymerizable group" means a group that can be polymerized by free radical polymerization or the like, such as a group containing multiple bonds between carbon atoms, such as vinyl double bonds. In the constitutive unit (a01), the multiple bonds of the polymerizable group will break to form the main chain.

[0029] As polymerizable groups in WO1, examples include vinyl, allyl, acrylonitrile, methacrylonitrile, fluorovinyl, difluorovinyl, trifluorovinyl, difluorotrifluoromethylvinyl, trifluoroallyl, perfluoroallyl, trifluoromethylacrylonitrile, nonylfluorobutylacrylonitrile, vinyl ether, fluorinated vinyl ether, allyl ether, fluorinated allyl ether, styrene, vinylnaphthyl, fluorinated styrene, fluorinated vinylnaphthyl, nor, fluorinated nor, silyl, etc.

[0030] As for the "base containing a polymerizable group" in WO1, it can be a base composed solely of a polymerizable group, or it can be a base composed of a polymerizable group and other groups besides the polymerizable group. Examples of other groups besides the polymerizable group include divalent hydrocarbon groups that may also have substituents and divalent linked groups that contain heteroatoms.

[0031] • It may also have a substituent divalent hydrocarbon group: When the other group besides the polymerizable group is a divalent hydrocarbon group that may also have a substituent, the hydrocarbon group may also be an aliphatic hydrocarbon group or an aromatic hydrocarbon group.

[0032] ••Aliphatic hydrocarbon groups other than the polymerizable group. Aliphatic hydrocarbon groups refer to hydrocarbon groups that do not possess aromaticity. These aliphatic hydrocarbon groups can be saturated or unsaturated, but saturation is generally preferred. Examples of the aforementioned aliphatic hydrocarbon groups include straight-chain or branched-chain aliphatic hydrocarbon groups, or aliphatic hydrocarbon groups whose structure includes rings.

[0033] ••• A straight-chain or branched-chain aliphatic hydrocarbon group. The straight-chain aliphatic hydrocarbon group preferably has 1 to 10 carbon atoms, more preferably 1 to 6 carbon atoms, and even more preferably 1 to 4 carbon atoms, with 1 to 3 carbon atoms being the most desirable. As a straight-chain aliphatic hydrocarbon group, a straight-chain alkyl group is preferred; specifically, examples include methylene [-CH2-], ethyl [-(CH2)2-], trimethylene [-(CH2)3-], tetramethylene [-(CH2)4-], and pentamethylene [-(CH2)5-]. The branched-chain aliphatic hydrocarbon group preferably has 2 to 10 carbon atoms, more preferably 3 to 6 carbon atoms, and even more preferably 3 or 4 carbon atoms, with 3 carbon atoms being the most desirable. As a branched chain aliphatic hydrocarbon group, a branched chain alkyl group is preferred. 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-. As for the alkyl group in alkyl extension, it is preferred to be a straight-chain alkyl group with 1 to 5 carbon atoms.

[0034] The aforementioned straight-chain or branched-chain aliphatic hydrocarbon group may or may not have substituents. Examples of such substituents include fluorine atoms, fluorinated alkyl groups with 1 to 5 carbon atoms substituted with fluorine atoms, and carbonyl groups.

[0035] •••Aliphatic hydrocarbon groups containing rings in their structure. Examples of aliphatic hydrocarbon groups containing rings in their structure include cyclic aliphatic hydrocarbon groups containing substituents with heteroatoms in their ring structure (groups with two hydrogen atoms removed from the aliphatic hydrocarbon ring), groups in which the aforementioned cyclic aliphatic hydrocarbon groups are bonded to the ends of straight-chain or branched-chain aliphatic hydrocarbon groups, and groups in which the aforementioned cyclic aliphatic hydrocarbon groups are intermediate in the middle of straight-chain or branched-chain aliphatic hydrocarbon groups. Examples of the aforementioned straight-chain or branched-chain aliphatic hydrocarbon groups are the same as those mentioned above. It is preferable that the cyclic aliphatic hydrocarbon group has 3 to 20 carbon atoms, and even more preferably 3 to 12 carbon atoms. The cyclic aliphatic hydrocarbon group can also be a polycyclic group or a monocyclic group. As a monocyclic alicyclic hydrocarbon group, it is preferable that it is a group in which two hydrogen atoms have been removed from a monocyclic alkane. For monocyclic alkanes, those with 3 to 6 carbon atoms are preferred; examples include cyclopentane and cyclohexane. For polycyclic alicyclic hydrocarbon groups, those consisting of a self-polycyclic cycloalkane with two hydrogen atoms removed are preferred; for polycyclic alkanes, those with 7 to 12 carbon atoms are preferred; examples include adamantane, noralane, isoalkanes, tricyclodecane, and tetracyclododecane.

[0036] The cyclic aliphatic hydrocarbon group may or may not have substituents. Examples of substituents include alkyl, alkoxy, halogen atom, alkyl halide, hydroxyl, and carbonyl groups. Among the aforementioned substituents, alkyl groups with 1 to 5 carbon atoms are preferred, with methyl, ethyl, propyl, n-butyl, and tert-butyl being the most desirable. Among the aforementioned substituents, alkoxy groups with 1 to 5 carbon atoms are preferred, with methoxy, ethoxy, n-propoxy, iso-propoxy, n-butoxy, and tert-butoxy being even more desirable, with methoxy and ethoxy being the most desirable. Among the aforementioned substituents, halogen atom groups include fluorine, chlorine, bromine, and iodine atoms, with fluorine being the most desirable. Among the aforementioned substituents, alkyl halide groups are groups in which some or all of the hydrogen atoms of the aforementioned alkyl group are substituted with the aforementioned halogen atom. The cyclic aliphatic hydrocarbon group is formed by the substitution of a portion of the carbon atoms constituting its ring structure with a substituent containing a heteroatom. The preferred substituents for containing the heteroatom are -O-, -C(=O)-O-, -S-, -S(=O)2-, and -S(=O)2-O-.

[0037] ••Aromatic hydrocarbon group in groups other than the polymerizable group. The aromatic hydrocarbon group is a hydrocarbon group having at least one aromatic ring. This aromatic ring is only required to be a cyclic conjugated system having 4n+2 π electrons, and is not particularly limited, and can be monocyclic or polycyclic. The number of carbon atoms in the aromatic ring is preferably 5 to 30, more preferably 5 to 20, even more preferably 6 to 15, and particularly preferably 6 to 12. However, the number of carbon atoms does not include the number of carbon atoms in the substituents. Specifically, aromatic hydrocarbon rings such as benzene, naphthalene, anthracene, and phenanthrene are examples of aromatic hydrocarbon rings; aromatic heterocycles in which a portion of the carbon atoms constituting the aforementioned aromatic hydrocarbon rings are substituted with heteroatoms are also examples. Examples of heteroatoms in aromatic heterocycles include oxygen atoms, sulfur atoms, and nitrogen atoms. Specifically, pyridine rings and thiophene rings are examples of aromatic heterocycles. Specifically, aromatic hydrocarbon groups include those derived from aromatic hydrocarbon rings or aromatic heterocycles by removing two hydrogen atoms (aryl or heteroaryl); those derived from aromatic compounds containing two or more aromatic rings (e.g., biphenyl, benzo[a], etc.) by removing two hydrogen atoms; and those derived from aromatic hydrocarbon rings or aromatic heterocycles by removing one hydrogen atom (aryl or heteroaryl) by substituting one hydrogen atom with an alkyl group (e.g., aryl groups derived from aryl alkyl groups such as benzyl, phenethyl, 1-naphthylmethyl, 2-naphthylmethyl, 1-naphthylethyl, 2-naphthylethyl, etc. by further removing one hydrogen atom). The alkyl group bonded to the aforementioned aryl or heteroaryl group preferably has 1 to 4 carbon atoms, more preferably 1 to 2 carbon atoms, and particularly preferably 1 carbon atom.

[0038] In the aforementioned aromatic hydrocarbon group, the hydrogen atoms of the aromatic hydrocarbon group may also be substituted by substituents. For example, the hydrogen atoms of the aromatic ring bonded to the aromatic hydrocarbon group may also be substituted by substituents. Examples of such substituents include alkyl, alkoxy, halogen atom, alkyl halide, and hydroxyl groups. Among the aforementioned substituents, alkyl groups with 1 to 5 carbon atoms are preferred, and methyl, ethyl, propyl, n-butyl, and tert-butyl are most suitable. Among the aforementioned substituents, examples of alkoxy, halogen atom, and alkyl halide groups are those that substitute for the hydrogen atoms of the aforementioned cyclic aliphatic hydrocarbon group.

[0039] • Divalent linking group containing heteroatoms: When the other group besides the polymerizable group is a divalent linking group containing heteroatoms, preferred examples of such linking groups include -O-, -C(=O)-O-, -C(=O)-, -OC(=O)-O-, -C(=O)-NH-, -NH-, -NH-C(=NH)- (H may also be substituted by alkyl, acetylated, etc. substituents), -S-, -S(=O)2-, -S(=O)2-O-, general formula -Y21-O-Y22-, -Y21-O-, -Y21-C(=O)-O-, -C(=O)-O-Y21-, -[Y21-C(=O)-O]m”-Y22-, The base represented by -Y21-OC(=O)-Y22- or -Y21-S(=O)2-O-Y22- [where Y21 and Y22 are each independently divalent hydrocarbon groups that may also have substituents, O is an oxygen atom, and m” is an integer from 0 to 3], etc. When the aforementioned divalent linking group containing heteroatoms is -C(=O)-NH-, -C(=O)-NH-C(=O)-, -NH-, or -NH-C(=NH)-, its H may also be substituted by substituents such as alkyl or acetyl groups. It is preferable that the number of carbon atoms (alkyl, acetyl, etc.) is 1 to 10, more preferably 1 to 8, and particularly preferably 1 to 5. In the general formulas -Y21-O-Y22-, -Y21-O-, -Y21-C(=O)-O-, -C(=O)-O-Y21-, -[Y21-C(=O)-O]m”-Y22-, -Y21-OC(=O)-Y22-, or -Y21-S(=O)2-O-Y22-, Y21 and Y22 are each independently divalent hydrocarbon groups, which may also have substituents. Examples of such divalent hydrocarbon groups are the same as those mentioned in the description of divalent linking groups (which may also have substituents). For Y21, a straight-chain aliphatic hydrocarbon group is preferred, a straight-chain alkyl group is even more preferred, a straight-chain alkyl group with 1 to 5 carbon atoms is more preferred, and methylene or ethyl groups are particularly preferred. Y22 is preferably a straight-chain or branched-chain aliphatic hydrocarbon group, and is more preferably methylene, ethyl, or alkylmethylene. The alkyl group in the alkylmethylene group is preferably a straight-chain alkyl group with 1 to 5 carbon atoms, more preferably a straight-chain alkyl group with 1 to 3 carbon atoms, and is most preferably methyl. In the group represented by the formula -[Y21-C(=O)-O]m”-Y22-, m” is an integer from 0 to 3, preferably an integer from 0 to 2, preferably 0 or 1, and particularly preferably 1. That is, the group represented by the formula -[Y21-C(=O)-O]m”-Y22- is particularly preferred. Among them, the group represented by the formula -(CH2)a'-C(=O)-O-(CH2)b'- is preferred. In this formula, a' is an integer from 1 to 10, preferably an integer from 1 to 8, even better if it is an integer from 1 to 5, and even better if it is 1 or 2, with 1 being the best.b' can be an integer from 1 to 10, preferably an integer from 1 to 8, preferably an integer from 1 to 5, preferably 1 or 2, and 1 is the best.

[0040] As for WO1, examples of groups represented by the chemical formula: C(RX11)(RX12)=C(RX13)-Yax0- are more suitable. In this chemical formula, RX11, RX12 and RX13 are each hydrogen atoms, alkyl groups with 1 to 5 carbon atoms or haloalkyl groups with 1 to 5 carbon atoms, and Yax0 is a single bond or a divalent linked group.

[0041] In RX11, RX12, and RX13, the alkyl group having 1 to 5 carbon atoms is preferably a straight-chain or branched-chain alkyl group having 1 to 5 carbon atoms. Specifically, examples include methyl, ethyl, propyl, isopropyl, n-butyl, isobutyl, tert-butyl, pentyl, isopentyl, and neopentyl. The alkyl halide having 1 to 5 carbon atoms is a group in which one or all of the hydrogen atoms of the aforementioned alkyl groups having 1 to 5 carbon atoms are substituted with halogen atoms. As for the halogen atom, fluorine atom is particularly preferred. Among these, for RX11 and RX12, it is preferred to have a hydrogen atom, an alkyl group having 1 to 5 carbon atoms, or a fluorinated alkyl group having 1 to 5 carbon atoms. In terms of industrial availability, hydrogen atom and methyl are more preferred, and hydrogen atom is particularly preferred. Furthermore, as RX13, it is preferable to have hydrogen atoms, an alkyl group with 1 to 5 carbon atoms, or a fluorinated alkyl group with 1 to 5 carbon atoms. In terms of industrial availability, hydrogen atoms and methyl groups are preferred, with methyl groups being particularly preferred.

[0042] There is no particular limitation on the divalent linking group in Yax0, but divalent hydrocarbon groups with substituents and divalent linking groups containing heteroatoms are also suitable, and each is the same as the above.

[0043] In the above, YaxO is preferably an ester bond [-C(=O)-O-, -OC(=O)-], an ether bond (-O-), a straight-chain or branched alkyl group, an aromatic hydrocarbon group, or a combination thereof, or a single bond. Among these, YaxO is preferably a combination of an ester bond [-C(=O)-O-, -OC(=O)-] and a straight-chain alkyl group, or a single bond, and even more preferably a single bond.

[0044] In the above general formula (a0-1), Xt is a base that forms a monocyclic or polycyclic alicyclic group together with Ct. This polycyclic alicyclic group can also be a condensed polycyclic hydrocarbon group with a condensed aromatic ring on the alicyclic group. Furthermore, the monocyclic or polycyclic alicyclic group can also be a group in which a portion of the carbon atom constituting the ring structure is substituted with a substituent containing a heteroatom. Examples of substituents containing the heteroatom include -O-, -C(=O)-O-, -S-, -S(=O)2-, and -S(=O)2-O-.

[0045] As a monocyclic alicyclic group, it is preferable to be a monocyclic alkane or a group formed by removing one hydrogen atom from a monocyclic alkene. As the monocyclic alkane, it is preferable to have 3 to 6 carbon atoms, specifically cyclopentane and cyclohexane are examples. As the monocyclic alkene, it is preferable to have 3 to 6 carbon atoms, specifically cyclopentene and cyclohexene are examples. As a polycyclic alicyclic group, it is preferable to be a polycyclic alkane or a group formed by removing one hydrogen atom from a polycyclic alkene. As the polycyclic alkane, it is preferable to have 7 to 12 carbon atoms, specifically adamantane, noralane, isoalane, tricyclodecane, tetracyclododecane, etc. Furthermore, as the polycyclic alkene, it is preferable to have 7 to 12 carbon atoms, specifically adamantene, noralene, isoalene, tricyclodecene, tetracyclododecene, etc. Examples of condensed polycyclic hydrocarbon groups with condensed aromatic rings on an alicyclic base include bicyclic compounds such as tetrahydronaphthalene and dihydroindene, which have one or more hydrogen atoms removed from their alicyclic rings.

[0046] The monocyclic or polycyclic alicyclic group formed by Xt and Ct may also have some or all of the hydrogen atoms in the monocyclic or polycyclic alicyclic group replaced by 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, the substituents are collectively referred to as "Ra06"). 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. Furthermore, 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 may be substituted with fluorine atoms. The aforementioned aliphatic cyclic hydrocarbon group may also have one or more of the above-mentioned substituents, or may have one or more of the above-mentioned substituents. Examples of monovalent chain saturated hydrocarbon groups with 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.

[0047] When the monocyclic or polycyclic alicyclic group formed by Xt and Ct has substituents, it is preferable that a portion of the carbon atoms constituting the ring structure are replaced by oxygen atoms.

[0048] In the above general formula (a0-1), Xt is preferably a group that forms a monocyclic alicyclic group together with Ct. As the monocyclic alicyclic group, it is preferably a group that has removed one hydrogen atom from a monocyclic alkane, and it is more preferably cyclopentyl, cyclohexyl, cycloheptyl, or cyclooctyl, and even more preferably cyclopentyl or cyclohexyl.

[0049] In the above general formula (a0-1), Ra01 is a straight-chain, branched-chain, or cyclic aliphatic hydrocarbon group. The aliphatic hydrocarbon group can be a saturated aliphatic hydrocarbon group or an unsaturated aliphatic hydrocarbon group, but a saturated aliphatic hydrocarbon group is preferred.

[0050] The straight-chain or branched-chain aliphatic hydrocarbon group in Ra01 includes, specifically, a straight-chain or branched-chain saturated hydrocarbon group (alkyl) or a straight-chain or branched-chain unsaturated hydrocarbon group.

[0051] Specific examples of the straight-chain or branched-chain alkyl group include methyl, ethyl, propyl, isopropyl, n-butyl, isobutyl, tert-butyl, pentyl, isopentyl, neopentyl, etc.

[0052] The unsaturated hydrocarbon group in the straight-chain or branched-chain unsaturated hydrocarbon group includes, more specifically, unsaturated hydrocarbon groups with double bonds such as alkenyl, diene, and triene; and unsaturated hydrocarbon groups with triple bonds such as alkyne, diyne with one hydrogen atom removed, and triyne with one hydrogen atom removed.

[0053] Specific examples of the straight-chain or branched-chain alkenyl group include straight-chain alkenyl groups such as vinyl, propenyl (allyl), and 2-butenyl; and branched-chain alkenyl groups such as 1-methyl vinyl, 2-methyl vinyl, 1-methyl propenyl, and 2-methyl propenyl.

[0054] Specific examples of the diene group include propadienyl and butadienyl. Specific examples of the triene group include butadienyl.

[0055] Specific examples of the straight-chain or branched-chain alkynyl group include straight-chain alkynyl groups such as ethynyl, propynyl, and 3-pentenyl; and branched-chain alkynyl groups such as 1-methylpropynyl.

[0056] Examples of a base that removes one hydrogen atom from the diacetylene include a base that removes one hydrogen atom from the diacetylene. Examples of a base that removes one hydrogen atom from the triacetylene include a base that removes one hydrogen atom from hexa-1,3,5-triacetylene.

[0057] The cyclic aliphatic hydrocarbon group in Ra01 includes, specifically, monocyclic alicyclic groups and polycyclic alicyclic groups.

[0058] As a monocyclic alicyclic group, it is preferable to be a monocyclic alkane or a group formed by removing one or more hydrogen atoms from a monocyclic alkene. As the monocyclic alkane, it is preferable to have 3 to 6 carbon atoms, specifically cyclopentane and cyclohexane are examples. As the monocyclic alkene, it is preferable to have 3 to 6 carbon atoms, specifically cyclopentene and cyclohexene are examples. As a polycyclic alicyclic group, it is preferable to be a polycyclic alkane or a group formed by removing one or more hydrogen atoms from a polycyclic alkene, specifically a polycyclic alkane with 7 to 12 carbon atoms, specifically adamantane, noralane, isoalane, tricyclodecane, tetracyclododecane, etc. Furthermore, as the polycyclic alkene, it is preferable to have 7 to 12 carbon atoms, specifically adamantene, noralene, isoalene, tricyclodecene, tetracyclododecene, etc.

[0059] In the above general formula (a0-1), Ra01 is preferably a straight-chain, branched-chain or cyclic aliphatic saturated hydrocarbon group, preferably a straight-chain or branched-chain alkyl group, or a monocyclic alicyclic group, and even more preferably a straight-chain or branched-chain alkyl group.

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

[0061] [In the formula, 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 linker, na01 is an integer from 0 to 2, Ct is a tertiary carbon atom, Xat is a group that forms a monocyclic aliphatic hydrocarbon group with Ct, and some or all of the hydrogen atoms in this monocyclic aliphatic hydrocarbon group may also be substituted by substituents, and some of the carbon atoms constituting the ring may also be substituted by heteroatoms, Ra01 is a straight-chain, branched-chain, or cyclic aliphatic hydrocarbon group].

[0062] In the above general formula (a01-1), R01 is a hydrogen atom, an alkyl group having 1 to 5 carbon atoms, or a alkyl halide having 1 to 5 carbon atoms. It is preferable that the alkyl group having 1 to 5 carbon atoms in R01 is a straight-chain or branched-chain alkyl group having 1 to 5 carbon atoms. Specifically, examples include methyl, ethyl, propyl, isopropyl, n-butyl, isobutyl, tert-butyl, pentyl, isopentyl, and neopentyl. The alkyl halide having 1 to 5 carbon atoms is a group in which some or all of the hydrogen atoms of the aforementioned alkyl group having 1 to 5 carbon atoms are substituted with halogen atoms. Fluorine atoms are particularly preferred as the halogen atom. It is preferable that R01 is a hydrogen atom, an alkyl group having 1 to 5 carbon atoms, or a fluoroalkyl group having 1 to 5 carbon atoms. From the perspective of industrial availability, hydrogen atoms or methyl groups are best.

[0063] In the above general formula (a01-1), Va01 is a divalent linker group. The divalent hydrocarbon group in Va01 can also be an aliphatic hydrocarbon group or an aromatic hydrocarbon group.

[0064] The aliphatic hydrocarbon group that is 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-chain aliphatic hydrocarbon groups, or aliphatic hydrocarbon groups whose structure contains rings.

[0065] The aforementioned straight-chain aliphatic hydrocarbon group is preferably composed of 1 to 10 carbon atoms, more preferably 1 to 6 carbon atoms, even more preferably 1 to 4 carbon atoms, and most preferably 1 to 3 carbon atoms. As a straight-chain aliphatic hydrocarbon group, a straight-chain alkyl group is preferred, specifically including methylene [-CH2-], ethyl [-(CH2)2-], trimethylene [-(CH2)3-], tetramethylene [-(CH2)4-], pentamethylene [-(CH2)5-], etc. The aforementioned branched-chain aliphatic hydrocarbon group is preferably composed of 2 to 10 carbon atoms, more preferably 3 to 6 carbon atoms, even more preferably 3 or 4 carbon atoms, and most preferably 3 carbon atoms. As a branched chain aliphatic hydrocarbon group, a branched chain alkyl group is preferred. 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-. As for the alkyl group in alkyl extension, it is preferred to be a straight-chain alkyl group with 1 to 5 carbon atoms.

[0066] Examples of aliphatic hydrocarbon groups containing a ring in the aforementioned 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-chain aliphatic hydrocarbon group, and alicyclic hydrocarbon groups separated from the middle of a straight-chain or branched-chain aliphatic hydrocarbon group. Examples of straight-chain or branched-chain aliphatic hydrocarbon groups include those identical to the aforementioned straight-chain or branched-chain aliphatic hydrocarbon groups. It is preferable that the aforementioned alicyclic hydrocarbon group has 3 to 20 carbon atoms, and even more preferably 3 to 12 carbon atoms. The aforementioned alicyclic hydrocarbon group can also be polycyclic or monocyclic. It is preferable that the monocyclic alicyclic hydrocarbon group has two hydrogen atoms removed from a monocyclic alkane. It is preferable that the monocyclic alkane has 3 to 6 carbon atoms; specifically, examples include cyclopentane and cyclohexane. As a polycyclic alicyclic hydrocarbon group, it is preferable to have a group consisting of two hydrogen atoms removed from a polycycloalkane. As for the polycycloalkane, it is preferable to have 7 to 12 carbon atoms. Specifically, examples include adamantane, norane, isoalkane, tricyclodecane, and tetracyclododecane.

[0067] The aromatic hydrocarbon group, which is the divalent hydrocarbon group in VaO1, is a hydrocarbon group having an aromatic ring. The relevant aromatic hydrocarbon group preferably has 3 to 30 carbon atoms, more preferably 5 to 30, even more preferably 5 to 20, particularly preferably 6 to 15, and best preferably 6 to 12. However, this number of carbon atoms does not include the number of carbon atoms in the substituents. Specifically, the aromatic ring possessed by the aromatic hydrocarbon group includes aromatic hydrocarbon rings of benzene, biphenyl, fentanyl, naphthalene, anthracene, phenanthrene, etc.; and aromatic heterocycles in which a portion of the carbon atoms constituting the aforementioned aromatic hydrocarbon rings are substituted with heteroatoms. Examples of heteroatoms in aromatic heterocycles include oxygen atoms, sulfur atoms, nitrogen atoms, etc. Specifically, examples of this aromatic hydrocarbon group include groups that have had two hydrogen atoms removed from the aforementioned aromatic hydrocarbon ring (aryl groups); and groups that have had one hydrogen atom removed from the aforementioned aromatic hydrocarbon ring (aryl groups) and then substituted with an alkyl group (e.g., benzyl, phenethyl, 1-naphthylmethyl, 2-naphthylmethyl, 1-naphthylethyl, 2-naphthylethyl, etc., aryl groups from aryl alkyl groups by further removing one hydrogen atom). The aforementioned alkyl group (the alkyl chain in an aryl alkyl group) preferably has 1 to 4 carbon atoms, more preferably 1 to 2, and particularly preferably 1.

[0068] In the above general formula (a01-1), na01 is an integer from 0 to 2, preferably 0 or 1, and even more preferably 0.

[0069] In the above general formula (a01-1), Xat is a group that forms a monocyclic aliphatic hydrocarbon group together with Ct. As the monocyclic alicyclic group, it is preferable to be a monocyclic alkane or a group formed by removing one hydrogen atom from a monocyclic alkene. As the monocyclic alkane, it is preferable to have 3 to 6 carbon atoms, specifically cyclopentane and cyclohexane are examples. As the monocyclic alkene, it is preferable to have 3 to 6 carbon atoms, specifically cyclopentene and cyclohexene are examples.

[0070] In the above general formula (a01-1), R01 is the same as R01 in the above general formula (a0-1).

[0071] The following are specific examples of the constituent unit (a01). In the following formulas, Rα represents a hydrogen atom, a methyl group, or a trifluoromethyl group.

[0072]

[0073]

[0074]

[0075] As a constituent unit (a01) in the inhibitor composition of this embodiment, it is preferable that the constituent unit is represented by any one of the above formulas (a01-1a-1) to (a01-1a-18), it is even more preferable that the constituent unit is represented by any one of the above formulas (a01-1a-1) to (a01-1a-4), (a01-1a-7) to (a01-1a-18), and it is even more preferable that the constituent unit is represented by any one of the above formulas (a01-1a-2) to (a01-1a-4), (a01-1a-10), (a01-1a-11), and (a01-1a-16).

[0076] The constituent unit (a01) of component (A1) may be one or more types. The proportion of the constituent unit (a01) in component (A1) relative to the total of all constituent units constituting component (100 mol%) is preferably 10-90 mol%, more preferably 20-80 mol%, and even more preferably 40-80 mol%. By setting the proportion of the constituent unit (a01) above the lower limit of the aforementioned preferred range, the efficiency of the deprotection reaction and the solubility of the developer can be adequately guaranteed, thus easily achieving the effects of the present invention. On the other hand, if the proportion is below the upper limit of the aforementioned preferred range, a balance with other constituent units can be achieved, resulting in better various photolithography properties.

[0077] • The compound represented by the general formula (a0-1) can be manufactured by, for example, a method having the following steps (i) and (ii).

[0078] Step (i); Step (i) is the step of reacting a compound (K1) represented by the following general formula (K-1) with a compound (G1) represented by the following general formula (G-1) or a compound (L1) represented by the following general formula (L-1) in a reaction solvent to obtain a compound (Alc1) represented by the following general formula (Alc-1).

[0079] [In the formula, Ra01 is a straight-chain, branched-chain, or cyclic aliphatic hydrocarbon group. X01 is a halogen atom. Ct is a tertiary carbon atom, and Xt is a hydrocarbon group that forms a monocyclic or polycyclic ring together with Ct. Some or all of the hydrogen atoms in this monocyclic or polycyclic hydrocarbon group may also be substituted by substituents, and some of the carbon atoms constituting the substituted ring may also be substituted by heteroatoms].

[0080] [In the formula, Ra01 is a straight-chain, branched-chain, or cyclic aliphatic hydrocarbon group. Ct is a tertiary carbon atom, and Xt is a hydrocarbon group that forms a monocyclic or polycyclic ring together with Ct. Some or all of the hydrogen atoms in this monocyclic or polycyclic hydrocarbon group may also be substituted by substituents, and some of the carbon atoms constituting the substituted ring may also be substituted by heteroatoms].

[0081] Ra01, Ct and Xt in the above formula are the same as Ra01, Ct and Xt in the above formula (a0-1). X01 in the above formula is a halogen atom, preferably a bromine atom.

[0082] The compound (L1) can be obtained by reacting a precursor of a compound (L1) in which, for example, the compound represented by the above general formula (L-1) has a hydrogen atom as a Li atom with an organolithium compound. Examples of organolithium compounds include methyllithium, ethyllithium, phenyllithium, n-butyllithium, sec-butyllithium, tert-butyllithium, etc.

[0083] As a reaction solvent, any solvent that can dissolve compound (K1) and compound (G1), or compound (K1) and compound (L1), and does not react with them is acceptable. Examples include dichloromethane, dichloroethane, trichloromethane, tetrahydrofuran, N,N-dimethylformamide, acetonitrile, propionitrile, N,N'-dimethylacetamide, dimethyl sulfoxide, etc.

[0084] In step (i), acids such as hydrochloric acid, nitric acid, sulfuric acid, formic acid, oxalic acid, and acetic acid may also be used.

[0085] The reaction temperature in step (i) is preferably -80~40℃, and even more preferably -20~20℃. The reaction time in step (i) may vary depending on the reactivity of compound (K1) and compound (G1) or compound (L1) or the reaction temperature, but is preferably 0.5~24 hours, and even more preferably 0.5~3 hours.

[0086] Step (ii); Step (ii) is a step in which a compound (Alc1) represented by the following general formula (Alc-1) is reacted with a compound (Car1) represented by the following general formula (Car-1) in a reaction solvent to obtain a compound represented by the following general formula (a0-1).

[0087] [In the formula, Ra01 is a straight-chain, branched-chain, or cyclic aliphatic hydrocarbon group. Ct is a tertiary carbon atom, Xt is a hydrocarbon group that forms a monocyclic or polycyclic ring with Ct, and some or all of the hydrogen atoms in this monocyclic or polycyclic hydrocarbon group may also be substituted by substituents, and some of the carbon atoms constituting the substituted ring may also be substituted by heteroatoms, WO1 is a group containing a polymerizable group, and X02 is a halogen atom].

[0088] In the above formula, W01, Ct, Xt and Ra01 are the same as W01, Ct, Xt and Ra01 in the above formula (a0-1). In the above formula, X02 is a halogen atom, preferably a chlorine atom.

[0089] As a reaction solvent, any solvent that can dissolve the compound (Alcl) and the compound (Carl) and does not react with them is acceptable. Examples include dichloromethane, dichloroethane, trichloromethane, tetrahydrofuran, N,N-dimethylformamide, acetonitrile, propionitrile, N,N'-dimethylacetamide, dimethyl sulfoxide, etc.

[0090] In step (ii), bases such as triethylamine, pyridine, and 4-dimethylaminopyridine may also be used.

[0091] The reaction temperature in step (ii) is preferably -40~80℃, and even more preferably -20~60℃. The reaction time in step (ii) may vary depending on the reactivity of compound (Alcl) and compound (Carl) or the reaction temperature, but is preferably 0.5~24 hours, and even more preferably 0.5~3 hours.

[0092] The compound represented by the above general formula (a0-1) obtained by step (ii) can also be separated and purified. Separation and purification can be performed using conventionally known methods, such as appropriate combinations of concentration, solvent extraction, distillation, crystallization, recrystallization, chromatography, etc. The structure of the compound represented by the above general formula (a0-1) obtained as described above can be identified by general organic analysis methods such as 1H-nuclear magnetic resonance (NMR) spectroscopy, 13C-NMR spectroscopy, infrared absorption (IR) spectroscopy, mass spectrometry (MS), elemental analysis, X-ray crystallography, etc.

[0093] ≪Other constituent units≫ (A1) In addition to the aforementioned constituent unit (a01), the component may also have other constituent units as necessary. 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 (but, those equivalent to the aforementioned constituent unit (a01) are removed); a constituent unit (a10) represented by the general formula (a10-1) described below; a constituent unit (a8) derived from a compound represented by the general formula (a8-1) described below; a constituent unit (a2) containing a cyclic group containing a lactone, a cyclic group containing -SO2-, or a cyclic group containing a carbonate (but, those equivalent to the aforementioned constituent unit (a01) or the aforementioned constituent unit (a1) are removed); a constituent unit (a3) ​​containing an aliphatic hydrocarbon group containing a polar group (but, those equivalent to the aforementioned constituent unit (a01), the aforementioned constituent unit (a1), or the aforementioned constituent unit (a2) are removed); a constituent unit (a4) containing an aliphatic cyclic group that is non-dissociable with an acid; styrene or a constituent unit (st) derived from styrene derivatives, etc.

[0094] Regarding the constituent unit (a1): The constituent unit (a1) is a constituent unit containing acid decomposition groups whose polarity increases due to the action of acid.

[0095] As an acid-dissociating group, examples of proposed acid-dissociating groups for base resins used as components of chemically amplifying inhibitors include "acetal-type acid-dissociating groups", "tertiary alkyl ester-type acid-dissociating groups", and "tertiary alkyloxycarbonyl acid-dissociating groups".

[0096] Acetal type acid dissociation group: Among the aforementioned polar groups, acid dissociation groups that are carboxyl groups or protected hydroxyl groups include, for example, the acid dissociation group represented by the following general formula (a1-r-1) (hereinafter sometimes referred to as "acetal type acid dissociation group").

[0097] [In the formula, Ra'1 and Ra'2 are hydrogen atoms or alkyl groups. Ra'3 is a hydrocarbon group, and Ra'3 can also bond with either Ra'1 or Ra'2 to form a ring].

[0098] In formula (a1-r-1), it is preferable that at least one of Ra'1 and Ra'2 is a hydrogen atom, and it is even more preferable that both are hydrogen atoms. When Ra'1 or Ra'2 is an alkyl group, the same alkyl group as those mentioned in the description of α-substituted acrylates above, which can also be bonded to the carbon atom at the α-position, is preferred, and it is preferred to be an alkyl group with 1 to 5 carbon atoms. Specifically, linear or branched alkyl groups are preferred. More specifically, methyl, ethyl, propyl, isopropyl, n-butyl, isobutyl, tert-butyl, pentyl, isopentyl, neopentyl, etc. are mentioned, with methyl or ethyl being even more preferable, and methyl being particularly preferred.

[0099] In formula (a1-r-1), the hydrocarbon group of Ra'3 can be a straight-chain or branched-chain alkyl group, or a cyclic hydrocarbon group. The straight-chain alkyl group preferably has 1 to 5 carbon atoms, more preferably 1 to 4 carbon atoms, and even more preferably 1 or 2 carbon atoms. Specifically, methyl, ethyl, n-propyl, n-butyl, n-pentyl, etc., are examples. Among these, methyl, ethyl, or n-butyl is preferred, and methyl or ethyl is even more preferred.

[0100] The branched chain alkyl group is preferably composed of 3 to 10 carbon atoms, and more preferably 3 to 5 carbon atoms. Specifically, isopropyl, isobutyl, tert-butyl, isopentyl, neopentyl, 1,1-diethylpropyl, 2,2-dimethylbutyl, etc., are examples, with isopropyl being preferred.

[0101] When Ra'3 becomes a cyclic hydrocarbon group, the hydrocarbon group can be an aliphatic hydrocarbon group or an aromatic hydrocarbon group, and can also be a polycyclic group or a monocyclic group. As a monocyclic aliphatic hydrocarbon group, it is preferable to be a group that has removed one hydrogen atom from a monocyclic alkane. As for the monocyclic alkane, it is preferable to have 3 to 6 carbon atoms, specifically cyclopentane, cyclohexane, etc. As a polycyclic aliphatic hydrocarbon group, it is preferable to be a group that has removed one hydrogen atom from a polycyclic alkane, specifically a polycyclic alkane that has 7 to 12 carbon atoms, specifically adamantane, noralane, isoalkanes, tricyclodecane, tetracyclododecane, etc.

[0102] When the cyclic hydrocarbon group of Ra'3 becomes an aromatic hydrocarbon group, the aromatic hydrocarbon group is a hydrocarbon group having at least one aromatic ring. This aromatic ring only needs to be a cyclic conjugated system with 4n+2 π electrons, and there are no particular limitations; it can be monocyclic or polycyclic. The number of carbon atoms in the aromatic ring is preferably 5-30, more preferably 5-20, even more preferably 6-15, and particularly preferably 6-12. Examples of aromatic rings include aromatic hydrocarbon rings of benzene, naphthalene, anthracene, and phenanthrene; and aromatic heterocycles in which a portion of the carbon atoms constituting the aforementioned aromatic hydrocarbon rings are substituted with heteroatoms. Examples of heteroatoms in aromatic heterocycles include oxygen, sulfur, and nitrogen atoms. Examples of aromatic heterocycles include pyridine rings and thiophene rings. Specifically, the aromatic hydrocarbon group in Ra'3 includes groups (aryl or heteroaryl) formed by removing one hydrogen atom from the aforementioned aromatic hydrocarbon ring or aromatic heterocycle; groups formed by removing one hydrogen atom from aromatic compounds containing two or more aromatic rings (e.g., biphenyl, fumonisin, etc.); and groups in which one hydrogen atom of the aforementioned aromatic hydrocarbon ring or aromatic heterocycle is substituted with an alkyl group (e.g., arylalkyl groups such as benzyl, phenethyl, 1-naphthylmethyl, 2-naphthylmethyl, 1-naphthylethyl, 2-naphthylethyl, etc.). It is preferable that the alkyl group bonded to the aforementioned aromatic hydrocarbon ring or aromatic heterocycle has 1 to 4 carbon atoms, more preferably 1 to 2 carbon atoms, and particularly preferably 1 carbon atom.

[0103] The cyclic hydrocarbon group in Ra'3 may also have substituents. Examples of such substituents are the same as those in Rax5 mentioned above.

[0104] When Ra'3 bonds with either Ra'1 or Ra'2 to form a ring, it is preferable that the ring is a 4-7 member ring, and even more preferable that it is a 4-6 member ring. Specific examples of such a ring include tetrahydropiperanyl and tetrahydrofuranyl.

[0105] Tertiary alkyl ester type acid-dissociative group: Among the above polar groups, examples of acid-dissociative groups that protect the carboxyl group include those represented by the following general formula (a1-r-2). Furthermore, among the acid-dissociative groups represented by the following formula (a1-r-2), those composed of alkyl groups are sometimes referred to as "tertiary alkyl ester type acid-dissociative groups" for convenience.

[0106] [In the formula, Ra'4~Ra'6 are each a hydrocarbon group, and Ra'5 and Ra'6 can also bond together to form a ring].

[0107] As the hydrocarbon group of Ra'4, examples include straight-chain or branched-chain alkyl groups, chain or cyclic alkenyl groups, or cyclic hydrocarbon groups. The straight-chain or branched-chain alkyl groups and cyclic hydrocarbon groups (monocyclic aliphatic hydrocarbon groups, polycyclic aliphatic hydrocarbon groups, aromatic hydrocarbon groups) in Ra'4 are examples identical to those in Ra'3. It is preferred that the chain or cyclic alkenyl group in Ra'4 has 2 to 10 carbon atoms. As the hydrocarbon groups of Ra'5 and Ra'6, examples are identical to those in Ra'3.

[0108] When Ra'5 and Ra'6 are bonded to each other to form a ring, appropriate examples include the base represented by the following general formula (a1-r2-1), the base represented by the following general formula (a1-r2-2), and the base represented by the following general formula (a1-r2-3). On the other hand, when Ra'4 to Ra'6 are not bonded to each other and are independent hydrocarbon groups, appropriate examples include the base represented by the following general formula (a1-r2-4).

[0109] [In formula (a1-r2-1), Ra'10 represents a linear or branched alkyl group with 1 to 12 carbon atoms, which may also be partially substituted 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, and 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 may also be substituted. Ra101 to Ra103 are each independently a monovalent linear saturated hydrocarbon group with 1 to 10 carbon atoms or a monovalent aliphatic cyclic saturated hydrocarbon group with 3 to 20 carbon atoms. Some or all of the hydrogen atoms in their linear saturated hydrocarbon group and aliphatic cyclic saturated hydrocarbon group may also be substituted. Two or more of Ra101 to Ra103 may also be bonded to each other to form a cyclic structure.] In formula (a1-r2-3), Yaa is a carbon atom. Xaa is a group that forms an aliphatic cyclic group with Yaa. Ra104 is an aromatic hydrocarbon group that may also have substituents. In formula (a1-r2-4), Ra'12 and Ra'13 are each independently a monovalent chain saturated hydrocarbon group or a hydrogen atom with 1 to 10 carbon atoms. Some or all of the hydrogen atoms in this chain saturated hydrocarbon group may also be substituted. Ra'14 represents a bond. * indicates a bond location.

[0110] In the above formula (a1-r2-1), Ra'10 is a linear or branched alkyl group with 1 to 12 carbon atoms, which may also be substituted by a halogen atom or a heteroatom-containing group.

[0111] As a straight-chain alkyl group in Ra'10, it is preferably composed of 1 to 12 carbon atoms, and particularly preferably 1 to 5 carbon atoms. As a branched-chain alkyl group in Ra'10, there are examples similar to those mentioned above in Ra'3.

[0112] The alkyl group in Ra'10 can also be substituted with a halogen atom or a heteroatom-containing group. For example, a portion of the hydrogen atom constituting the alkyl group can also be substituted with a halogen atom or a heteroatom-containing group. Furthermore, a portion of the carbon atom constituting the alkyl group (such as a methylene group) can also be substituted with a heteroatom-containing group. Examples of heteroatoms include oxygen, sulfur, 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.

[0113] 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) that is 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 preferred, and cyclopentyl is even more preferred.

[0114] In formula (a1-r2-2), the cyclic hydrocarbon group formed by Xa and Ya together includes the group in Ra'3 of formula (a1-r-1) that removes one or more hydrogen atoms from the cyclic monovalent hydrocarbon group (aliphatic hydrocarbon group). The cyclic hydrocarbon group formed by Xa and Ya together may also have substituents. As substituents, there are examples of substituents that are the same as those that may be present in the cyclic hydrocarbon group in Ra'3. In formula (a1-r2-2), Ra101 to Ra103 are monovalent chain saturated hydrocarbon groups with 1 to 10 carbon atoms, such as methyl, ethyl, propyl, butyl, pentyl, hexyl, heptyl, octyl, decyl, etc. Among Ra101 to Ra103, 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. From the viewpoint of ease of synthesis, monovalent chain saturated hydrocarbon groups with 1 to 10 carbon atoms are preferred among Ra101 to Ra103, with hydrogen atoms, methyl, and ethyl atoms being more preferred, and hydrogen atoms being particularly preferred.

[0115] As a substituent of the chain saturated hydrocarbon group or aliphatic cyclic saturated hydrocarbon group represented by Ra101 to Ra103 above, there are examples of groups that are the same as Rax5 above.

[0116] 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, methylcyclohexenyl, cyclopentylenevinyl, and cyclohexylenevinyl. Among these, cyclopentenyl, cyclohexenyl, and cyclopentylenevinyl are preferred from the viewpoint of ease of synthesis.

[0117] In formula (a1-r2-3), the aliphatic cyclic group formed by Xaa and Yaa together is preferably an aliphatic hydrocarbon group that is a monocyclic or polycyclic group of Ra'3 in formula (a1-r-1). In formula (a1-r2-3), the aromatic hydrocarbon group in Ra104 is preferably a group that has removed one or more hydrogen atoms from an aromatic hydrocarbon ring having 5 to 30 carbon atoms. Among them, it is preferable that Ra104 is a group that has removed one or more hydrogen atoms from an aromatic hydrocarbon ring having 6 to 15 carbon atoms, it is even more preferable that it is a group that has removed one or more hydrogen atoms from benzene, naphthalene, anthracene or phenanthrene, it is even more preferable that it is a group that has removed one or more hydrogen atoms from benzene, naphthalene or anthracene, it is particularly preferable that it is a group that has removed one or more hydrogen atoms from benzene or naphthalene, and it is best that it is a group that has removed one or more hydrogen atoms from benzene.

[0118] Substituents that Ra104 in formula (a1-r2-3) may also have include, for example, methyl, ethyl, propyl, hydroxyl, carboxyl, halogen atom, alkoxy (methoxy, ethoxy, propoxy, butoxy, etc.), alkyloxy carbonyl, etc.

[0119] In formula (a1-r2-4), Ra'12 and Ra'13 are each independently a monovalent chain saturated hydrocarbon group or a hydrogen atom with 1 to 10 carbon atoms. Among Ra'12 and Ra'13, those identical to the monovalent chain saturated hydrocarbon groups with 1 to 10 carbon atoms in Ra101 to Ra103 mentioned above are examples of monovalent chain saturated hydrocarbon groups with 1 to 10 carbon atoms. Some or all of the hydrogen atoms in this chain saturated hydrocarbon group may also be substituted. It is preferable that Ra'12 and Ra'13 are hydrogen atoms or alkyl groups with 1 to 5 carbon atoms, further preferably alkyl groups with 1 to 5 carbon atoms, methyl or ethyl is more preferred, and methyl is particularly preferred. When the chain saturated hydrocarbon groups represented by Ra'12 and Ra'13 are substituted, examples of substituents are groups identical to those in Rax5 mentioned above.

[0120] In formula (a1-r2-4), Ra'14 represents a bond. Examples of hydrocarbon groups in Ra'14 include straight-chain or branched-chain alkyl groups or cyclic hydrocarbon groups.

[0121] In Ra'14, the linear alkyl group 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.

[0122] In Ra'14, the branched chain alkyl group preferably has 3 to 10 carbon atoms, and more preferably 3 to 5. Specifically, isopropyl, isobutyl, tert-butyl, isopentyl, neopentyl, 1,1-diethylpropyl, 2,2-dimethylbutyl, etc., with isopropyl being preferred.

[0123] When Ra'14 becomes a cyclic hydrocarbon group, the hydrocarbon group can be an aliphatic hydrocarbon group or an aromatic hydrocarbon group, and can also be a polycyclic group or a monocyclic group. As a monocyclic aliphatic hydrocarbon group, it is preferable to be a group that has removed one hydrogen atom from a monocyclic alkane. As for the monocyclic alkane, it is preferable to have 3 to 6 carbon atoms, specifically cyclopentane, cyclohexane, etc. As a polycyclic aliphatic hydrocarbon group, it is preferable to be a group that has removed one hydrogen atom from a polycyclic alkane, specifically a polycyclic alkane that has 7 to 12 carbon atoms, specifically adamantane, noralane, isoalkanes, tricyclodecane, tetracyclododecane, etc.

[0124] As for the aromatic hydrocarbon group in Ra'14, there are examples of the same aromatic hydrocarbon group as that in Ra104. Among them, it is preferable that Ra'14 is a group in which one or more hydrogen atoms are removed from an aromatic hydrocarbon ring having 6 to 15 carbon atoms, it is even more preferable that it is a group in which one or more hydrogen atoms are removed from benzene, naphthalene, anthracene or phenanthrene, it is even more preferable that it is a group in which one or more hydrogen atoms are removed from benzene, naphthalene or anthracene, it is particularly preferable that it is a group in which one or more hydrogen atoms are removed from naphthalene or anthracene, and it is best that it is a group in which one or more hydrogen atoms are removed from naphthalene. As for the substituents that may also be present in Ra'14, there are examples of the same substituents that may also be present in Ra104.

[0125] When Ra'14 in formula (a1-r2-4) is naphthyl, the position of the bond with the tertiary carbon atom in the aforementioned formula (a1-r2-4) can also be any one of the 1st or 2nd position of the naphthyl group. When Ra'14 in formula (a1-r2-4) is anthraceneyl, the position of the bond with the tertiary carbon atom in the aforementioned formula (a1-r2-4) can also be any one of the 1st, 2nd, or 9th position of the anthraceneyl group.

[0126] Specific examples of the basis represented by the aforementioned formula (a1-r2-1) are given below.

[0127]

[0128]

[0129]

[0130] Specific examples of the basis represented by the aforementioned formula (a1-r2-2) are given below.

[0131]

[0132]

[0133]

[0134] Specific examples of the basis represented by the aforementioned formula (a1-r2-3) are given below.

[0135]

[0136] Specific examples of the basis represented by the aforementioned formula (a1-r2-4) are given below.

[0137]

[0138] Tri-alkyloxycarbonyl acid dissociation group: Among the aforementioned polar groups, the acid dissociation group that serves as the protective hydroxyl group is, for example, the acid dissociation group represented by the following general formula (a1-r-3) (hereinafter sometimes referred to as "tri-alkyloxycarbonyl acid dissociation group" for convenience).

[0139] [In the formula, Ra'7~Ra'9 are each alkyl groups].

[0140] In formula (a1-r-3), it is preferable that Ra'7 to Ra'9 are each an alkyl group having 1 to 5 carbon atoms, and even more preferable that they are alkyl groups having 1 to 3 carbon atoms. Furthermore, it is preferable that the total number of carbon atoms of each alkyl group is 3 to 7, even more preferable that it is 3 to 5 carbon atoms, and most preferably that it is 3 to 4 carbon atoms.

[0141] Examples of constituent units (a1) include acrylates derived from acrylates in which the hydrogen atom bonded to the carbon atom at the α-position can also be substituted by a substituent; a constituent unit derived from acrylamide; a constituent unit derived from hydroxystyrene or hydroxystyrene derivatives in which at least a portion of the hydrogen atom in the hydroxyl group is protected by a substituent containing the aforementioned acid-degrading group; and a constituent unit derived from ethylene benzoic acid or ethylene benzoic acid derivatives in which at least a portion of the hydrogen atom in the -C(=O)-OH group is protected by a substituent containing the aforementioned acid-degrading group.

[0142] As a constituent unit (a1), it is preferable that the constituent unit is derived from an acrylate whose hydrogen atom bonded to the carbon atom at the α-position can also be replaced by a substituent. As a preferred specific example of the relevant constituent unit (a1), the constituent unit represented by the following general formula (a1-1) or (a1-2) is given.

[0143] [In the formula, R is a hydrogen atom, an alkyl group with 1 to 5 carbon atoms, or a haloalkyl group with 1 to 5 carbon atoms, and Va1 is a divalent hydrocarbon group that may also have an ether bond. na1 is an integer from 0 to 2. Ra1 is an acid-dissociable group represented by the above general formula (a1-r-1) or (a1-r-2). Wa1 is a na2+1 valent hydrocarbon group, na2 is an integer from 1 to 3, and Ra2 is an acid-dissociable group represented by the above general formula (a1-r-1) or (a1-r-3).]

[0144] In the aforementioned formula (a1-1), it is preferable that the alkyl group of R, which has 1 to 5 carbon atoms, is a straight-chain or branched-chain alkyl group with 1 to 5 carbon atoms. Specifically, examples include methyl, ethyl, propyl, isopropyl, n-butyl, isobutyl, tert-butyl, pentyl, isopentyl, and neopentyl. The alkyl halide with 1 to 5 carbon atoms is a group in which one or all of the hydrogen atoms of the aforementioned alkyl group with 1 to 5 carbon atoms are substituted with halogen atoms. Fluorine atoms are particularly preferred as halogen atoms. It is preferable that R is a hydrogen atom, an alkyl group with 1 to 5 carbon atoms, or a fluorinated alkyl group with 1 to 5 carbon atoms. In terms of industrial availability, hydrogen atoms or methyl groups are the most preferred.

[0145] In the aforementioned formula (a1-1), the divalent hydrocarbon group in Va1 can also be an aliphatic hydrocarbon group or an aromatic hydrocarbon group.

[0146] The aliphatic hydrocarbon group that is the divalent hydrocarbon group in Va1 can be saturated or unsaturated, but saturation is generally preferred. More specifically, examples of such aliphatic hydrocarbon groups include straight-chain or branched-chain aliphatic hydrocarbon groups, or aliphatic hydrocarbon groups whose structure contains rings.

[0147] The aforementioned straight-chain aliphatic hydrocarbon group is preferably composed of 1 to 10 carbon atoms, more preferably 1 to 6 carbon atoms, even more preferably 1 to 4 carbon atoms, and most preferably 1 to 3 carbon atoms. As a straight-chain aliphatic hydrocarbon group, a straight-chain alkyl group is preferred, specifically including methylene [-CH2-], ethyl [-(CH2)2-], trimethylene [-(CH2)3-], tetramethylene [-(CH2)4-], pentamethylene [-(CH2)5-], etc. The aforementioned branched-chain aliphatic hydrocarbon group is preferably composed of 2 to 10 carbon atoms, more preferably 3 to 6 carbon atoms, even more preferably 3 or 4 carbon atoms, and most preferably 3 carbon atoms. As a branched chain aliphatic hydrocarbon group, a branched chain alkyl group is preferred. 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-. As for the alkyl group in alkyl extension, it is preferred to be a straight-chain alkyl group with 1 to 5 carbon atoms.

[0148] Examples of aliphatic hydrocarbon groups containing a ring in the aforementioned 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-chain aliphatic hydrocarbon group, and alicyclic hydrocarbon groups separated from the middle of a straight-chain or branched-chain aliphatic hydrocarbon group. Examples of straight-chain or branched-chain aliphatic hydrocarbon groups include those identical to the aforementioned straight-chain or branched-chain aliphatic hydrocarbon groups. It is preferable that the aforementioned alicyclic hydrocarbon group has 3 to 20 carbon atoms, and even more preferably 3 to 12 carbon atoms. The aforementioned alicyclic hydrocarbon group can also be polycyclic or monocyclic. It is preferable that the monocyclic alicyclic hydrocarbon group has two hydrogen atoms removed from a monocyclic alkane. It is preferable that the monocyclic alkane has 3 to 6 carbon atoms; specifically, examples include cyclopentane and cyclohexane. As a polycyclic alicyclic hydrocarbon group, it is preferable to have a group consisting of two hydrogen atoms removed from a polycycloalkane. As for the polycycloalkane, it is preferable to have 7 to 12 carbon atoms. Specifically, examples include adamantane, norane, isoalkane, tricyclodecane, and tetracyclododecane.

[0149] The aromatic hydrocarbon group that forms the divalent hydrocarbon group in Va1 is a hydrocarbon group having an aromatic ring. The relevant aromatic hydrocarbon group preferably has 3 to 30 carbon atoms, more preferably 5 to 30, even more preferably 5 to 20, particularly preferably 6 to 15, and best preferably 6 to 12. However, this number of carbon atoms does not include the number of carbon atoms in the substituents. Specifically, the aromatic ring possessed by the aromatic hydrocarbon group includes aromatic hydrocarbon rings of benzene, biphenyl, fentanyl, naphthalene, anthracene, phenanthrene, etc.; and aromatic heterocycles in which a portion of the carbon atoms constituting the aforementioned aromatic hydrocarbon ring is substituted with heteroatoms. Examples of heteroatoms in aromatic heterocycles include oxygen atoms, sulfur atoms, nitrogen atoms, etc. Specifically, examples of this aromatic hydrocarbon group include groups that have had two hydrogen atoms removed from the aforementioned aromatic hydrocarbon ring (aryl groups); and groups that have had one hydrogen atom removed from the aforementioned aromatic hydrocarbon ring (aryl groups) and then substituted with an alkyl group (e.g., benzyl, phenethyl, 1-naphthylmethyl, 2-naphthylmethyl, 1-naphthylethyl, 2-naphthylethyl, etc., aryl groups from aryl alkyl groups by further removing one hydrogen atom). The aforementioned alkyl group (the alkyl chain in an aryl alkyl group) preferably has 1 to 4 carbon atoms, more preferably 1 to 2, and particularly preferably 1.

[0150] In the aforementioned formula (a1-1), Ra1 is the acid dissociative group represented by the above formula (a1-r-1) or (a1-r-2).

[0151] In the aforementioned formula (a1-2), the hydrocarbon group with a valence of na2+1 in Wa1 can be an aliphatic hydrocarbon group or an aromatic hydrocarbon group. The aliphatic hydrocarbon group refers to a hydrocarbon group that does not possess aromaticity, and can be saturated or unsaturated, with saturation being generally preferred. Examples of the aforementioned aliphatic hydrocarbon group include straight-chain or branched-chain aliphatic hydrocarbon groups, aliphatic hydrocarbon groups containing rings in their structure, or a combination of straight-chain or branched-chain aliphatic hydrocarbon groups and aliphatic hydrocarbon groups containing rings in their structure. A valence of na2+1 is preferably 2 to 4, with 2 or 3 being even more preferred.

[0152] In the aforementioned formula (a1-2), Ra2 is the acid dissociative group represented by the above general formula (a1-r-1) or (a1-r-3).

[0153] The following are specific examples of the constituent units represented by the aforementioned formula (a1-1). In the following formulas, Rα represents a hydrogen atom, a methyl group, or a trifluoromethyl group.

[0154]

[0155]

[0156]

[0157]

[0158]

[0159]

[0160]

[0161]

[0162] (A1) The constituent unit (a1) may be one or more types. As a constituent unit (a1), it is preferable to be a constituent unit represented by the aforementioned formula (a1-1) in order to more easily improve the characteristics (sensitivity, shape, etc.) of the photolithography obtained by electron beam or EUV. Among them, it is particularly preferable to be a constituent unit (a1) that includes a constituent unit represented by the following general formula (a1-1-1).

[0163] [In the formula, Ra1” is an acid dissociative group represented by the general formula (a1-r2-1), (a1-r2-3) or (a1-r2-4).

[0164] In the aforementioned formula (a1-1-1), R, Va1, and na1 are the same as R, Va1, and na1 in the aforementioned formula (a1-1). The explanation of the acid dissociation groups represented by the general formulas (a1-r2-1), (a1-r2-3), or (a1-r2-4) is as described above. Among these, considering the suitability for improving reactivity in EB or EUV applications, cyclic groups are preferred for acid dissociation groups.

[0165] In the aforementioned formula (a1-1-1), Ra1” is preferably represented by the acid dissociative group in the general formula (a1-r2-1).

[0166] The proportion of the constituent unit (a1) in component (A1) relative to the total number of all constituent units constituting component (100 mol%) is preferably 1 to 50 mol%, and more preferably 1 to 30 mol%. By setting the proportion of the constituent unit (a1) within the aforementioned preferred range, the efficiency of the deprotection reaction and the solubility of the developer can be adequately guaranteed, thus making it easier to obtain the effects of the present invention.

[0167] Regarding the constituent unit (a10): The constituent unit (a10) is the constituent unit represented by the following general formula (a10-1).

[0168] [In the formula, R is a hydrogen atom, an alkyl group with 1 to 5 carbon atoms, or a haloalkyl group with 1 to 5 carbon atoms. Yax1 is a single bond or a divalent linked group. Wax1 is an aromatic hydrocarbon group that may also have substituents. nax1 is an integer of 1 or more].

[0169] In the aforementioned formula (a10-1), R is a hydrogen atom, an alkyl group having 1 to 5 carbon atoms, or a alkyl halide having 1 to 5 carbon atoms. It is preferable that the alkyl group having 1 to 5 carbon atoms in R is a straight-chain or branched-chain alkyl group having 1 to 5 carbon atoms; specifically, examples include methyl, ethyl, propyl, isopropyl, n-butyl, isobutyl, tert-butyl, pentyl, isopentyl, neopentyl, etc. The alkyl halide having 1 to 5 carbon atoms in R is a group in which some or all of the hydrogen atoms of the aforementioned alkyl group having 1 to 5 carbon atoms are substituted with halogen atoms. Fluorine atoms are particularly preferred as the halogen atom. It is preferable that R is a hydrogen atom, an alkyl group having 1 to 5 carbon atoms, or a fluoroalkyl group having 1 to 5 carbon atoms; from the perspective of industrial availability, hydrogen, methyl, or trifluoromethyl is even more preferred, hydrogen or methyl is more preferred, and methyl is particularly preferred.

[0170] In the aforementioned formula (a10-1), Yax1 is a single bond or a divalent linker. In the aforementioned chemical formula, there is no particular limitation on the divalent linker in Yax1, but divalent hydrocarbon groups with substituents or divalent linkers containing heteroatoms are also suitable examples.

[0171] • It may also have a substituent divalent hydrocarbon group: When Yax1 is a divalent hydrocarbon group that may also have a substituent, the hydrocarbon group may also be an aliphatic hydrocarbon group or an aromatic hydrocarbon group.

[0172] ••The aliphatic hydrocarbon group in Yax1 refers to a hydrocarbon group that does not have aromaticity. The aliphatic hydrocarbon group can be saturated or unsaturated, but saturation is usually preferred. Examples of the aforementioned aliphatic hydrocarbon groups include straight-chain or branched-chain aliphatic hydrocarbon groups, or aliphatic hydrocarbon groups whose structure contains rings.

[0173] ••• A straight-chain or branched-chain aliphatic hydrocarbon group. The straight-chain aliphatic hydrocarbon group preferably has 1 to 10 carbon atoms, more preferably 1 to 6 carbon atoms, even more preferably 1 to 4 carbon atoms, and most preferably 1 to 3 carbon atoms. As a straight-chain aliphatic hydrocarbon group, a straight-chain alkyl group is preferred; specifically, examples include methylene [-CH2-], ethyl [-(CH2)2-], trimethylene [-(CH2)3-], tetramethylene [-(CH2)4-], and pentamethylene [-(CH2)5-]. The branched-chain aliphatic hydrocarbon group preferably has 2 to 10 carbon atoms, more preferably 3 to 6 carbon atoms, even more preferably 3 or 4 carbon atoms, and most preferably 3 carbon atoms. As a branched chain aliphatic hydrocarbon group, a branched chain alkyl group is preferred. 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-. As for the alkyl group in alkyl extension, it is preferred to be a straight-chain alkyl group with 1 to 5 carbon atoms.

[0174] The aforementioned straight-chain or branched-chain aliphatic hydrocarbon groups may or may not have substituents. Examples of such substituents include fluorine atoms, fluorinated alkyl groups with 1 to 5 carbon atoms substituted with fluorine atoms, and carbonyl groups.

[0175] •••Aliphatic hydrocarbon groups containing rings in their structure. Examples of aliphatic hydrocarbon groups containing rings in their structure include cyclic aliphatic hydrocarbon groups (groups with two hydrogen atoms removed from an aliphatic hydrocarbon ring) containing heteroatoms in their ring structure and which may also have substituents; groups in which the aforementioned cyclic aliphatic hydrocarbon groups are bonded to the ends of straight-chain or branched-chain aliphatic hydrocarbon groups; and groups in which the aforementioned cyclic aliphatic hydrocarbon groups are intermediate in straight-chain or branched-chain aliphatic hydrocarbon groups. Examples of the aforementioned straight-chain or branched-chain aliphatic hydrocarbon groups include those identical to those described above. It is preferable that the cyclic aliphatic hydrocarbon group has 3 to 20 carbon atoms, and even more preferably 3 to 12 carbon atoms. The cyclic aliphatic hydrocarbon group may also be a polycyclic group or a monocyclic group. As a monocyclic alicyclic hydrocarbon group, it is preferable that it is a group in which two hydrogen atoms have been removed from a monocyclic alkane. For monocyclic alkanes, those with 3 to 6 carbon atoms are preferred; examples include cyclopentane and cyclohexane. For polycyclic alicyclic hydrocarbon groups, those consisting of a self-polycyclic cycloalkane with two hydrogen atoms removed are preferred; for polycyclic alkanes, those with 7 to 12 carbon atoms are preferred; examples include adamantane, noralane, isoalkanes, tricyclodecane, and tetracyclododecane.

[0176] The cyclic aliphatic hydrocarbon group may or may not have substituents. Examples of substituents include alkyl, alkoxy, halogen atom, alkyl halide, hydroxyl, and carbonyl groups. Among the aforementioned substituents, alkyl groups with 1 to 5 carbon atoms are preferred, with methyl, ethyl, propyl, n-butyl, and tert-butyl being even more preferred. Among the aforementioned substituents, alkoxy groups with 1 to 5 carbon atoms are preferred, with methoxy, ethoxy, n-propoxy, iso-propoxy, n-butoxy, and tert-butoxy being even more preferred, and methoxy and ethoxy being even more preferred. Among the aforementioned substituents, fluorine atoms are preferred. Among the aforementioned substituents, alkyl halide groups are those in which some or all of the hydrogen atoms of the aforementioned alkyl group are substituted with the aforementioned halogen atom. The cyclic aliphatic hydrocarbon group is formed by the substitution of a portion of the carbon atoms constituting its ring structure with a substituent containing a heteroatom. The preferred substituents for containing the heteroatom are -O-, -C(=O)-O-, -S-, -S(=O)2-, and -S(=O)2-O-.

[0177] ••The aromatic hydrocarbon group in Yax1 is a hydrocarbon group having at least one aromatic ring. This aromatic ring only needs to have a cyclic conjugated system with 4n+2 π electrons, and is not particularly limited; it can be monocyclic or polycyclic. The number of carbon atoms in the aromatic ring is preferably 5-30, more preferably 5-20, even more preferably 6-15, and particularly preferably 6-12. However, this number of carbon atoms does not include the number of carbon atoms in the substituents. Examples of aromatic rings include aromatic hydrocarbon rings of benzene, naphthalene, anthracene, and phenanthrene; and aromatic heterocycles in which a portion of the carbon atoms constituting the aforementioned aromatic hydrocarbon rings are substituted with heteroatoms. Examples of heteroatoms in aromatic heterocycles include oxygen, sulfur, and nitrogen atoms. Examples of aromatic heterocycles include pyridine rings and thiophene rings. Specifically, aromatic hydrocarbon groups include those derived from aromatic hydrocarbon rings or aromatic heterocycles by removing two hydrogen atoms (aryl or heteroaryl); those derived from aromatic compounds containing two or more aromatic rings (e.g., biphenyl, benzo[a], etc.) by removing two hydrogen atoms; and those derived from aromatic hydrocarbon rings or aromatic heterocycles by removing one hydrogen atom (aryl or heteroaryl) by substituting one hydrogen atom with an alkyl group (e.g., aryl groups derived from aryl alkyl groups such as benzyl, phenethyl, 1-naphthylmethyl, 2-naphthylmethyl, 1-naphthylethyl, 2-naphthylethyl, etc. by further removing one hydrogen atom). The alkyl group bonded to the aforementioned aryl or heteroaryl group preferably has 1 to 4 carbon atoms, more preferably 1 to 2 carbon atoms, and particularly preferably 1 carbon atom.

[0178] In the aforementioned aromatic hydrocarbon group, the hydrogen atoms of the aromatic hydrocarbon group may also be substituted by substituents. For example, the hydrogen atoms of the aromatic ring bonded to the aromatic hydrocarbon group may also be substituted by substituents. Examples of such substituents include alkyl, alkoxy, halogen atom, alkyl halide, and hydroxyl groups. Among the aforementioned substituents, alkyl groups having 1 to 5 carbon atoms are preferred, and methyl, ethyl, propyl, n-butyl, and tert-butyl are even more preferred. Among the aforementioned substituents, examples of alkoxy, halogen atom, and alkyl halide groups are those that substitute for the hydrogen atoms of the aforementioned cyclic aliphatic hydrocarbon group.

[0179] • Divalent linker containing heteroatoms: When Yax1 is a divalent linker containing heteroatoms, preferred examples of such linkers include -O-, -C(=O)-O-, -OC(=O)-, -C(=O)-, -OC(=O)-O-, -C(=O)-NH-, -NH-, -NH-C(=NH)- (HH can also be substituted by alkyl, acetylated, etc. substituents), -S-, -S(=O)2-, -S(=O)2-O-, general formula -Y21-O-Y22-, -Y21-O-, -Y21-C(=O)-O-, The radicals represented by -C(=O)-O-Y21-, -[Y21-C(=O)-O]m”-Y22-, -Y21-OC(=O)-Y22-, or -Y21-S(=O)2-O-Y22- [where Y21 and Y22 are each independently divalent hydrocarbon groups that may also have substituents, O is an oxygen atom, and m” is an integer from 0 to 3], etc. When the aforementioned divalent linking group containing heteroatoms is -C(=O)-NH-, -C(=O)-NH-C(=O)-, -NH-, or -NH-C(=NH)-, its H may also be substituted by substituents such as alkyl or acetyl groups. It is preferable that the number of carbon atoms (alkyl, acetyl, etc.) is 1 to 10, more preferably 1 to 8, and particularly preferably 1 to 5. In the general formulas -Y21-O-Y22-, -Y21-O-, -Y21-C(=O)-O-, -C(=O)-O-Y21-, -[Y21-C(=O)-O]m”-Y22-, -Y21-OC(=O)-Y22-, or -Y21-S(=O)2-O-Y22-, Y21 and Y22 are each independently divalent hydrocarbon groups, which may also have substituents. Examples of such divalent hydrocarbon groups are those described as the divalent linker in the aforementioned Yax1 (divalent hydrocarbon groups that may also have substituents). For Y21, a straight-chain aliphatic hydrocarbon group is preferred, a straight-chain alkyl group is even more preferred, a straight-chain alkyl group with 1 to 5 carbon atoms is more preferred, and methylene or ethyl groups are particularly preferred. Y22 is preferably a straight-chain or branched-chain aliphatic hydrocarbon group, and is more preferably methylene, ethyl, or alkylmethylene. The alkyl group in the alkylmethylene group is preferably a straight-chain alkyl group with 1 to 5 carbon atoms, more preferably a straight-chain alkyl group with 1 to 3 carbon atoms, and is most preferably methyl. In the group represented by the formula -[Y21-C(=O)-O]m”-Y22-, m” is an integer from 0 to 3, preferably an integer from 0 to 2, preferably 0 or 1, and particularly preferably 1. That is, the group represented by the formula -[Y21-C(=O)-O]m”-Y22- is particularly preferred. Among them, the group represented by the formula -(CH2)a'-C(=O)-O-(CH2)b'- is preferred. In this formula, a' is an integer from 1 to 10, preferably an integer from 1 to 8, even better if it is an integer from 1 to 5, and even better if it is 1 or 2, with 1 being the best.b' can be an integer from 1 to 10, preferably an integer from 1 to 8, preferably an integer from 1 to 5, preferably 1 or 2, and 1 is the best.

[0180] In the above, Yax1 is preferably a single bond, an ester bond [-C(=O)-O-, -OC(=O)-], an ether bond (-O-), a straight-chain or branched-chain alkyl group, or a combination thereof, and preferably a single bond, an ester bond [-C(=O)-O-, -OC(=O)-].

[0181] In the aforementioned formula (a10-1), Wax1 is an aromatic hydrocarbon group that may also have substituents. Examples of aromatic hydrocarbon groups in Wax1 include those derived from an aromatic ring that may also have substituents, by removing (nax1+1) hydrogen atoms. The aromatic ring is not particularly limited as long as it is a cyclic conjugated system with 4n+2 π electrons, and can be monocyclic or polycyclic. It is preferable that the number of carbon atoms in the aromatic ring is 5 to 30, even more preferable that it is 5 to 20, and even more preferable that it is 6 to 15, with 6 to 12 being particularly preferred. Specifically, examples of aromatic rings include aromatic hydrocarbon rings of benzene, naphthalene, anthracene, and phenanthrene; and aromatic heterocycles in which a portion of the carbon atoms constituting the aforementioned aromatic hydrocarbon ring is substituted with heteroatoms. Examples of heteroatoms in aromatic heterocycles include oxygen atoms, sulfur atoms, and nitrogen atoms. Examples of aromatic heterocycles include pyridine rings and thiophene rings. Furthermore, the aromatic hydrocarbon group in Wax1 can be a group consisting of an aromatic compound containing an aromatic ring (e.g., biphenyl, naphthalene, etc.) with (nax1+1) hydrogen atoms removed. Of these, Wax1 is preferably a group with (nax1+1) hydrogen atoms removed from benzene, naphthalene, anthracene, or biphenyl; it is further preferably a group with (nax1+1) hydrogen atoms removed from benzene or naphthalene; and it is even more preferably a group with (nax1+1) hydrogen atoms removed from benzene.

[0182] The aromatic hydrocarbon group in Wax1 may or may not have substituents. Examples of the aforementioned substituents include alkyl, alkoxy, halogen atom, and alkyl halide. Examples of the aforementioned substituents, such as alkyl, alkoxy, halogen atom, and alkyl halide, are the same as those listed as substituents for the cyclic aliphatic hydrocarbon group in Wax1. It is preferable that the aforementioned substituent is a straight-chain or branched-chain alkyl group having 1 to 5 carbon atoms, further preferably a straight-chain or branched-chain alkyl group having 1 to 3 carbon atoms, and even more preferably an ethyl or methyl group, with methyl being particularly preferred. It is preferable that the aromatic hydrocarbon group in Wax1 is unsubstituented.

[0183] In the aforementioned formula (a10-1), nax1 is an integer greater than or equal to 1, preferably an integer from 1 to 10, even more preferably an integer from 1 to 5, and even better if it is 1, 2 or 3, and especially preferably 1 or 2.

[0184] The following are specific examples of the constituent unit (a10) represented by the aforementioned formula (a10-1). In the following formulas, Rα represents a hydrogen atom, a methyl group, or a trifluoromethyl group.

[0185]

[0186]

[0187]

[0188]

[0189] The constituent unit (a10) of component (A1) may be one or more types. When component (A1) has constituent unit (a10), the proportion of constituent unit (a10) in component (A1) relative to the total of all constituent units constituting component (100 mol%) is preferably 10-80 mol%, more preferably 20-60 mol%, and even more preferably 30-60 mol%. By setting the proportion of constituent unit (a10) within the aforementioned preferred range, the efficiency of proton supply in the resist film is increased, and the solubility of the developer can be adequately guaranteed, thus making it easier to obtain the effects of the present invention.

[0190] Regarding the constituent unit (a8): The constituent unit (a8) is a constituent unit derived from a compound represented by the following general formula (a8-1).

[0191] [In the formula, W2 is a polymerizable group, Yax2 is a single bond or a (nax2+1) valence linking group, Yax2 can also form a condensation ring with W2, R1 is a fluorinated alkyl group with 1 to 12 carbon atoms, R2 is an organic group or hydrogen atom with 1 to 12 carbon atoms that may also have fluorine atoms, and nax2 is an integer from 1 to 3].

[0192] In formula (a8-1), the polymerizable group in W2 is the same as the polymerizable group in W01 in the above general formula (a0-1).

[0193] In formula (a8-1), Yax2 is a single bond or (nax2+1) valence, that is, a 2-valent, 3-valent or 4-valent linker.

[0194] As a divalent linker in Yax2, examples include those identical to those described for the divalent linker in Yax0, which is W01 in the above general formula (a0-1). As a trivalent linker in Yax2, examples include a base from which one hydrogen atom is removed from the aforementioned divalent linker, or a base from which the aforementioned divalent linker is further bonded. As a tetravalent linker, examples include a base from which two hydrogen atoms are removed from the aforementioned divalent linker.

[0195] Yax2 and W2 can also form condensation rings. When Yax2 and W2 form condensation rings, examples of their ring structures include condensation rings of alicyclic hydrocarbons and aromatic hydrocarbons. The condensation rings formed by Yax2 and W2 can also have heteroatoms. In the condensation rings formed by Yax2 and W2, the alicyclic hydrocarbon portion can be monocyclic or polycyclic. Examples of condensation rings formed by Yax2 and W2 include condensation rings formed by a polymerizable group at the W2 site and Yax2, and condensation rings formed by a group other than a polymerizable group at the W2 site and Yax2. Specifically, examples include bicyclic condensation rings of cycloalkenes and aromatic rings, tricyclic condensation rings of cycloalkenes and two aromatic rings, bicyclic condensation rings of cycloalkanes with polymerizable substituents and aromatic rings, and tricyclic condensation rings of cycloalkanes with polymerizable substituents and aromatic rings.

[0196] The condensation ring formed by Yax2 and W2 may also have substituents. Examples of such substituents include methyl, ethyl, propyl, hydroxy, hydroxyalkyl, carboxyl, halogen (fluorine, chlorine, bromine, etc.), alkoxy (methoxy, ethoxy, propoxy, butoxy, etc.), acetyl, alkyloxycarbonyl, alkylcarbonyloxy, etc.

[0197] The following are specific examples of condensation rings formed by Yax2 and W2. Wα represents a polymerizable group.

[0198]

[0199] In formula (a8-1), R1 is a fluorinated alkyl group having 1 to 12 carbon atoms. The fluorinated alkyl group having 1 to 12 carbon atoms is a group in which one or all of the hydrogen atoms of the alkyl group having 1 to 12 carbon atoms are substituted with fluorine atoms. The aforementioned alkyl group can also be linear or branched. Examples of linear fluorinated alkyl groups having 1 to 12 carbon atoms include methyl, ethyl, propyl, butyl, pentyl, hexyl, heptyl, octyl, nonyl, decyl, undecyl, and dodecyl groups in which one or all of the hydrogen atoms are substituted with fluorine atoms. As a branched chain fluorinated alkyl group having 1 to 12 carbon atoms, examples include 1-methylethyl, 1,1-dimethylethyl, 1-methylpropyl, 2-methylpropyl, 1-methylbutyl, 2-methylbutyl, 3-methylbutyl, 1-ethylbutyl, 2-ethylbutyl, 1-methylpentyl, 2-methylpentyl, 3-methylpentyl, and 4-methylpentyl groups in which one or all of the hydrogen atoms are substituted with fluorine atoms.

[0200] As R1, the fluorinated alkyl group having 1 to 12 carbon atoms is preferably a fluorinated alkyl group having 1 to 5 carbon atoms, and more particularly preferably a trifluoromethyl group.

[0201] In formula (a8-1), R2 is an organic group or hydrogen atom with 1 to 12 carbon atoms, which may also have fluorine atoms.

[0202] As R2, an organogroup having 1 to 12 carbon atoms and also having fluorine atoms includes a monovalent hydrocarbon group having 1 to 12 carbon atoms. As a hydrocarbon group, straight-chain or branched-chain alkyl groups or cyclic hydrocarbon groups are included. As a straight-chain alkyl group, examples include methyl, ethyl, propyl, butyl, pentyl, hexyl, heptyl, octyl, nonyl, decyl, undecyl, and dodecyl. As a branched-chain alkyl group, examples include 1-methylethyl, 1,1-dimethylethyl, 1-methylpropyl, 2-methylpropyl, 1-methylbutyl, 2-methylbutyl, 3-methylbutyl, 1-ethylbutyl, 2-ethylbutyl, 1-methylpentyl, 2-methylpentyl, 3-methylpentyl, and 4-methylpentyl.

[0203] When R2 is a cyclic hydrocarbon group, the hydrocarbon group can be an aliphatic hydrocarbon group or an aromatic hydrocarbon group, and can be a polycyclic group or a monocyclic group. As a monocyclic aliphatic hydrocarbon group, it is preferable to have one hydrogen atom removed from a monocyclic alkane. As for the monocyclic alkane, it is preferable to have 3 to 6 carbon atoms; examples include cyclopentane and cyclohexane. As a polycyclic aliphatic hydrocarbon group, it is preferable to have one hydrogen atom removed from a polycyclic alkane; as for the polycyclic alkane, it is preferable to have 7 to 12 carbon atoms; examples include adamantane, noralane, isoalkanes, tricyclodecane, and tetracyclododecane.

[0204] When the cyclic hydrocarbon group of R2 is an aromatic hydrocarbon group, the aromatic hydrocarbon group is a hydrocarbon group having at least one aromatic ring. Specifically, examples of such aromatic hydrocarbon groups include groups that have one hydrogen atom removed from the aromatic hydrocarbon rings of benzene, naphthalene, anthracene, phenanthrene, biphenyl, and fumonisin.

[0205] The organic group with 1 to 12 carbon atoms in R2 may also have substituents other than fluorine atoms. Examples of such substituents include hydroxyl, carboxyl, halogen (chlorine, bromine, etc.), alkoxy (methoxy, ethoxy, propoxy, butoxy, etc.), and alkyloxycarbonyl.

[0206] R2 is preferably a fluorinated alkyl group with 1 to 12 carbon atoms, preferably a fluorinated alkyl group with 1 to 5 carbon atoms, and even more preferably a trifluoromethyl group.

[0207] In formula (a8-1), nax2 is an integer from 1 to 3, with 1 or 2 being preferred, and 1 being even more preferred.

[0208] It is preferable that the constituent unit (a8) is a constituent unit (a81) derived from a compound represented by the following general formula (a8-1-1).

[0209] [In formula (a8-1-1), W2 is a polymerizable group, Wax2 is a cyclic group with a (nax2+1) valence, W2 and Wax2 can also form a condensation ring, R1 is a fluorinated alkyl group with 1 to 12 carbon atoms, R2 is an organic group or hydrogen atom with 1 to 12 carbon atoms that may also have fluorine atoms, and nax2 is an integer from 1 to 3].

[0210] In formula (a8-1-1), W2, R1, R2 and nax2 are the same as W2, R1, R2 and nax2 in the above general formula (a8-1).

[0211] In formula (a8-1-1), Wax2 is a cyclic group with a valence of (nax2+1). Examples of cyclic groups in Wax2 include aliphatic cyclic groups and aromatic cyclic groups, and it can also be monocyclic or polycyclic.

[0212] As a monocyclic group, an aliphatic cyclic group is preferably a group that has removed one hydrogen atom from a monocyclic alkane. The monocyclic alkane is preferably one with 3 to 6 carbon atoms, specifically examples include cyclopentane and cyclohexane. As a polycyclic group, an aliphatic cyclic group is preferably a group that has removed one hydrogen atom from a polycyclic alkane, specifically examples include groups that have removed one or more hydrogen atoms from polycyclic alkanes such as decahydronaphthalene, perhydroazine, and perhydroanthracene.

[0213] An aromatic cyclic group is a hydrocarbon group having at least one aromatic ring. This aromatic ring only needs to be a cyclic conjugated system having 4n+2 π electrons, and there are no particular limitations. The number of carbon atoms in the aromatic ring is preferably 5 to 30, more preferably 5 to 20, even more preferably 6 to 15, and particularly preferably 6 to 12. Examples of aromatic rings include aromatic hydrocarbon rings such as benzene, naphthalene, anthracene, and phenanthrene; and aromatic heterocycles in which a portion of the carbon atoms constituting the aforementioned aromatic hydrocarbon rings are substituted with heteroatoms. Examples of heteroatoms in aromatic heterocycles include oxygen atoms, sulfur atoms, and nitrogen atoms. Examples of aromatic heterocycles include pyridine rings and thiophene rings. Specifically, the aromatic hydrocarbon group can be categorized as a group (aryl or heteroaryl) formed by removing one hydrogen atom from the aforementioned aromatic hydrocarbon ring or aromatic heterocycle; a group formed by removing one hydrogen atom from an aromatic compound containing two or more aromatic rings (e.g., biphenyl, benzo[a]), or a group in which one hydrogen atom of the aforementioned aromatic hydrocarbon ring or aromatic heterocycle is substituted with an alkyl group (e.g., arylalkyl groups such as benzyl, phenethyl, 1-naphthylmethyl, 2-naphthylmethyl, 1-naphthylethyl, 2-naphthylethyl, etc.). It is preferable that the alkyl group bonded to the aforementioned aromatic hydrocarbon ring or aromatic complex ring has 1 to 4 carbon atoms, more preferably 1 to 2, and particularly preferably 1.

[0214] Substituents that can be found in the cyclic group of Wax2 include, for example, carboxyl groups, halogen atoms (fluorine atoms, chlorine atoms, bromine atoms, etc.), alkoxy groups (methoxy, ethoxy, propoxy, butoxy, etc.), alkyloxy carbonyl groups, etc.

[0215] W2 and Wax2 can also form a condensation ring, and the description is the same as that of the condensation ring formed by Yax2 and W2 in the aforementioned formula (a8-1).

[0216] The following are specific examples of the constituent unit (a8). In the following formula, Rα represents a hydrogen atom, a methyl group, or a trifluoromethyl group.

[0217]

[0218] In the above example, it is preferable that the constituent unit (a8) is represented by the chemical formula (a8-1-09).

[0219] (A1) The constituent unit (a8) may be one or more types. When the (A1) component has a constituent unit (a8), the proportion of the constituent unit (a8) relative to the total of all constituent units constituting the (A1) component (100 mol%) is preferably 1 to 30 mol%, more preferably 3 to 20 mol%, and even more preferably 5 to 15 mol%. By setting the proportion of the constituent unit (a8) above the preferred lower limit, the compatibility with the developing solution and cleaning solution can be improved. On the other hand, if it is below the preferred upper limit, a balance with other constituent units can be achieved, resulting in good various lithography properties.

[0220] Regarding the constituent unit (a2): The (A1) component may further have a constituent unit (a2) containing a cyclic group containing lactone, a cyclic group containing -SO2-, or a cyclic group containing carbonate (but, those equivalent to the aforementioned constituent unit (a01) or the aforementioned constituent unit (a1) are removed). When the (A1) component is used in the formation of the resist film, the cyclic group containing lactone, the cyclic group containing -SO2-, or the cyclic group containing carbonate of the constituent unit (a2) is more effective in improving the adhesion of the resist film to the substrate. Furthermore, by having the constituent unit (a2), the photolithography properties are better, for example, by appropriately adjusting the acid diffusion length, improving the adhesion of the resist film to the substrate, and appropriately adjusting the solubility during development.

[0221] "A cyclic group containing lactone" refers to a cyclic group whose ring skeleton contains a ring (lactone ring) including -OC (=O)-. Counting with the lactone ring as the first ring, a group with only a lactone 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 lactone can be either a monocyclic group or a polycyclic group. There is no particular limitation on the cyclic group containing lactone that is a constituent unit (a2), and any group can be used. Specifically, groups represented by the following general formulas (a2-r-1) to (a2-r-7) are given examples.

[0222] [In the formula, Ra'21 is 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, which may also contain oxygen atom (-O-) or sulfur atom (-S-); n' is an integer from 0 to 2; m' is 0 or 1].

[0223] In the aforementioned general formulas (a2-r-1) to (a2-r-7), the alkyl group of Ra'21 is preferably an alkyl group having 1 to 6 carbon atoms. It is preferable that the alkyl group is straight-chain or branched-chain. Specifically, examples include methyl, ethyl, propyl, isopropyl, n-butyl, isobutyl, tert-butyl, 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. It is preferable that the alkoxy group is straight-chain or branched-chain. Specifically, examples include alkyl groups mentioned above that are linked to an oxygen atom (-O-). The halogen atom in Ra'21 is preferably a fluorine atom. As a haloalkyl group in Ra'21, there are groups in which some or all of the hydrogen atoms of the aforementioned alkyl group in Ra'21 are replaced by the aforementioned halogen atoms. As such a haloalkyl group, a fluorinated alkyl group is preferred, especially a perfluoroalkyl group.

[0224] In Ra'21, in "-COOR" and "-OC(=O)R", R is a hydrogen atom, an alkyl group, a cyclic group containing lactones, a cyclic group containing carbonates, or a cyclic group containing -SO2-. The alkyl group in "R" can be linear, branched, or cyclic, with 1 to 15 carbon atoms being preferred. When "R" is a linear or branched alkyl group, 1 to 10 carbon atoms are preferred, 1 to 5 carbon atoms are more preferred, and methyl or ethyl is particularly preferred. When "R" is a cyclic alkyl group, 3 to 15 carbon atoms are preferred, 4 to 12 carbon atoms are more preferred, and 5 to 10 carbon atoms are optimal. Specifically, examples include groups derived from monocyclic alkanes that may be substituted with or unsubstituted with fluorine atoms or fluorinated alkyl groups, having removed one or more hydrogen atoms; and groups derived from polycyclic alkanes such as bicyclic alkanes, tricyclic alkanes, and tetracyclic alkanes, having removed one or more hydrogen atoms. More specifically, examples include groups derived from monocyclic alkanes such as cyclopentane and cyclohexane, having removed one or more hydrogen atoms; and groups derived from polycyclic alkanes such as adamantane, noralane, isoalkanes, tricyclic decane, and tetracyclic dodecane, having removed one or more hydrogen atoms. As for the lactone-containing cyclic group in "R", examples include those identical to those represented by the aforementioned general formulas (a2-r-1) to (a2-r-7). As for the carbonate-containing cyclic group in "R", examples include those identical to the carbonate-containing cyclic groups described later, and specifically, examples include those represented by the general formulas (ax3-r-1) to (ax3-r-3). As for the -SO2- cyclic group in R", examples include those identical to the -SO2- cyclic groups described later, and specifically, examples are those represented by the general formulas (a5-r-1) to (a5-r-4). As for the hydroxyalkyl group in Ra'21, it is preferred to have 1 to 6 carbon atoms, and specifically, examples include groups in Ra'21 where at least one hydrogen atom of the aforementioned alkyl group is substituted with a hydroxyl group.

[0225] 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-chain 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, specific examples include those with a -O- or -S- group 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 preferable to have an alkyl group having 1 to 5 carbon atoms or -O-, and even more preferable to have an alkyl group having 1 to 5 carbon atoms, with methylene being the most desirable.

[0226] The following are specific examples of bases, each represented by the general form (a2-r-1) to (a2-r-7).

[0227]

[0228]

[0229] "A cyclic group containing -SO2-" means 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. The ring containing -SO2- in the ring skeleton is counted as the first ring; when only this ring is present, it is called a monocyclic group; and when other ring structures are present, regardless of their structure, they are called polycyclic groups. Cyclic groups containing -SO2- can be monocyclic or polycyclic. Cyclic groups containing -SO2- are particularly preferred if their ring skeleton contains -O-SO2-, that is, cyclic groups containing a sultone ring in which -OS- in -O-SO2- forms part of the ring skeleton. More specifically, examples of cyclic groups containing -SO2- are represented by the following general formulas (a5-r-1) to (a5-r-4).

[0230] [In the formula, Ra'51 is 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, which may also contain oxygen atom or sulfur atom, and n' is an integer from 0 to 2].

[0231] 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). The alkyl, alkoxy, halogen atom, haloalkyl, -COOR”, -OC(=O)R”, and hydroxyalkyl groups in Ra'51 are each the same as those given in the description of Ra'21 in the aforementioned general formulas (a2-r-1) to (a2-r-7). Specific examples of groups represented by the general formulas (a5-r-1) to (a5-r-4) are given below. In these formulas, “Ac” represents acetyl.

[0232]

[0233]

[0234]

[0235] "Cyclic groups containing carbonate rings" refers to cyclic groups whose ring skeleton contains a ring consisting of -OC (=O)-O- (carbonate ring). Counting with the carbonate ring as the first ring, a group containing 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. Cyclic groups containing carbonate rings can be either monocyclic or polycyclic. There is no particular limitation on the type of cyclic group containing a carbonate ring; any type can be used. Specifically, examples are given of groups represented by the following general formulas (ax3-r-1) to (ax3-r-3).

[0236] [In the formula, Ra'x31 is 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, which may also contain oxygen atom or sulfur atom, p' is an integer from 0 to 3, q' is 0 or 1].

[0237] 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). The alkyl, alkoxy, halogen atom, haloalkyl, -COOR”, -OC(=O)R”, and hydroxyalkyl groups in Ra'31 are each the same as those given in the description of Ra'21 in the aforementioned general formulas (a2-r-1) to (a2-r-7). Specific examples of groups represented by the general formulas (ax3-r-1) to (ax3-r-3) are given below.

[0238]

[0239] As a constituent unit (a2), it is preferable that it is a constituent unit derived from an acrylate in which the hydrogen atom bonded to the carbon atom at the α-position can also be replaced by a substituent. It is preferable that the constituent unit (a2) is represented by the following general formula (a2-1).

[0240] [In the formula, R is a hydrogen atom, an alkyl group with 1 to 5 carbon atoms, or a haloalkyl group with 1 to 5 carbon atoms, and Ya21 is a single bond or a divalent linkage. La21 is -O-, -COO-, -CON(R')-, -OCO-, -CONHCO-, or -CONHCS-, and R' represents a hydrogen atom or a methyl group. However, when La21 is -O-, Ya21 will not become -CO-. Ra21 is a cyclic group containing lactone, a cyclic group containing carbonate, or a cyclic group containing -SO2-].

[0241] In the aforementioned formula (a2-1), R is the same as described above. It is preferable that R is a hydrogen atom, an alkyl group having 1 to 5 carbon atoms, or a fluorinated alkyl group having 1 to 5 carbon atoms. In terms of industrial availability, it is particularly preferable that it is a hydrogen atom or a methyl group.

[0242] In the aforementioned formula (a2-1), there are examples of dual-valent linkage bases in Ya21 that are the same as the dual-valent linkage bases in Yax0 of W01 in the above general formula (a0-1).

[0243] In the above, Ya21 is preferably a single bond, an ester bond [-C(=O)-O-], an ether bond (-O-), a straight-chain or branched chain alkyl group, or a combination thereof.

[0244] In the aforementioned formula (a2-1), Ra21 is a cyclic group containing lactone, a cyclic group containing -SO2-, or a cyclic group containing carbonate. Suitable examples of the lactone-containing cyclic group, the -SO2- containing cyclic group, and the carbonate-containing cyclic group in Ra21 include groups represented by the aforementioned general formulas (a2-r-1) to (a2-r-7), groups represented by the general formulas (a5-r-1) to (a5-r-4), and groups represented by the general formulas (ax3-r-1) to (ax3-r-3). Preferably, it is a cyclic group containing lactone or a cyclic group containing -SO2-, and even more preferably, it is a group represented by the aforementioned general formulas (a2-r-1), (a2-r-2), (a2-r-6), or (a5-r-1). Specifically, it is preferable to use a base represented by any of the aforementioned chemical formulas (r-lc-1-1)~(r-lc-1-7), (r-lc-2-1)~(r-lc-2-18), (r-lc-6-1), (r-sl-1-1), (r-sl-1-18), and it is even more preferable to use a base represented by the aforementioned chemical formula (r-lc-2-1).

[0245] (A1) The constituent unit (a2) may be one or more types. When the (A1) component has a constituent unit (a2), the proportion of the constituent unit (a2) relative to the total of all constituent units constituting the (A1) component (100 mol%) is preferably 1 to 40 mol%, and even more preferably 10 to 30 mol%. By setting the proportion of the constituent unit (a2) above the preferred lower limit, the effects obtained by containing the constituent unit (a2) can be fully obtained as described above. If it is below the upper limit, a balance with other constituent units can be achieved, and various photolithography properties are better.

[0246] Regarding the constituent unit (a3): The (A1) component may further have a constituent unit (a3) ​​containing an aliphatic hydrocarbon group with a polar group (but, those equivalent to constituent units (a01), (a1), (a2), or (a8) are removed). By having a constituent unit (a3) ​​in the (A1) component, the hydrophilicity of the (A1) component is increased, resulting in improved resolution. Furthermore, the acid diffusion length can be appropriately adjusted.

[0247] Examples of polar groups include hydroxyl, cyano, and carboxyl groups, with hydroxyl being particularly preferred. Examples of aliphatic hydrocarbon groups include straight-chain or branched-chain hydrocarbon groups (preferably alkyl groups) with 1 to 10 carbon atoms, or cyclic aliphatic hydrocarbon groups (cyclic groups). These cyclic groups can also be monocyclic or polycyclic, and can be appropriately selected from a variety of proposals, for example, in resins used as resist components for ArF excimer lasers.

[0248] When the cyclic group is a monocyclic group, it is preferable that the number of carbon atoms is 3 to 10. It is even more preferable that the constituent unit is derived from an acrylate containing an aliphatic monocyclic group containing a hydroxyl, cyano, or carboxyl group. Examples of this monocyclic group 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 industrially preferred.

[0249] When the cyclic group is a polycyclic group, it is preferable that the number of carbon atoms in the polycyclic group is 7 to 30. It is even more preferable that the constituent unit is derived from an acrylate containing an aliphatic polycyclic group containing a hydroxyl, cyano, or carboxyl group. Examples of such polycyclic groups include groups that have removed two or more hydrogen atoms from bicyclic alkanes, tricyclic alkanes, tetracyclic alkanes, etc. Specifically, examples include groups that have removed two or more hydrogen atoms from polycyclic alkanes such as adamantane, noralane, isoalkanes, tricyclic decane, and tetracyclic dodecane. Among these polycyclic groups, groups that have removed two or more hydrogen atoms from adamantane, groups that have removed two or more hydrogen atoms from noralane, and groups that have removed two or more hydrogen atoms from tetracyclic dodecane are industrially preferred.

[0250] As a constituent unit (a3), any unit containing an aliphatic hydrocarbon group with a polar group is acceptable and is not particularly limited. It is preferable that the constituent unit (a3) ​​is derived from an acrylate ester whose hydrogen atom bonded to the α-carbon atom can also be substituted by a substituent, and that it contains an aliphatic hydrocarbon group with a polar group. When the hydrocarbon group in the aliphatic hydrocarbon group containing the polar group is a straight-chain or branched chain with 1 to 10 carbon atoms, it is preferable that the constituent unit is derived from a hydroxyethyl ester of acrylic acid. Furthermore, it is preferable that the constituent unit (a3) ​​is represented by the following formula (a3-1) and the constituent unit (a3-2).

[0251] [In the formula, R is the same as above, j is an integer from 1 to 3, and k is an integer from 1 to 3].

[0252] In formula (a3-1), j is preferably 1 or 2, and 1 is more preferred. When j is 2, it is preferred that the hydroxyl group is bonded to the 3- or 5-position of the adamantyl alkyl group. When j is 1, it is preferred that the hydroxyl group is bonded to the 3-position of the adamantyl alkyl group. When j is 1, it is preferred that the hydroxyl group is bonded to the 3-position of the adamantyl alkyl group, which is particularly preferred.

[0253] In formula (a3-2), k is preferably 1. It is preferred that the cyano group is bonded to the 5th or 6th position of the deoxygenated group.

[0254] (A1) The constituent unit (a3) ​​may be one or more types. When the (A1) component has a constituent unit (a3), the proportion of the constituent unit (a3) ​​relative to the total of all constituent units constituting the (A1) component (100 mol%) 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 the constituent unit (a3) ​​above the preferred lower limit, the effects obtained by containing the constituent unit (a3) ​​can be fully obtained through the aforementioned effects. If it is below the preferred upper limit, a balance with other constituent units can be achieved, and various photolithography properties become better.

[0255] 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), the (A1) component can improve the dry etching resistance of the formed resist pattern. Furthermore, it can improve the hydrophobicity of the (A1) component. The improvement in hydrophobicity, especially in solvent imaging processes, can contribute to the improvement of resolution, resist pattern shape, etc. The "acid-non-dissociative cyclic group" in the constituent unit (a4) is a cyclic group that does not dissociate and remains directly in the constituent unit when acid is generated in the resist composition due to exposure (for example, when acid is generated from the constituent unit or component (B) due to exposure).

[0256] As a constituent unit (a4), it is preferable to use a constituent unit derived from an acrylate containing an acid-non-dissociable aliphatic cyclic group. This cyclic group can be one of the most commonly used resin components in resist compositions for ArF excimer lasers, KrF excimer lasers (preferably ArF excimer lasers), etc. From an industrially readily available point of view, this cyclic group is particularly preferred to be selected from at least one of tricyclic decyl, adamantyl, tetracyclic dodecyl, isoyl, and decyl. These polycyclic groups may also have a straight-chain or branched-chain alkyl group having 1 to 5 carbon atoms as a substituent. Specifically, as a constituent unit (a4), examples can be shown of constituent units represented by the following general formulas (a4-1) to (a4-7).

[0257] [In the formula, Rα is the same as above].

[0258] (A1) The constituent unit (a4) may be one or more types. When the (A1) component has a constituent unit (a4), the proportion of the constituent unit (a4) relative to the total of all constituent units constituting the (A1) component (100 mol%) is preferably 1 to 40 mol%, and even more preferably 1 to 20 mol%. By setting the proportion of the constituent unit (a4) above the preferred lower limit, the effects 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.

[0259] Regarding the constituent unit (st): The constituent unit (st) is a constituent unit derived from styrene or a styrene derivative. "Constant unit derived from styrene" means a constituent unit formed by the cleavage of the vinyl double bond of styrene. "Constant unit derived from styrene derivative" means a constituent unit formed by the cleavage of the vinyl double bond of a styrene derivative (but, excluding those equivalent to constituent unit (a10)).

[0260] "Styrene derivatives" means compounds in which at least some of the hydrogen atoms of styrene are substituted by substituents. Examples of styrene derivatives include those in which the α-hydrogen atom of styrene is substituted by a substituent, those in which one or more hydrogen atoms of the benzene ring of styrene are substituted by a substituent, and those in which the α-hydrogen atom of styrene and one or more hydrogen atoms of the benzene ring are substituted by a substituent.

[0261] Examples of substituents for the α-hydrogen atom of styrene include alkyl groups having 1 to 5 carbon atoms or alkyl halides having 1 to 5 carbon atoms. Among the aforementioned alkyl groups having 1 to 5 carbon atoms, linear or branched alkyl groups having 1 to 5 carbon atoms are preferred; specifically, examples include methyl, ethyl, propyl, isopropyl, n-butyl, isobutyl, tert-butyl, pentyl, isopentyl, and neopentyl. The aforementioned alkyl halides having 1 to 5 carbon atoms are groups in which some or all of the hydrogen atoms of the aforementioned alkyl groups having 1 to 5 carbon atoms are substituted with halogen atoms. Fluorine atoms are particularly preferred as the halogen atom. Among the substituents for the α-hydrogen atom of styrene, alkyl groups having 1 to 5 carbon atoms or fluorinated alkyl groups having 1 to 5 carbon atoms are preferred, alkyl groups having 1 to 3 carbon atoms or fluorinated alkyl groups having 1 to 3 carbon atoms are even more preferred, and methyl is more preferred in terms of industrial availability.

[0262] Examples of substituents for replacing the hydrogen atoms of the benzene ring in styrene include alkyl groups, alkoxy groups, halogen atoms, and alkyl halides. Among the aforementioned substituents, alkyl groups having 1 to 5 carbon atoms are preferred, with methyl, ethyl, propyl, n-butyl, and tert-butyl being even more preferred. Among the aforementioned substituents, alkoxy groups having 1 to 5 carbon atoms are preferred, with methoxy, ethoxy, n-propoxy, iso-propoxy, n-butoxy, and tert-butoxy being even more preferred, and methoxy and ethoxy being even more preferred. Among the aforementioned substituents, fluorine atoms are preferred. Among the aforementioned substituents, alkyl halides are groups in which some or all of the hydrogen atoms of the aforementioned alkyl group are substituted with the aforementioned halogen atom. Among the substituents for replacing the hydrogen atoms of the benzene ring in styrene, alkyl groups having 1 to 5 carbon atoms are preferred, with methyl or ethyl being even more preferred, and methyl being even more preferred.

[0263] As a constituent unit (st), it is preferable to be a constituent unit derived from styrene, or a constituent unit derived from a styrene derivative in which the α-hydrogen atom of styrene is replaced by an alkyl group or a halogenated alkyl group in which one to five carbon atoms are substituted, it is even more preferable to be a constituent unit derived from styrene, or a constituent unit derived from a styrene derivative in which the α-hydrogen atom of styrene is replaced by a methyl group, and it is even more preferable to be a constituent unit derived from styrene.

[0264] (A1) The constituent unit (st) may be one or more types. When the constituent unit (A1) has a constituent unit (st), the proportion of the constituent unit (st) relative to the total of all constituent units (100 mol%) constituting the constituent unit (A1) is preferably 1 to 30 mol%, and even more preferably 1 to 20 mol%.

[0265] The (A1) component contained in the inhibitor composition may be used alone or in combination with two or more. In the inhibitor composition of this embodiment, the (A1) component is a resin component having a constituent unit (a01). Examples of relevant (A1) components include polymeric compounds containing only repeating structures of constituent units (a01); polymeric compounds having repeating structures of constituent units (a01) and constituent units (a10); polymeric compounds having repeating structures of constituent units (a01), constituent units (a10), and constituent units (a8); polymeric compounds having repeating structures of constituent units (a01), constituent units (a10), and constituent units (a3); polymeric compounds having repeating structures of constituent units (a01), constituent units (a10), constituent units (a2), and constituent units (a3); polymeric compounds having repeating structures of constituent units (a01) and constituent units (a2) are more suitable. Among them, polymeric compounds having repeating structures of constituent units (a01) and constituent units (a10) are preferred.

[0266] In a polymeric compound containing repeating structures of constituent units (a01) and (a10), the proportion of constituent units (a01) in the polymeric compound relative to the total number of constituent units constituting the polymeric compound (100 mol%) is preferably 20-90 mol%, more preferably 40-80 mol%, and even more preferably 40-70 mol%. Furthermore, the proportion of constituent units (a10) in the polymeric compound relative to the total number of constituent units constituting the polymeric compound (100 mol%) is preferably 10-80 mol%, more preferably 20-60 mol%, and even more preferably 30-60 mol%.

[0267] In a polymer compound having a repeating structure of constituent units (a01), (a10), and (a8), the proportion of constituent units (a01) in the polymer compound relative to the total number of constituent units constituting the polymer compound (100 mol%) is preferably 20-80 mol%, more preferably 30-50 mol%, and even more preferably 35-45 mol%. Furthermore, the proportion of constituent units (a10) in the polymer compound relative to the total number of constituent units constituting the polymer compound (100 mol%) is preferably 30-70 mol%, more preferably 40-60 mol%, and even more preferably 45-55 mol%. Furthermore, the proportion of the constituent unit (a8) in the polymer compound relative to the total number of all constituent units constituting the polymer compound (100 mol%) is preferably 1 to 30 mol%, more preferably 3 to 20 mol%, and even more preferably 5 to 15 mol%.

[0268] A polymeric compound having a repeating structure of constituent units (a01), (a10), and (a3), wherein the proportion of constituent units (a01) in the polymeric compound relative to the total number of constituent units constituting the polymeric compound (100 mol%) is preferably 20-80 mol%, more preferably 30-50 mol%, and even more preferably 35-45 mol%. Furthermore, the proportion of constituent units (a10) in the polymeric compound relative to the total number of constituent units constituting the polymeric compound (100 mol%) is preferably 30-70 mol%, more preferably 40-60 mol%, and even more preferably 45-55 mol%. Furthermore, the proportion of the constituent unit (a3) ​​in the polymer compound relative to the total number of all constituent units constituting the polymer compound (100 mol%) is preferably 1 to 30 mol%, more preferably 3 to 20 mol%, and even more preferably 5 to 15 mol%.

[0269] In a polymer compound having a repeating structure of constituent units (a01), (a10), (a2), and (a3), the proportion of constituent units (a01) in the polymer compound relative to the total number of constituent units constituting the polymer compound (100 mol%) is preferably 20-80 mol%, more preferably 30-50 mol%, and even more preferably 35-45 mol%. Furthermore, the proportion of constituent units (a10) in the polymer compound relative to the total number of constituent units constituting the polymer compound (100 mol%) is preferably 10-50 mol%, more preferably 20-40 mol%, and even more preferably 25-35 mol%. Furthermore, the proportion of the constituent unit (a2) in the polymer compound relative to the total number of all constituent units constituting the polymer compound (100 mol%) is preferably 1-30 mol%, more preferably 10-30 mol%, and even more preferably 15-25 mol%. Furthermore, the proportion of the constituent unit (a3) ​​in the polymer compound relative to the total number of all constituent units constituting the polymer compound (100 mol%) is preferably 1-30 mol%, more preferably 3-20 mol%, and even more preferably 5-15 mol%.

[0270] The related (A1) component can be manufactured by dissolving the monomers of each derived constituent unit in a polymerization solvent, whereby, for example, a free radical polymerization initiator such as azobisisobutyronitrile (AIBN) or dimethyl azobisisobutyrate (e.g., V-601) is added, and then polymerizing. Alternatively, the related (A1) component can be manufactured by dissolving the monomers of the derived constituent unit (a01) and the monomers of other constituent units besides the necessary derived constituent unit (a01) (e.g., compounds protecting the hydroxyl groups of the monomers of the derived constituent unit (a10)) in a polymerization solvent, whereby the free radical polymerization initiator as described above is added, and then polymerizing, followed by a deprotection reaction. Furthermore, during polymerization, for example, by using a chain moving agent such as HS-CH2-CH2-CH2-C(CF3)2-OH, a -C(CF3)2-OH group can also be introduced at the end. Thus, copolymers of hydroxyalkyl groups in which a portion of the hydrogen atom of the introduced alkyl group is replaced by a fluorine atom are more effective in reducing imaging defects or LER (line edge roughness: unevenness of the sidewalls of the line).

[0271] The mass average molecular weight (Mw) of component (based on polystyrene obtained by gel permeation chromatography (GPC)) of component (A1) is not particularly limited, but is preferably 1,000 to 50,000, more preferably 2,000 to 30,000, and even more preferably 3,000 to 20,000. If the Mw of component (A1) is below the upper limit of this range, it has sufficient solubility in the inhibitor solvent when used as an inhibitor; if it is above the lower limit of this range, it has better resistance to dry etching or better inhibitor pattern profile. The dispersibility (Mw / Mn) of component (A1) is not particularly limited, but is preferably 1.0 to 4.0, more preferably 1.0 to 3.0, and especially preferably 1.0 to 2.0. Mn represents the number average molecular weight.

[0272] • Regarding component (A2), in the resist composition of this embodiment, component (A) may also be used in conjunction with a substrate component (hereinafter referred to as "component (A2)") that is not equivalent to the aforementioned component (A1) and whose solubility in the developer changes due to the action of acid. There are no particular limitations on component (A2), and it may be selected from most of the substrate components known in the past as chemical amplification type resist compositions. Component (A2) may be used alone with one polymer compound or one low-molecular-weight compound, or it may be used in combination with two or more compounds.

[0273] The proportion of component (A1) in component (A) relative to the total mass of component (A) is preferably 25% by mass or more, preferably 50% by mass or more, preferably 75% by mass or more, and can also be 100% by mass. If this proportion is 25% by mass or more, it is easy to form a resist pattern with excellent lithography properties such as high sensitivity, resolution, and roughness improvement.

[0274] In the resist composition of this embodiment, the content of component (A) is adjusted according to the thickness of the resist film to be formed.

[0275] <Other Components> In addition to component (A) mentioned above, the inhibitor composition of this embodiment may also contain other components. Examples of other components include components (B), (D), (E), (F), and (S) as shown below.

[0276] ≪Acid Generating Agent Component (B)≫ In addition to component (A), the inhibitor composition of this embodiment may further contain an acid generating agent component (B) that generates acid upon exposure (hereinafter referred to as "component (B)"). There are no particular limitations on component (B), and any acid generating agent currently proposed for use in chemically amplifying inhibitor compositions may be used. Examples of such acid generating agents include onium salt acid generating agents such as monazite 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.

[0277] As a onium salt acid generator, examples include compounds represented by the general formula (b-1) (hereinafter also referred to as "(b-1) component"), compounds represented by the general formula (b-2) (hereinafter also referred to as "(b-2) component"), or compounds represented by the general formula (b-3) (hereinafter also referred to as "(b-3) component").

[0278] [In the formula, R101 and R104~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 also 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 or a single bond containing an oxygen atom. V101~V103 are each independently a single bond, an alkyl group, or a fluorinated alkyl group. L101~L102 are each independently a single bond or an oxygen atom. L103~L105 are each independently a single bond, -CO-, or -SO2-. m is an integer greater than or equal to 1, and Mm+ is an onium cation with an m valence].

[0279] {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.

[0280] It may also have a substituent cyclic group: the cyclic group is preferably a cyclic hydrocarbon group, which may also 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 saturation is usually preferred.

[0281] 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 best preferably 6 to 10. However, this number of carbon atoms does not include the number of carbon atoms in the substituents. Specifically, the aromatic ring possessed by the aromatic hydrocarbon group in R101 includes benzene, naphthalene, anthracene, phenanthrene, biphenyl, or aromatic heterocycles in which a portion of the carbon atoms constituting such aromatic rings are substituted with heteroatoms. Examples of heteroatoms in aromatic heterocycles include oxygen atoms, sulfur atoms, and nitrogen atoms. As for the aromatic hydrocarbon group in R101, examples include groups that have one hydrogen atom removed from the aforementioned aromatic ring (aryl: for example, phenyl, naphthyl, etc.), and groups that have one hydrogen atom of the aforementioned aromatic ring substituted with 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.

[0282] In R101, the cyclic aliphatic hydrocarbon group includes aliphatic hydrocarbon groups whose structure contains a ring. Examples of aliphatic hydrocarbon groups containing a ring 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-chain aliphatic hydrocarbon group, and alicyclic hydrocarbon groups intermediate in the middle of a straight-chain or branched-chain aliphatic hydrocarbon group. The aforementioned alicyclic hydrocarbon group preferably has 3 to 20 carbon atoms, and more preferably 3 to 12. The aforementioned alicyclic hydrocarbon group can also be a polycyclic or 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. The polycyclic alicyclic hydrocarbon group is preferably a group that has removed one or more hydrogen atoms from the polycycloalkane, and the polycycloalkane preferably has 7 to 30 carbon atoms. Among them, the polycycloalkane is preferably a polycycloalkane with a cross-linked ring system, such as adamantane, noralkyl, isoalkyl, tricyclodecane, tetracyclododecane, etc.; and polycycloalkane with a condensed ring system, such as a cyclic group with a steroid skeleton, is even more preferred.

[0283] 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, and is even more preferably a group that has removed one hydrogen atom from a polycyclic alkane. It is particularly preferred to be adamantyl or daunoalkyl, and is best to be adamantyl.

[0284] The linear aliphatic hydrocarbon group that can be bonded to the alicyclic hydrocarbon group preferably has 1 to 10 carbon atoms, more preferably 1 to 6, even more preferably 1 to 4, and most preferably 1 to 3. As a linear aliphatic hydrocarbon group, a linear alkyl group is preferred, specifically including methylene [-CH2-], ethyl [-(CH2)2-], trimethylene [-(CH2)3-], tetramethylene [-(CH2)4-], pentamethylene [-(CH2)5-], etc. The branched aliphatic hydrocarbon group that can be bonded to the alicyclic hydrocarbon group preferably has 2 to 10 carbon atoms, more preferably 3 to 6, even more preferably 3 or 4, and most preferably 3. As a branched chain aliphatic hydrocarbon group, it is preferable to have a branched chain alkyl group, specifically including 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-. As for the alkyl group in alkyl extension, it is preferred to be a straight-chain alkyl group with 1 to 5 carbon atoms.

[0285] 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 heterocyclic groups represented by other chemical formulas (r-hr-1) to (r-hr-16). In the formula, * indicates the bond at the Y101 in formula (b-1).

[0286]

[0287] Examples of substituents in the cyclic group of R101 include alkyl, alkoxy, halogen atom, alkyl halide, hydroxyl, carbonyl, and nitro groups. Among the alkyl substituents, alkyl groups with 1 to 5 carbon atoms are preferred, with methyl, ethyl, propyl, n-butyl, and tert-butyl being the most desirable. Among the alkoxy substituents, alkoxy groups with 1 to 5 carbon atoms are preferred, with methoxy, ethoxy, n-propoxy, iso-propoxy, n-butoxy, and tert-butoxy being even more desirable, with methoxy and ethoxy being the most desirable. Among the halogen atom substituents, fluorine, chlorine, bromine, and iodine atoms are examples, with fluorine being the most desirable. Among the alkyl halide substituents, alkyl groups with 1 to 5 carbon atoms are examples of groups in which one or all of the hydrogen atoms of methyl, ethyl, propyl, n-butyl, and tert-butyl groups are substituted with the aforementioned halogen atom. The carbonyl group, as a substituent, is a methylene (-CH2-) group that replaces the cyclic hydrocarbon group.

[0288] The cyclic hydrocarbon group in R101 may also be a condensed cyclic group comprising a condensed ring of an aliphatic hydrocarbon group and an aromatic ring. Examples of the aforementioned condensed ring include polycycloalkanes with a cross-linked ring system and one or more aromatic rings condensed together. Specific examples of the aforementioned cross-linked polycycloalkanes include bicycloalkanes such as bicyclo[2.2.1]heptane (noralane) and bicyclo[2.2.2]octane. As for the aforementioned condensed cyclic group, it is preferable to have a condensed ring comprising a bicycloalkane and two or three aromatic rings, and even more preferably, a condensed ring comprising bicyclo[2.2.2]octane and two or three aromatic rings condensed together. Specific examples of the condensed cyclic group in R101 include those represented by the following formulas (r-br-1) ~ (r-br-2). In the formula, * indicates that the bond is located at the Y101 bond in formula (b-1).

[0289]

[0290] Substituents that may also be present in the condensed cyclic group of R101 include, for example, alkyl, alkoxy, halogen atom, alkyl halide, hydroxyl, carbonyl, nitro, aromatic hydrocarbon group, alicyclic hydrocarbon group, etc. Examples of alkyl, alkoxy, halogen atom, and alkyl halide substituents for the aforementioned condensed cyclic group are the same as those listed for substituents of the cyclic group in R101. Examples of aromatic hydrocarbon substituents for 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, arylalkyl groups such as benzyl, phenethyl, 1-naphthylmethyl, 2-naphthylmethyl, 1-naphthylethyl, 2-naphthylethyl, etc.), and heterocyclic groups each represented by the above formulas (r-hr-1) to (r-hr-6). Examples of alicyclic hydrocarbon groups that are substituents for the aforementioned condensed cyclic groups include groups derived from monocyclic alkanes such as cyclopentane and cyclohexane by removing one hydrogen atom; groups derived from polycyclic alkanes such as adamantane, noralane, isoalkanes, tricyclic decane, and tetracyclic dodecane by removing one hydrogen atom; cyclic groups containing lactones, each represented by the aforementioned general formulas (a2-r-1) to (a2-r-7); cyclic groups containing -SO2-, each represented by the aforementioned general formulas (a5-r-1) to (a5-r-4); and heterocyclic groups, each represented by the aforementioned formulas (r-hr-7) to (r-hr-16).

[0291] Also, chain alkyl groups with substituents may be used: The chain alkyl group as R101 may be either straight-chain or branched-chain. 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-chain alkyl group, it is preferred to have 3 to 20 carbon atoms, more preferably 3 to 15, and most preferably 3 to 10. 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.

[0292] The alkenyl group may also have substituents: The alkenyl group of R101 may be either linear or branched, preferably with 2 to 10 carbon atoms, more preferably with 2 to 5 carbon atoms, even more preferably with 2 to 4 carbon atoms, and particularly preferably with 3 carbon atoms. Examples of linear alkenyl groups include vinyl, allyl, and butenyl. Examples of branched alkenyl groups include 1-methylvinyl, 2-methylvinyl, 1-methylpropenyl, and 2-methylpropenyl. Among the above-mentioned linear alkenyl groups, linear alkenyl groups are preferred, vinyl and allyl groups are more preferred, and vinyl groups are particularly preferred.

[0293] Examples of substituents in the chain-like alkyl or alkenyl groups of R101 include alkoxy groups, halogen atoms, alkyl halides, hydroxyl groups, carbonyl groups, nitro groups, amino groups, and cyclic groups in the aforementioned R101.

[0294] In the above, R101 is preferably a cyclic group that may also have substituents, and is even more preferably a cyclic hydrocarbon group that may also have substituents. More specifically, it is preferably a group that has removed one or more hydrogen atoms from phenyl, naphthyl, or polycycloalkane; a cyclic group containing lactone represented by the aforementioned general formula (a2-r-1) to (a2-r-7); or a cyclic group containing -SO2- represented by the aforementioned general formula (a5-r-1) to (a5-r-4).

[0295] In formula (b-1), Y101 is a single bond or a divalent group containing an oxygen atom. When Y101 is a divalent group containing an oxygen atom, it may also 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 groups containing oxygen atoms include non-hydrocarbon oxygen-containing groups such as oxygen atoms (ether bond: -O-), ester bond (-C(=O)-O-), oxycarbonyl group (-OC(=O)-), amide bond (-C(=O)-NH-), carbonyl group (-C(=O)-), carbonate bond (-OC(=O)-O-), etc.; combinations of such non-hydrocarbon oxygen-containing groups with alkyl groups, etc. Sulfonyl groups (-SO2-) may also be further linked in such combinations. Examples of related divalent bonding groups containing oxygen atoms include bonding groups represented by the following general formulas (y-al-1) to (y-al-7). Furthermore, in the following general formulas (y-al-1) to (y-al-7), the bonded to R101 in formula (b-1) is V'101 in the following general formulas (y-al-1) to (y-al-7).

[0296] [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].

[0297] In V'102, the divalent saturated hydrocarbon group is preferably an alkyl group with 1 to 30 carbon atoms, preferably an alkyl group with 1 to 10 carbon atoms, and preferably an alkyl group with 1 to 5 carbon atoms.

[0298] The alkyl group in V'101 and V'102 can be either a straight-chain alkyl group or a branched-chain alkyl group, with a straight-chain alkyl group being preferred. Specifically, the 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 ethyl [-CH2CH2-]; alkyl ethyl groups such as -CH(CH3)CH2-, -CH(CH3)CH(CH3)-, -C(CH3)2CH2-, and -CH(CH2CH3)CH2-; alkyl trimethylene groups such as (n-propyl) [-CH2CH2CH2-]; alkyl trimethylene groups such as -CH(CH3)CH2CH2- and -CH2CH(CH3)CH2-; and tetramethylene [-CH2CH2CH2CH2-]. Alkyl tetramethylene groups such as -CH(CH3)CH2CH2CH2- and -CH2CH(CH3)CH2CH2-; pentamethylene groups such as [-CH2CH2CH2CH2CH2-]. Furthermore, in V'101 or V'102, a portion of the methylene groups in the aforementioned alkyl groups may also be substituted with a divalent aliphatic cyclic group having 5 to 10 carbon atoms. This aliphatic cyclic group is preferably a divalent group formed by removing one hydrogen atom from the cyclic aliphatic hydrocarbon group (monocyclic or polycyclic) of Ra'3 in the aforementioned formula (a1-r-1), and is further preferably cyclohexyl, 1,5-adidamyl, or 2,6-adidamyl.

[0299] As Y101, it is preferable to be a divalent linker containing an ester bond or a divalent linker containing an ether bond, and it is even more preferable to be a linker represented by the above formulas (y-al-1) to (y-al-5).

[0300] In formula (b-1), V101 is a single bond, an alkyl group, or a fluorinated alkyl group. It is preferred that the alkyl group or fluorinated alkyl group in V101 has 1 to 4 carbon atoms. As the fluorinated alkyl group in V101, there are groups in which one or all of the hydrogen atoms of the alkyl group in V101 are substituted with fluorine atoms. It is preferred that V101 is a single bond or a fluorinated alkyl group having 1 to 4 carbon atoms.

[0301] In formula (b-1), R102 is a fluorine atom or a fluorinated alkyl group having 1 to 5 carbon atoms. It is preferable that R102 is a fluorine atom or a perfluoroalkyl group having 1 to 5 carbon atoms, and even more preferable that it is a fluorine atom.

[0302] As a specific example of the anion portion represented by the aforementioned formula (b-1), when Y101 is a single bond, it is a fluorinated alkyl sulfonate anion such as trifluoromethane sulfonate anion or perfluorobutane sulfonate anion; when Y101 is a divalent linkage containing an oxygen atom, it is an anion represented by any of the following formulas (an-1) to (an-3).

[0303] [In the formula, R”101 is an aliphatic cyclic group that may also have substituents, a monovalent heterocyclic group represented by the above chemical formulas (r-hr-1) to (r-hr-6), a condensed cyclic group represented by the above formulas (r-br-1) or (r-br-2), or a chain alkyl group that may also have substituents; R”102 is an aliphatic cyclic group that may also have substituents, a condensed cyclic group represented by the above formulas (r-br-1) or (r-br-2), or a group represented by the above general formulas (a2-r-1), (a2-r-3) to (a2-r-7). The cyclic group containing lactone, or the cyclic group containing -SO2- represented by the aforementioned general formula (a5-r-1)~(a5-r-4), R”103 is an aromatic cyclic group that may have substituents, an aliphatic cyclic group that may have substituents, 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).

[0304] The aliphatic cyclic groups of R”101, R”102 and R”103 that may also have substituents are preferably those exemplified as the cyclic aliphatic hydrocarbon group in R101 of the aforementioned formula (b-1). As the aforementioned substituents, there are substituents that are the same as those that may also replace the cyclic aliphatic hydrocarbon group in R101 of the aforementioned formula (b-1).

[0305] The aromatic cyclic group in R”103 that may also have substituents is preferably the aromatic hydrocarbon group in the cyclic hydrocarbon group in R101 of the aforementioned formula (b-1). As the aforementioned substituent, there are substituents that are the same as those that may also replace the aromatic hydrocarbon group in R101 of the aforementioned formula (b-1).

[0306] The chain alkyl group in R”101 that may also have substituents is preferably the group exemplified as the chain alkyl group in R101 in the aforementioned formula (b-1). The chain alkenyl group in R”103 that may also have substituents is preferably the group exemplified as the chain alkenyl group in R101 in the aforementioned formula (b-1).

[0307] • 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, each being the same as R101 in formula (b-1). However, R104 and R105 may also be bonded to each other to form a ring. It is preferable that R104 and R105 are chain alkyl groups with substituents, preferably straight-chain or branched-chain alkyl groups, or straight-chain or branched-chain fluorinated alkyl groups. It is preferable that the number of carbon atoms of the chain alkyl group is 1 to 10, more preferably 1 to 7, and even more preferably 1 to 3. It is preferable that the number of carbon atoms of the chain alkyl group of R104 and R105 is within the above-mentioned range, because it also has good solubility in solvents for inhibitors. Furthermore, in the chain alkyl groups of R104 and R105, the more hydrogen atoms replaced by fluorine atoms, the stronger the acid becomes, and the better the 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, each being 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.

[0308] • In the anionic formula (b-3) of component (b-3), R106~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, each of which is the same as R101 in formula (b-1). In formula (b-3), L103~L105 are each independently a single bond, -CO- or -SO2-.

[0309] In the above, the anionic portion of component (B) is preferably an anionic component of component (b-1). Among these, it is even more preferable that the anionic component is represented by any one of the above general formulas (an-1) to (an-3), it is even more preferable that the anionic component is represented by any one of the general formulas (an-1) or (an-2), and it is particularly preferable that the anionic component is represented by the general formula (an-2).

[0310] {Cation Section} In the aforementioned formulas (b-1), (b-2), and (b-3), Mm+ represents an onium cation with a valence of m. Preferably, it is a strontium cation or a monium cation. m is an integer greater than or equal to 1.

[0311] As a preferred cation portion ((Mm+)1 / m), there are examples of organic cations represented by the following general formulas (ca-1) to (ca-5).

[0312] [In the formula, R201~R207 and R211~R212 each independently represent aryl, alkyl or alkenyl groups that may also have substituents; R201~R203, R206~R207, R211~R212 may also bond with each other to form a ring with the sulfur atom in the formula; R208~R209 each independently represent hydrogen atoms or alkyl groups with 1~5 carbon atoms; R210 is an aryl group that may also have substituents, an alkyl group that may also have substituents, an alkenyl group that may also have substituents, or a cyclic group containing -SO2- that may also 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 linkage group].

[0313] In the above general formulas (ca-1) to (ca-5), the aryl groups in R201 to R207 and R211 to R212 are preferably unsubstituted aryl groups with 6 to 20 carbon atoms, and phenyl or naphthyl is preferred. The alkyl groups in R201 to R207 and R211 to R212 are preferably chain-like or cyclic alkyl groups with 1 to 30 carbon atoms. The alkenyl groups in R201 to R207 and R211 to R212 are preferably alkenyl groups with 2 to 10 carbon atoms. Substituents that may also be present in R201 to R207 and R210 to R212 include, for example, alkyl, halogen atom, haloalkyl, carbonyl, cyano, amino, aryl, and groups each represented by the following general formulas (ca-r-1) to (ca-r-7).

[0314] [In the formula, R'201 can be a hydrogen atom, or a cyclic group with substituents, or a chain alkyl group with substituents, or a chain alkenyl group with substituents.]

[0315] The cyclic group may also have substituents: It is preferred that the cyclic group is a cyclic hydrocarbon group, which may also be an aromatic hydrocarbon group or an aliphatic hydrocarbon group. An aliphatic hydrocarbon group refers to a hydrocarbon group that is not aromatic. Furthermore, the aliphatic hydrocarbon group may be saturated or unsaturated, but saturation is usually preferred.

[0316] The aromatic hydrocarbon group in R'201 is a hydrocarbon group having an aromatic ring. It is preferable that the aromatic hydrocarbon group has 3 to 30 carbon atoms, more preferably 5 to 30, even more preferably 5 to 20, particularly preferably 6 to 15, and best preferably 6 to 10. However, this number of carbon atoms does not include the number of carbon atoms in the substituents. Specifically, examples of aromatic rings in the aromatic hydrocarbon group of R'201 include benzene, naphthalene, anthracene, phenanthrene, biphenyl, or aromatic heterocycles in which a portion of the carbon atoms constituting such aromatic rings are substituted with heteroatoms. Examples of heteroatoms in aromatic heterocycles include oxygen atoms, sulfur atoms, and nitrogen atoms. As for the aromatic hydrocarbon group in R'201, examples include groups that have one hydrogen atom removed from the aforementioned aromatic ring (aryl: for example, phenyl, naphthyl, etc.), and groups that have one hydrogen atom of the aforementioned aromatic ring substituted with 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 carbon atoms, and particularly preferably 1 carbon atom.

[0317] R'201 includes aliphatic hydrocarbon groups whose structure contains a ring. Examples of aliphatic hydrocarbon groups containing a ring 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-chain aliphatic hydrocarbon group, and alicyclic hydrocarbon groups intermediate in a straight-chain or branched-chain aliphatic hydrocarbon group. The aforementioned alicyclic hydrocarbon groups preferably have 3 to 20 carbon atoms, and more preferably 3 to 12. The aforementioned alicyclic hydrocarbon groups can also be polycyclic or monocyclic. As for monocyclic alicyclic hydrocarbon groups, groups with one or more hydrogen atoms removed from a monocyclic alkane are preferred. As for such monocyclic alkanes, those with 3 to 6 carbon atoms are preferred, specifically cyclopentane and cyclohexane. The polycyclic alicyclic hydrocarbon group is preferably a group that has removed one or more hydrogen atoms from the polycycloalkane, and the polycycloalkane preferably has 7 to 30 carbon atoms. Among them, the polycycloalkane is preferably a polycycloalkane with a cross-linked ring system, such as adamantane, noralkyl, isoalkyl, tricyclodecane, tetracyclododecane, etc.; and polycycloalkane with a condensed ring system, such as a cyclic group with a steroid skeleton, is even more preferred.

[0318] Among them, the cyclic aliphatic hydrocarbon group in R'201 is preferably a group that has removed one or more hydrogen atoms from a monocyclic alkane or polycyclic alkane, and is even more preferably a group that has removed one hydrogen atom from a polycyclic alkane. It is particularly preferred to be adamantyl or daunoalkyl, and is best to be adamantyl.

[0319] The aliphatic hydrocarbon group that can be bonded to the alicyclic hydrocarbon group is preferably a straight-chain or branched chain with 1 to 10 carbon atoms, preferably 1 to 6 carbon atoms, even more preferably 1 to 4 carbon atoms, and particularly preferably 1 to 3 carbon atoms. As a straight-chain aliphatic hydrocarbon group, a straight-chain alkyl group is preferred, specifically including methylene [-CH2-], ethyl [-(CH2)2-], trimethylene [-(CH2)3-], tetramethylene [-(CH2)4-], pentamethylene [-(CH2)5-], etc. As a branched chain aliphatic hydrocarbon group, it is preferable to have a branched chain alkyl group, specifically including 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-. As for the alkyl group in alkyl extension, it is preferred to be a straight-chain alkyl group with 1 to 5 carbon atoms.

[0320] Furthermore, the cyclic hydrocarbon group in R'201 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 heterocyclic groups represented by other aforementioned chemical formulas (r-hr-1) to (r-hr-16).

[0321] Examples of substituents in the cyclic group of R'201 include alkyl, alkoxy, halogen atom, alkyl halide, hydroxyl, carbonyl, and nitro groups. Among the alkyl substituents, alkyl groups with 1 to 5 carbon atoms are preferred, with methyl, ethyl, propyl, n-butyl, and tert-butyl being the most desirable. Among the alkoxy substituents, alkoxy groups with 1 to 5 carbon atoms are preferred, with methoxy, ethoxy, n-propoxy, iso-propoxy, n-butoxy, and tert-butoxy being even more desirable, with methoxy and ethoxy being the most desirable. Among the halogen atom, fluorine atoms are preferred. Among the alkyl halide substituents, alkyl groups with 1 to 5 carbon atoms include groups where one or all of the hydrogen atoms of methyl, ethyl, propyl, n-butyl, and tert-butyl are substituted with the aforementioned halogen atom. Among the carbonyl substituents, a methylene (-CH2-) group that substitutes for the cyclic hydrocarbon group is preferred.

[0322] The alkyl group may also be a chain with substituents: The chain alkyl group of R'201 may be either straight-chain or branched-chain. As a straight-chain alkyl group, it is preferred to have 1 to 20 carbon atoms, more preferably 1 to 15 carbon atoms, and most preferably 1 to 10 carbon atoms. As a branched-chain alkyl group, it is preferred to have 3 to 20 carbon atoms, more preferably 3 to 15 carbon atoms, and most preferably 3 to 10 carbon atoms. 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.

[0323] Chain-like alkenyl groups with substituents may also be present: The chain-like alkenyl group of R'201 may be either straight-chain or branched-chain, preferably with 2 to 10 carbon atoms, more preferably with 2 to 5 carbon atoms, even more preferably with 2 to 4 carbon atoms, and particularly preferably with 3 carbon atoms. Examples of straight-chain alkenyl groups include vinyl, allyl, and butenyl. Examples of branched-chain alkenyl groups include 1-methylvinyl, 2-methylvinyl, 1-methylpropenyl, and 2-methylpropenyl. Of the chain-like alkenyl groups mentioned above, straight-chain alkenyl groups are preferred, vinyl and allyl groups are more preferred, and vinyl is particularly preferred.

[0324] Substituents in the chain-like alkyl or alkenyl groups of R'201 include, for example, alkoxy groups, halogen atoms, alkyl halides, hydroxyl groups, carbonyl groups, nitro groups, amino groups, and cyclic groups in the above-mentioned R'201.

[0325] R'201 may be a cyclic group with substituents, a chain alkyl group with substituents, or a chain alkenyl group with substituents, in addition to the above, there are examples that are the same as the acid dissociative groups represented by the above formula (a1-r-2) as cyclic groups with substituents or chain alkyl groups with substituents.

[0326] Wherein, R'201 is preferably a cyclic group that may also have substituents, and is even more preferably a cyclic hydrocarbon group that may also have substituents. More specifically, examples include groups from phenyl, naphthyl, and polycycloalkanes that have removed one or more hydrogen atoms; 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).

[0327] 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 and form a ring together with the sulfur atom in the formula, they can also be bonded by heteroatoms such as sulfur atom, oxygen atom, and nitrogen atom, or functional groups such as carbonyl, -SO-, -SO2-, -SO3-, -COO-, -CONH-, or -N(RN)- (where RN is an alkyl group with 1 to 5 carbon atoms). As for the formed ring, it is preferable that one ring containing the sulfur atom in its ring skeleton is a 3 to 10-membered ring, and a 5 to 7-membered ring is particularly preferred. Specific examples of the rings formed include thiophene rings, thiazole rings, benzothiophene rings, dibenzothiophene rings, 9H-thioxanthium rings, thioxanthone rings, thiothioxanthox rings, tetrahydrothiophene rings, and tetrahydrothiopiperanthium rings.

[0328] R208~R209 each independently represent an alkyl group with 1 to 5 hydrogen atoms or carbon atoms, preferably an alkyl group with 1 to 3 hydrogen atoms or carbon atoms. When it is an alkyl group, it can also bond with each other to form a ring.

[0329] R210 may be an aryl group, an alkyl group, an alkenyl group, or a cyclic group containing -SO2- that may have substituents. Examples of aryl groups in R210 include unsubstituted aryl groups with 6 to 20 carbon atoms, with phenyl or naphthyl being preferred. Examples of alkyl groups in R210 include chain or cyclic alkyl groups, with 1 to 30 carbon atoms being preferred. Examples of alkenyl groups in R210 include alkenyl groups with 2 to 10 carbon atoms being preferred. Examples of cyclic groups containing -SO2- that may have substituents in R210 include polycyclic groups containing -SO2-, and groups represented by the general formula (a5-r-1) are even more preferred.

[0330] Y201 each independently represents an aryl, alkyl, or alkenyl group. Examples of aryl groups in Y201 are those aryl groups exemplified as aromatic hydrocarbon groups in R101 of formula (b-1) above, in which one hydrogen atom has been removed. Examples of alkyl and alkenyl groups in Y201 are those alkyl or alkenyl groups exemplified as chain alkyl or chain alkenyl groups in R101 of formula (b-1) above, in which one hydrogen atom has been removed.

[0331] In the aforementioned formula (ca-4), x is 1 or 2. W201 is a (x+1) valence group, that is, a divalent or trivalent linker. As the divalent linker in W201, it is preferable to be a divalent hydrocarbon group that may also have substituents, and examples can be divalent hydrocarbon groups that may also have substituents, such as Ya21 in the above general formula (a2-1). The divalent linker in W201 may also be any of the following: straight chain, branched chain, or cyclic, with a cyclic form being preferred. Among them, it is preferable to have a group with two carbonyl groups combined at both ends of the aryl group. Examples of aryl groups include phenyl and naphthyl, with phenyl being particularly preferred. As the trivalent linker in W201, examples include a group that removes one hydrogen atom from the divalent linker in the aforementioned W201, or a group that further bonds the aforementioned divalent linker to the aforementioned divalent linker. As a trivalent linker in W201, it is preferable to have a group that bonds two carbonyl groups to an aryl group.

[0332] Specifically, the following cations, each represented by the chemical formula (ca-1-1) to (ca-1-78), are examples of suitable cations represented by the aforementioned formula (ca-1-1) to (ca-1-78).

[0333]

[0334]

[0335] [In the formula, g1, g2, and g3 represent the number of repetitions, g1 is an integer from 1 to 5, g2 is an integer from 0 to 20, and g3 is an integer from 0 to 20].

[0336]

[0337]

[0338]

[0339] [In the formula, R”201 is a hydrogen atom or a substituent, and the substituent is the same as those listed above as substituents that may also be present in R201~R207 and R210~R212].

[0340] Specific examples of suitable cations represented by the aforementioned formula (ca-2) include diphenyl citronium cation, bis(4-tert-butylphenyl) citronium cation, etc.

[0341] Specifically, suitable cations represented by the aforementioned formula (ca-3) include cations represented by the following formulas (ca-3-1) to (ca-3-6).

[0342]

[0343] Specifically, suitable cations represented by the aforementioned formula (ca-4) are given examples of cations represented by the following formulas (ca-4-1) to (ca-4-2).

[0344]

[0345] As suitable cations represented by the aforementioned formula (ca-5), examples are given of cations represented by the following general formulas (ca-5-1) to (ca-5-3).

[0346]

[0347] In the above, it is preferable that the cation part ((Mm+)1 / m) is a cation represented by the general formula (ca-1).

[0348] As component (B) in the inhibitor composition of this embodiment, it is preferable to include a compound represented by the following general formula (b0) as described above.

[0349] [In the formula, 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; Yb0 is a divalent linker containing an oxygen atom; V101 is a single bond, an alkyl group, or a fluorinated alkyl group; R102 is a fluorinated alkyl group or a fluorine atom with 1 to 5 carbon atoms; Mm+ represents an m-valent organic cation, where m is an integer greater than or equal to 1].

[0350] R101, V101 and R102 in the above general formula (b0) are the same as R101, V101 and R102 in the above general formula (b-1).

[0351] In the above general formula (b0), there are examples of Yb0 that are the same as the divalent linkage group containing oxygen atoms in Y101 in the above general formula (b-1).

[0352] The compound represented by the general formula (b0) above must have a divalent linker containing an oxygen atom as a necessary component, compared to the compound represented by the general formula (b-1) above. Therefore, the compound represented by the general formula (b0) above can appropriately control the diffusion of acid generated by exposure compared to a compound with the same structure but without a divalent linker containing an oxygen atom, thus further improving CDU and resolution in resist pattern formation.

[0353] As the inhibitor composition of this embodiment, component (B) is preferably a compound represented by the following general formula (b0-1).

[0354] [In the formula, 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; Yb0 is a divalent linker containing an oxygen atom; V101 is a single bond, an alkyl group, or a fluorinated alkyl group; R102 is a fluorinated alkyl group or a fluorine atom with 1 to 5 carbon atoms; Rb1 is an aryl group with a fluorine atom or an aryl group with a fluorinated alkyl group; Rb2 and Rb3 are each independently an aryl group that may have substituents, or they are bonded together with the sulfur atom in the formula to form a ring].

[0355] • Regarding the anionic portion, the anionic portion of the compound represented by the above general formula (b0-1) is the same as the anionic portion of the compound represented by the above general formula (b0).

[0356] • Regarding the cation portion, in the above general formula (b0-1), Rb1 is an aryl group having a fluorine atom or an aryl group having a fluorinated alkyl group. Examples of such aryl groups are those identical to the aryl groups in R201 to R203 in the above general formula (ca-1).

[0357] The fluorinated alkyl group comprising the aryl group in Rb1 specifically includes groups in which one or all of the hydrogen atoms of an alkyl group having 1 to 12 carbon atoms are substituted with fluorine atoms. The alkyl group may also be linear or branched. Specifically, linear fluorinated alkyl groups having 1 to 12 carbon atoms specifically include groups in which one or all of the hydrogen atoms of methyl, ethyl, propyl, butyl, pentyl, hexyl, heptyl, octyl, nonyl, decyl, undecyl, and dodecyl groups are substituted with fluorine atoms. As a branched chain fluorinated alkyl group having 1 to 12 carbon atoms, examples include 1-methylethyl, 1,1-dimethylethyl, 1-methylpropyl, 2-methylpropyl, 1-methylbutyl, 2-methylbutyl, 3-methylbutyl, 1-ethylbutyl, 2-ethylbutyl, 1-methylpentyl, 2-methylpentyl, 3-methylpentyl, and 4-methylpentyl groups in which one or all of the hydrogen atoms are substituted with fluorine atoms.

[0358] As the fluorinated alkyl group of the aryl group in Rb1, it is more preferably a group in which one or all of the hydrogen atoms of an alkyl group having 1 to 5 carbon atoms are substituted with fluorine atoms, it is even more preferably a group in which one or all of the hydrogen atoms of an alkyl group having 1 to 3 carbon atoms are substituted with fluorine atoms, and it is more preferably a trifluoromethyl group.

[0359] In the above general formula (b0-1), Rb1 is preferably an aryl group having fluorine atoms, or an aryl group having fluorinated alkyl groups having 1 to 5 carbon atoms, and even more preferably an aryl group having fluorine atoms.

[0360] As for the aryl group that may also have substituents in Rb2 and Rb3, and the ring formed by Rb2 and Rb3 bonded to each other and together with the sulfur atom in the formula, there are examples of the same aryl group that may also have substituents in R201 to R203 in the above general formula (ca-1), and the ring formed by R201 to R203 bonded to each other and together with the sulfur atom in the formula.

[0361] In the above general formula (b0-1), Rb2 and Rb3 are preferably aryl groups that may also have substituents. More specifically, it is preferable that at least one of Rb2 and Rb3 is an aryl group having a fluorine atom or an aryl group having a fluorinated alkyl group.

[0362] In the above general formula (b0-1), it is preferable that the number of fluorine atoms in the aryl groups of Rb1 to Rb3 is 2 to 8, and even more preferably 2 to 6. If the number of fluorine atoms in the aryl groups of Rb1 to Rb3 is 2 or more, it will promote the decomposition caused by exposure of the compound represented by the above general formula (b0-1) and further improve the sensitivity. On the other hand, if the number of fluorine atoms in the aryl groups of Rb1 to Rb3 is 6 or less, it can further improve the solubility in the developing solution.

[0363] The compound represented by the above general formula (b0-1) must include an aryl group having a fluorine atom on the cationic portion or an aryl group having a fluorinated alkyl group as an essential component, compared to the compound represented by the above general formula (b0-1) which does not contain an aryl group having a fluorine atom on the cationic portion or an aryl group having a fluorinated alkyl group. Therefore, the compound represented by the above general formula (b0-1) promotes decomposition caused by exposure, thus further improving the sensitivity in resist pattern formation.

[0364] The following are specific examples of suitable components (B) in the inhibitor composition of this embodiment.

[0365]

[0366] As the inhibitor composition of this embodiment, component (B) is preferably a compound represented by the above chemical formula (B-2).

[0367] In the inhibitor composition of this embodiment, component (B) can be used alone or in combination with two or more components. When the inhibitor composition contains component (B), the content of component (B) relative to 100 parts by mass of component (A) is preferably less than 60 parts by mass, more preferably 20 to 50 parts by mass, and even more preferably 30 to 45 parts by mass. By setting the content of component (B) within the aforementioned preferred range, sufficient pattern formation can be achieved. Furthermore, when each component of the inhibitor composition is dissolved in an organic solvent, a homogeneous solution is easily obtained, resulting in better storage stability of the inhibitor composition, which is therefore preferable.

[0368] ≪Base Component (D)≫ In the resist composition of this embodiment, in addition to component (A), a base component ((D) component) that inhibits acid generated by exposure (i.e., inhibits acid diffusion) may also be included. Component (D) in the resist composition acts as a quencher (acid diffusion inhibitor) for inhibiting acid generated by exposure. Examples of component (D) include photodisintegrating base (D1) (hereinafter referred to as "(D1) component") that loses its acid diffusion inhibition property due to exposure decomposition, and nitrogen-containing organic compound (D2) (hereinafter referred to as "(D2) component") that is not equivalent to component (D1). Among these, the photodisintegrating base ((D1) component) is preferred in terms of its ability to easily improve high sensitivity, reduce roughness, and inhibit the occurrence of coating defects.

[0369] • Regarding the (D1) component, when a resist pattern is formed by using a resist composition containing the (D1) component, the contrast between the exposed and unexposed areas of the resist film can be further improved. The (D1) component is not particularly limited; it can be any compound that loses its acid diffusion inhibition properties due to exposure decomposition. It is preferable to select one or more compounds from the group consisting of compounds represented by the following general formula (d1-1) (hereinafter referred to as "(d1-1) component"), compounds represented by the following general formula (d1-2) (hereinafter referred to as "(d1-2) component"), and compounds represented by the following general formula (d1-3) (hereinafter referred to as "(d1-3) component"). Since components (d1-1) to (d1-3) decompose and lose their acid diffusion inhibition properties (basicity) in the exposed areas of the resist film, they are not used as quenchers but are used as quenchers in the unexposed areas of the resist film.

[0370] [In the formula, Rd1~Rd4 are cyclic groups that may have substituents, chain alkyl groups that may have substituents, or chain alkenyl groups that may have substituents. However, in Rd2 of formula (d1-2), there is no fluorine atom bonded to the carbon atom adjacent to the S atom. Yd1 is a single bond or a divalent linked group. m is an integer greater than or equal to 1, and Mm+ are each an independent organic cation with an m valence].

[0371] {(d1-1) Components} •• In the anionic formula (d1-1), Rd1 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, and examples are the same as those mentioned above for R'201. Among these, it is preferable that Rd1 is 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 these groups include hydroxyl, side oxygen, alkyl, aryl, fluorine atom, fluorinated alkyl, lactone-containing cyclic groups each represented by the above general formulas (a2-r-1) to (a2-r-7), ether bonds, ester bonds, or combinations thereof. When ether or ester bonds are included as substituents, an alkyl group may be interposed as a substituent, preferably a linking group represented by formulas (y-al-1) to (y-al-5) above. Furthermore, when the aromatic hydrocarbon group, aliphatic cyclic group, or chain alkyl group in Rd1 has a linking group represented by the general formulas (y-al-1) to (y-al-7) above as a substituent, in formulas (y-al-1) to (y-al-7), the carbon atom of the aromatic hydrocarbon group, aliphatic cyclic group, or chain alkyl group in Rd1 of formula (d3-1) is bonded to V'101 in the general formulas (y-al-1) to (y-al-7). As the aforementioned aromatic hydrocarbon group, phenyl, naphthyl, and polycyclic structures containing a bicyclic octane skeleton (polycyclic structures containing a bicyclic octane skeleton and other cyclic structures) are preferred. As for the aforementioned aliphatic cyclic group, it is preferable to have a group formed by removing one or more hydrogen atoms from polycycloalkanes such as adamantane, noralkyl, isoalkyl, tricyclodecane, and tetracyclododecane. As for the aforementioned chain-like alkyl group, it is preferable to have 1 to 10 carbon atoms, specifically including straight-chain alkyl groups such as methyl, ethyl, propyl, butyl, pentyl, hexyl, heptyl, octyl, nonyl, and decyl; and branched-chain 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.

[0372] When the aforementioned chain-like alkyl group has a fluorine atom as a substituent or a fluorinated alkyl group, it is preferable that the fluorinated alkyl group has 1 to 11 carbon atoms, more preferably 1 to 8, and even more preferably 1 to 4. The fluorinated alkyl group may also contain atoms other than fluorine atoms. Examples of atoms other than fluorine atoms include oxygen atoms, sulfur atoms, and nitrogen atoms.

[0373] The following are preferred examples of the anionic portion of the (d1-1) component.

[0374]

[0375] ••In the cation formula (d1-1), Mm+ is an organic cation with an m valence. Suitable examples of the organic cation Mm+ are those identical to the cations represented by the aforementioned general formulas (ca-1) to (ca-5), with the cation represented by the aforementioned general formula (ca-1) being more preferred, and the cation represented by the aforementioned formulas (ca-1-1) to (ca-1-78) being even more preferred. The (d1-1) component can be used alone or in combination of two or more.

[0376] {(d1-2) Components} •• In the anionic formula (d1-2), Rd2 can be a cyclic group with substituents, a chain alkyl group with substituents, or a chain alkenyl group with substituents, and examples include those similar to R'201 mentioned above. However, in Rd2, there are no fluorine atoms bonded to the carbon atom adjacent to the S atom (no fluorination substitution). Therefore, the anion of the (d1-2) component becomes a moderately weak acid anion, and the quenching energy as the (D) component is enhanced. It is preferable that Rd2 is a chain alkyl group with substituents or an aliphatic cyclic group with substituents. It is preferable that the chain alkyl group has 1 to 10 carbon atoms, and even more preferably 3 to 10. As an aliphatic cyclic group, it is a group that has removed one or more hydrogen atoms from adamantane, norane, isoane, tricyclodecane, tetracyclododecane, etc. (it may also have substituents); a group that has removed one or more hydrogen atoms from camphor structures, etc., is preferred. The hydrocarbon group of Rd2 may also have substituents, and examples of such substituents include those that are the same as those of the hydrocarbon group (aromatic hydrocarbon group, aliphatic cyclic group, chain alkyl group) in Rd1 of the aforementioned formula (d1-1).

[0377] The following are preferred examples of the anionic portion of the (d1-2) component.

[0378]

[0379] ••In the cation part of formula (d1-2), Mm+ is an m-valent organic cation, which is the same as Mm+ in the aforementioned formula (d1-1). Component (d1-2) can be used alone or in combination of two or more.

[0380] {(d1-3) Components} •• In the anionic formula (d1-3), Rd3 can be a cyclic group with substituents, a chain alkyl group with substituents, or a chain alkenyl group with substituents. Examples include those similar to R'201 mentioned above, preferably a cyclic group containing fluorine atoms, a chain alkyl group, or a chain alkenyl group. Among these, a fluorinated alkyl group is preferred, and one similar to the fluorinated alkyl group of Rd1 mentioned above is even more preferred.

[0381] In formula (d1-3), Rd4 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, and examples are the same as those mentioned above for R'201. Among them, it is preferable that it is an alkyl, alkoxy, alkenyl, or cyclic group that may have substituents. It is preferable that the alkyl group in Rd4 is a straight-chain or branched-chain alkyl group with 1 to 5 carbon atoms, and examples include methyl, ethyl, propyl, isopropyl, n-butyl, isobutyl, tert-butyl, pentyl, isopentyl, neopentyl, etc. Part of the hydrogen atom of the alkyl group in Rd4 may also be substituted with hydroxyl, cyano, etc. It is preferable that the alkoxy group in Rd4 is an alkoxy group with 1 to 5 carbon atoms, and examples of alkoxy groups with 1 to 5 carbon atoms include methoxy, ethoxy, n-propoxy, isopropoxy, n-butoxy, tert-butoxy. Among them, methoxy and ethoxy are preferred.

[0382] Among the alkenyl groups in Rd4, those that are the same as those in R'201 mentioned above are preferably vinyl, propenyl (allyl), 1-methylpropenyl, or 2-methylpropenyl. These groups may further have an alkyl group with 1 to 5 carbon atoms or a haloalkyl group with 1 to 5 carbon atoms as a substituent.

[0383] Among the cyclic groups in Rd4, those identical to those in R'201 mentioned above are preferably alicyclic groups formed by removing one or more hydrogen atoms from cycloalkanes such as cyclopentane, cyclohexane, adamantane, noralkyl, isoalkyl, tricyclodecane, and tetracyclododecane, or aromatic groups such as phenyl or naphthyl. When Rd4 is an alicyclic group, the resist composition dissolves well in organic solvents, resulting in better lithography properties. Furthermore, when Rd4 is an aromatic group, the resist composition exhibits superior light absorption efficiency and better sensitivity or lithography properties in lithography using EUV or similar exposure sources.

[0384] 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) having substituents, and divalent linkage groups containing heteroatoms. These examples are the same as those given regarding the divalent linkage in Ya21 of formula (a2-1) above, which may also have substituents and divalent linkage groups containing heteroatoms. Yd1 is preferably a carbonyl group, an ester bond, a amide bond, an alkyl group, or a combination thereof. As an alkyl group, a straight-chain or branched-chain alkyl group is more preferred, and methylene or ethyl groups are even more preferred.

[0385] The following are preferred examples of the anionic portion of the (d1-3) components.

[0386]

[0387]

[0388] ••In the cation part of formula (d1-3), Mm+ is an m-valent organic cation, which is the same as Mm+ in the aforementioned formula (d1-1). Component (d1-3) can be used alone or in combination of two or more.

[0389] Component (D1) can be any one of components (d1-1) to (d1-3) mentioned above, or it can be used in combination with two or more. When the resist composition contains component (D1), the content of component (D1) in the resist composition is preferably 1 to 20 parts by mass relative to 100 parts by mass of component (A1), preferably 3 to 15 parts by mass, and even more preferably 5 to 10 parts by mass. If the content of component (D1) is above the lower limit of the preferred value, it is easy to obtain particularly good lithography characteristics and resist pattern shape. On the other hand, if it is below the upper limit value, sensitivity can be maintained well, and the yield is also better.

[0390] (D1) Manufacturing method: There is no particular limitation on the manufacturing method of the aforementioned components (d1-1) and (d1-2), and they can be manufactured by known methods. Furthermore, there is no particular limitation on the manufacturing method of component (d1-3), and it can be manufactured in the same manner as, for example, the method described in US2012-0149916.

[0391] • Regarding component (D2), as component (D), it may also contain nitrogen-containing organic compound components that are not equivalent to component (D1) above (hereinafter referred to as "component (D2)"). As component (D2), there are no particular limitations as long as it acts as an acid diffusion inhibitor and is not equivalent to component (D1), and it may be used freely from those known. Among them, aliphatic amines are preferred, and in particular, secondary or tertiary aliphatic amines are even more preferred. Aliphatic amines refer to amines having one or more aliphatic groups, and it is preferred that the aliphatic group has 1 to 12 carbon atoms. As aliphatic amines, examples include amines (alkylamines or alkylolamines) or cyclic amines in which at least one hydrogen atom of ammonia NH3 is substituted with 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-octanolamine, and tri-n-octanolamine. Of these, trialkylamines with 5 to 10 carbon atoms are preferred, and tri-n-pentylamine or tri-n-octylamine are particularly preferred.

[0392] Examples of cyclic amines include heterocyclic compounds containing a nitrogen atom as a heteroatom. These heterocyclic compounds can be monocyclic (aliphatic monocyclic amines) or polycyclic (aliphatic polycyclic amines). Examples of aliphatic monocyclic amines include pyridine and piperazine. Examples of aliphatic polycyclic amines include those with 6 to 10 carbon atoms, such as 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.

[0393] 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.

[0394] Furthermore, aromatic amines may also be used as (D2) component. Examples of aromatic amines include 4-dimethylaminopyridine, pyrrole, indole, pyrazole, imidazole or derivatives thereof, tribenzylamine, 2,6-diisopropylaniline, N-tert-butoxycarbonylpyrrolidine, etc.

[0395] Component (D2) can be used alone or in combination of two or more. When the inhibitor composition contains component (D2), the content of component (D2) in the inhibitor 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 inhibitor pattern shape can be improved, and the stability over time can be extended.

[0396] ≪At least one compound (E) selected from the group consisting of organic carboxylic acids and oxyacids of phosphorus and their derivatives≫ In the inhibitor composition of this embodiment, for the purpose of preventing sensitivity deterioration or improving inhibitor pattern shape, extending time stability, etc., any component may contain at least one compound (E) selected from the group consisting of organic carboxylic acids and oxyacids of phosphorus and their derivatives (hereinafter referred to as "(E) component"). As organic carboxylic acids, acetic acid, malonic acid, citric acid, malic acid, succinic acid, benzoic acid, salicylic acid, etc. are more suitable. As oxyacids of phosphorus, phosphoric acid, phosphorous acid, phosphonic acid, etc. are mentioned, among which phosphorous acid is particularly preferred. As derivatives of oxyacids of phosphorus, esters in which the hydrogen atoms of the above-mentioned oxyacids are replaced by hydrocarbon groups are mentioned, and as the aforementioned hydrocarbon groups, alkyl groups having 1 to 5 carbon atoms and aryl groups having 6 to 15 carbon atoms are mentioned. Examples of phosphoric acid derivatives include phosphate esters such as di-n-butyl phosphate and diphenyl phosphate. Examples of phosphorous acid derivatives include phosphite esters such as dimethyl phosphite, di-n-butyl phosphite, phenylphosphite, diphenyl phosphite, and dibenzyl phosphite. Examples of phosphonic acid derivatives include phosphonate esters and phenylphosphonic acid. In the inhibitor composition of this embodiment, component (E) may be used alone or in combination with two or more components. When the inhibitor composition contains component (E), the content of component (E) is generally used in the range of 0.01 to 5 parts by mass relative to 100 parts by mass of component (A1).

[0397] ≪Fluorine Additive Component (F)≫ The resist composition of this embodiment may also contain a fluorine additive component (hereinafter referred to as "(F) component") in order to impart water-repellent properties to the resist film or to improve lithography properties. As the (F) component, fluorine-containing polymeric compounds such as those 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 can be used. More specifically, polymers having constituent units (f1) represented by the following general formula (f1-1) are examples of the (F) component. The polymer is a homopolymer composed solely of the constituent unit (f1) represented by the following formula (f1-1); a copolymer of the constituent unit (f1) and the aforementioned constituent unit (a1); or preferably 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.

[0398] [In the formula, R is the same as above, Rf102 and Rf103 each independently represent a hydrogen atom, a halogen atom, an alkyl group with 1 to 5 carbon atoms or a alkyl halide with 1 to 5 carbon atoms, and Rf102 and Rf103 may also be the same or different. nf1 is an integer from 0 to 5, and Rf101 is an organic group containing a fluorine atom].

[0399] In formula (f1-1), R bonded to the carbon atom at the α-position is the same as described above. R is preferably a hydrogen atom or a methyl atom. In formula (f1-1), the halogen atom of Rf102 and Rf103 is preferably a fluorine atom. The alkyl group having 1 to 5 carbon atoms in Rf102 and Rf103 is preferably the same as the alkyl group having 1 to 5 carbon atoms as described above, and is preferably methyl or ethyl. Specifically, the alkyl halide having 1 to 5 carbon atoms in Rf102 and Rf103 is preferably a group in which one or all of the hydrogen atoms of the alkyl group having 1 to 5 carbon atoms are substituted with halogen atoms. The halogen atom is preferably a fluorine atom. Among these, Rf102 and Rf103 are preferably hydrogen atoms, fluorine atoms, or alkyl groups having 1 to 5 carbon atoms, and are preferably hydrogen atoms, fluorine atoms, methyl, or ethyl. In formula (f1-1), nf1 is an integer from 0 to 5, preferably an integer from 0 to 3, and even better if it is 1 or 2.

[0400] In formula (f1-1), Rf101 is an organic group containing fluorine atoms, preferably a hydrocarbon group containing fluorine atoms. The hydrocarbon group containing fluorine atoms can be linear, branched, or cyclic, preferably with 1 to 20 carbon atoms, even more preferably with 1 to 15 carbon atoms, and particularly preferably with 1 to 10 carbon atoms. Furthermore, it is preferable that at least 25% of the hydrogen atoms in the hydrocarbon group containing fluorine atoms are fluorinated, even more preferably with at least 50%, and particularly preferably with at least 60% fluorination to improve the hydrophobicity of the resist film during immersion exposure. Among them, as Rf101, it is more preferred to be a fluorinated hydrocarbon group with 1 to 6 carbon atoms, and it is particularly preferred to be trifluoromethyl, -CH2-CF3, -CH2-CF2-CF3, -CH(CF3)2, -CH2-CH2-CF3, or -CH2-CH2-CF2-CF2-CF2-CF3.

[0401] (F) The weight average molecular weight (Mw) of the component (based on polystyrene obtained by gel permeation chromatography) is preferably 1,000 to 50,000, more preferably 5,000 to 40,000, and best of all is 10,000 to 30,000. If it is below the upper limit of this range, it has sufficient solubility in the solvent for the resist agent when used as a resist agent. If it is above the lower limit of this range, the water repellency of the resist agent film is better. The dispersibility (Mw / Mn) of the component (F) is preferably 1.0 to 5.0, more preferably 1.0 to 3.0, and best of all is 1.0 to 2.5.

[0402] In the inhibitor composition of this embodiment, component (F) may be used alone or in combination with two or more components. When the inhibitor composition contains component (F), the content of component (F) is usually used in a ratio of 0.5 to 10 parts by mass relative to 100 parts by mass of component (A1).

[0403] ≪Organic Solvent Component (S)≫ The inhibitor composition of this embodiment can be manufactured by dissolving the inhibitor material in an organic solvent component (hereinafter referred to as "(S) component"). As the (S) component, it can be any solvent that can dissolve the components used and form a homogeneous solution, and can be appropriately selected from those known as solvents for chemically amplified inhibitor compositions. As (S) components, examples include lactones such as γ-butyrolactone; ketones such as acetone, methyl ethyl ketone, cyclohexanone, methyl-n-pentyl ketone, methyl isopentyl ketone, and 2-heptanone; polyols such as ethylene glycol, diethylene glycol, propylene glycol, and dipropylene glycol; compounds with ester bonds such as ethylene glycol monoacetate, diethylene glycol monoacetate, propylene glycol monoacetate, or dipropylene glycol monoacetate; polyol derivatives such as monomethyl ether, monoethyl ether, monopropyl ether, monobutyl ether, monoalkyl ether, or monophenyl ether of the aforementioned polyols or compounds with the aforementioned ester bonds [among these]. [Preferably propylene glycol monomethyl ether acetate (PGMEA) and propylene glycol monomethyl ether (PGME); cyclic ethers such as dioxane, or 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 anisole, ethyl benzyl ether, cresol methyl ether, diphenyl ether, dibenzyl ether, phenethyl ether, butyl phenyl ether, ethylbenzene, diethylbenzene, pentylbenzene, isopropylbenzene, toluene, xylene, isopropyltoluene, mesitylene, etc., and dimethyl sulfoxide (DMSO). In the inhibitor 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.

[0404] Furthermore, as component (S), a mixed solvent of PGMEA and a polar solvent is preferred. The mixing ratio (mass ratio) can be appropriately determined by considering the compatibility of PGMEA and the polar solvent, and is preferably 1:9 to 9:1, and even 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, and even more preferably 2:8 to 8:2. Furthermore, when PGME is mixed as a polar solvent, the mass ratio of PGMEA:PGME is preferably 1:9 to 9:1, even more preferably 2:8 to 8:2, and even more preferably 3:7 to 7:3. Moreover, a mixed solvent of PGMEA and PGME with cyclohexanone is preferred. Furthermore, as component (S), a mixed solvent selected from at least one of 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 by mass. The amount of component (S) used is not particularly limited, but should be appropriately set according to the concentration required for coating on the substrate and the thickness of the coating film. Generally, component (S) is used in a range of 0.1 to 20% by mass, preferably 0.2 to 15% by mass, of the solid content of the resist composition.

[0405] The inhibitor composition of this embodiment may further contain, as desired, appropriate additives with miscibility, such as addition-type resins, dissolution inhibitors, plasticizers, stabilizers, colorants, halos-inhibiting agents, dyes, etc., used to improve the performance of the inhibitor film.

[0406] The inhibitor composition of this embodiment can also be used to remove impurities after the inhibitor material is dissolved in component (S). For example, filters made of polyimide porous membranes, filters made of polyimide porous membranes, and filters made of polyimide porous membranes can also be used to filter the inhibitor composition. Examples of the aforementioned polyimide porous membranes and polyimide porous membranes include those described in Japanese Patent Application Publication No. 2016-155121.

[0407] The resist composition of this embodiment described above contains a resin component (A1), which has the aforementioned constituent unit (a01). The constituent unit (a01) has an acid-dissociating group represented by "-(CtXt)-C≡C-Ra01" in formula (a0-1). In this acid-dissociating group, a triple bond is present at the α-position of the tertiary carbon atom (Ct), and Ra01 (a straight-chain, branched-chain, or cyclic aliphatic hydrocarbon group) is present at the end of the triple bond. Therefore, this acid-dissociating group is easily deprotected by acid. On the other hand, conventional acid-dissociating groups, when the end is a hydrogen atom, are more difficult to deprotect by acid and tend to degrade the imaging properties. In addition, the constituent unit (a01) has a monocyclic or polycyclic aliphatic hydrocarbon group, thus allowing for appropriate adjustment of the diffusion control of acid and the solubility of the developing solution. The above are all resist components of this embodiment that can improve any one of sensitivity, CDU, and resolution.

[0408] (Resistant Pattern Forming Method) The resistant pattern forming method related to the second aspect of the present invention includes the steps of forming a resist film by using the resistant composition related to the first aspect of the present invention on a support, exposing the resist film, and developing the exposed resist film to form a resistant pattern. As one embodiment of the related resistant pattern forming method, there is an example of a resistant pattern forming method performed as follows.

[0409] First, the resist composition of the above embodiment is coated onto a support using a spinner or the like. A baking (post-exposure baking (PAB)) process is applied at a temperature of, for example, 80-150°C for 40-120 seconds, preferably 60-90 seconds, to form a resist film. Next, the resist film is subjected to selective exposure using an exposure apparatus such as an electron beam lithography apparatus or an EUV exposure apparatus. This exposure is either through a photomask (photomask pattern) with a specific pattern formed on it, or through direct irradiation of electron lines without the photomask pattern. Then, a baking (post-exposure baking (PEB)) process is applied at a temperature of, for example, 80-150°C for 40-120 seconds, preferably 60-90 seconds. Finally, the resist film is developed. When the developing process is an alkaline developing process, an alkaline developing solution is used; when the developing process is a solvent developing process, a developing solution containing organic solvents (organic developing solution) is used.

[0410] After development, it is preferable to perform a cleaning process. For alkaline development processes, it is preferable to use pure water for cleaning; for solvent development processes, it is preferable to use a cleaning solution containing an organic solvent. In solvent development processes, after the aforementioned development or cleaning process, a process can also be performed to remove the developer or cleaning solution adhering to the pattern using a supercritical fluid. After development or cleaning, drying is performed. Furthermore, depending on the circumstances, a baking process (post-baking) can also be performed after the aforementioned development process. In this way, a resist pattern can be formed.

[0411] There are no particular limitations on the support body; conventionally known materials can be used, such as substrates for electronic components, or substrates with specific wiring patterns formed thereon. More specifically, examples include metal substrates made of silicon wafers, copper, chromium, iron, aluminum, etc., or glass substrates. Materials for the wiring patterns can include, for example, copper, aluminum, nickel, gold, etc. Furthermore, the support body can also be an inorganic and / or organic film formed on the aforementioned substrate. Examples of inorganic films include inorganic anti-reflective films (inorganic BARC). Examples of organic films include organic anti-reflective films (organic BARC), or organic films such as the lower organic film in a multilayer resist method. Here, the multilayer resist method refers to a method in which at least one organic film (lower organic film) and at least one resist film (upper resist film) are deposited on a substrate, and the resist pattern formed on the upper resist film is used as a photomask to pattern the lower organic film, thereby forming a high aspect ratio pattern. In other words, by means of the multilayer resist method, since the required thickness can be ensured by the lower organic film, the resist film can be thinned, and a high aspect ratio fine pattern can be formed. The multilayer resist method is basically divided into a two-layer structure method (2-layer resist method) with an upper resist film and a lower organic film, and a three-layer or more multilayer structure method (3-layer resist method) with one or more intermediate layers (such as metal thin films) between the upper resist film and the lower organic film.

[0412] There is no particular limitation on the wavelength used for exposure; radiation such as ArF excimer laser, KrF excimer laser, F2 excimer laser, EUV (extreme ultraviolet), VUV (vacuum ultraviolet), EB (electron beam), X-ray, and soft X-ray can be used. The aforementioned resist composition is more useful for use with KrF excimer laser, ArF excimer laser, EB, or EUV, and even more useful for use with ArF excimer laser, EB, or EUV. That is, the resist pattern forming method of this embodiment is a method that is particularly useful when the step of exposing the resist film includes exposure of the aforementioned resist film with ArF excimer laser, EUV (extreme ultraviolet), or EB (electron beam).

[0413] The exposure method for the resist film can be either general exposure (dry exposure) in an inert gas such as air or nitrogen, or liquid immersion lithography. Liquid immersion lithography involves pre-filling the space between the resist film and the lens at the lowest position of the exposure apparatus with a solvent (liquid immersion solvent) having a refractive index greater than that of air, and then exposing the film in this state (immersion exposure). As for the liquid immersion solvent, it is preferable to use a solvent with a refractive index greater than that of air and less than that of the exposed resist film. The refractive index of the relevant solvent is not particularly limited as long as it is within the aforementioned range. Examples of solvents with a refractive index greater than that of air and less than that of the aforementioned resist film include water, fluorinated inert liquids, silica-oxygen solvents, and hydrocarbon solvents. Specific examples of fluorinated inert liquids include liquids with fluorinated compounds such as C3HCl2F5, C4F9OCH3, C4F9OC2H5, and C5H3F7 as the main component, with a boiling point of 70-180°C being preferred, and 80-160°C being even more preferred. If the fluorinated inert liquid has a boiling point within the above range, it is preferable to remove the solvent used for immersion using a simple method after exposure. As for fluorinated inert liquids, perfluoroalkyl compounds in which all hydrogen atoms of the alkyl group are replaced by fluorine atoms are particularly preferred. Specifically, perfluoroalkyl ether compounds and perfluoroalkylamine compounds can be cited as examples of perfluoroalkyl ether compounds. Furthermore, specifically, perfluoro(2-butyltetrahydrofuran) (boiling point 102°C) can be cited as an example of a perfluoroalkyl ether compound, and perfluorotributylamine (boiling point 174°C) can be cited as an example of a perfluoroalkylamine compound. Water is the preferred choice as a liquid immersion solvent, considering factors such as cost, safety, environmental impact, and versatility.

[0414] Examples of alkaline developing solutions used in alkaline developing processes include 0.1-10% by mass tetramethylammonium hydroxyl (TMAH) aqueous solutions. For organic developing solutions used in solvent developing processes, the organic solvent contained in the developing solution can be any solvent capable of dissolving component (A) (component (A) before exposure), and can be appropriately selected from known organic solvents. Specifically, examples include polar solvents such as ketone solvents, ester solvents, alcohol solvents, nitrile solvents, amide solvents, and ether solvents, as well as hydrocarbon solvents. 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. Acrylamine solvents are organic solvents whose structure contains an acetamine group. Ether solvents are organic solvents whose structure contains COC. There are also organic solvents whose structure contains multiple functional groups characteristic of the solvents described above; however, in this case, it is equivalent to any solvent containing any of the functional groups possessed by that organic solvent. For example, diethylene glycol monomethyl ether is equivalent to either an alcohol solvent or an ether solvent in the above classification. Hydrocarbon solvents are hydrocarbon solvents formed from hydrocarbons that can also be halogenated, and which do not have substituents other than halogen atoms. Fluorine atoms are preferred as halogen atoms. Among the organic solvents contained in organic developing solutions, polar solvents are preferred, such as ketone solvents, ester solvents, and nitrile solvents.

[0415] Examples of ketone solvents include 1-octanone, 2-octanone, 1-nonanone, 2-nonanone, acetone, 4-heptanone, 1-hexanone, 2-hexanone, diisobutyl ketone, cyclohexanone, methylcyclohexanone, phenylacetone, methyl ethyl ketone, methyl isobutyl ketone, acetoacetone, acetone-based acetone, ionone, diacetone alcohol, acetoethanol, acetophenone, methyl naphthyl ketone, isophorone, propyl carbonate, γ-butyrolactone, and methylpentanone (2-heptanone). Among these, methylpentanone (2-heptanone) is preferred as a ketone solvent.

[0416] Examples of ester 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-methoxybutyl acetate, 4-methoxybutyl acetate 2-Propoxybutylacetic acid, 2-Methoxypentylacetic acid, 3-Methoxypentylacetic acid, 4-Methoxypentylacetic acid, 2-Methyl-3-Methoxypentylacetic acid, 3-Methyl-3-Methoxypentylacetic acid, 3-Methyl-4-Methoxypentylacetic acid, 4-Methyl-4-Methoxypentylacetic acid, propylene glycol diacetate, methyl formate, ethyl formate, butyl formate, propyl formate, ethyl lactate, butyl lactate Propyl lactate, ethyl carbonate, propyl carbonate, butyl carbonate, methyl pyruvate, ethyl pyruvate, propyl pyruvate, butyl pyruvate, methyl acetoacetate, ethyl acetoacetate, 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.

[0417] As nitrile solvents, examples include acetonitrile, propionitrile, valerate, and butyronitrile.

[0418] Known additives may be added to organic developing solutions as necessary. Examples of such additives include surfactants. There are no particular limitations on the surfactant, but ionic or nonionic fluorinated and / or silicate surfactants may be used. Nonionic surfactants are preferred, especially nonionic fluorinated surfactants or nonionic silicate surfactants. When a surfactant is added, its amount relative to the total amount of the organic developing solution is typically 0.001 to 5% by mass, preferably 0.005 to 2% by mass, and even more preferably 0.01 to 0.5% by mass.

[0419] Imaging processing can be carried out by known imaging methods, such as immersing the support in the developing solution for a certain time (immersion method), raising the developing solution on the surface of the support by surface tension for a certain time and then letting it stand still (stirring method), spraying the developing solution onto the surface of the support (spraying method), and continuously applying the developing solution while scanning the developing solution coating nozzle at a certain speed on a support that is rotating at a certain speed (dynamic implementation method), etc.

[0420] The organic solvent contained in the cleaning solution used for cleaning after development in the solvent-based developing process, for example, is selected from the organic solvents mentioned above that are used as organic solvents in the aforementioned organic developing solutions, and is suitable for dissolving inhibitor patterns. Generally, a solvent selected from at least one of hydrocarbon solvents, ketone solvents, ester solvents, alcohol solvents, amide solvents, and ether solvents is used. Among these, it is preferable to select at least one of hydrocarbon solvents, ketone solvents, ester solvents, alcohol solvents, and amide solvents; it is even more preferable to select at least one of alcohol solvents and ester solvents; and it is particularly preferable to use an alcohol solvent. The alcohol solvent used in the cleaning solution is preferably a monohydric alcohol having 6 to 8 carbon atoms, and the monohydric alcohol may also 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, with 1-hexanol and 2-hexanol being even more preferred. Any one of these organic solvents can be used alone or in combination with two or more. Furthermore, it can be used in combination with other organic solvents or water. However, considering the imaging characteristics, the amount of water added to the cleaning solution relative to the total amount of the cleaning solution is preferably 30% by mass or less, even more preferably 10% by mass or less, even better preferably 5% by mass or less, and particularly preferably 3% by mass or less. Known additives can be added to the cleaning solution as needed. Examples of such additives include surfactants. The surfactants mentioned above are preferably nonionic, especially nonionic fluorinated surfactants or nonionic silicate surfactants. When blending surfactants, the amount blended relative to the total amount of the cleaning solution is usually 0.001 to 5% by mass, preferably 0.005 to 2% by mass, and preferably 0.01 to 0.5% by mass.

[0421] The cleaning process using a cleaning solution (washing process) can be carried out by known cleaning methods. Examples of such cleaning processes include a method of continuously applying cleaning solution to a support rotating at a certain speed (spin coating method), a method of immersing the support in the cleaning solution for a certain time (immersion method), and a method of spraying cleaning solution onto the surface of the support (spraying method).

[0422] By using the resist pattern forming method of this embodiment described above, since the resist composition of the above embodiment is used, it is possible to form a resist pattern that aims for high sensitivity and has good CDU and resolution. [Example]

[0423] Hereinafter, the present invention will be described in further detail by way of examples, but the present invention is not limited to these examples.

[0424] <Synthesis Example of Compound> [Synthesis Example of Compound (m-a0-1)] 24 g of cyclobutanone was added dropwise to 688 ml of 1-propynyl magnesium bromide (THF solution, 0.5 mol / L) at -20°C and stirred for 1 hour. Then, 17.9 g of methacrylic acid chloride was dissolved in 36.0 g of THF, followed by extraction with 300 g of heptane. The solvent of the organic layer was distilled off, and the mixture was further purified by distillation to obtain compound (m-a0-1).

[0425]

[0426] The obtained compound (m-a0-1) was subjected to NMR (CDCl3) determination, and its structure was identified by the following results: δ (ppm) = 6.02-6.05 (s, C=CH, 1H), 5.51-5.48 (m, C=CH, 1H), 2.05-2.08 (m, CH2, 2H), 1.91-1.94 (s, CH3, 3H), 1.88-1.90 (m, CH2, 2H), 1.82-1.85 (s, CH3, 3H), 1.72-1.75 (m, CH2, 2H)

[0427] [Synthesis Example of Compound (m-a0-2)] 29 g of cyclopentanone was added dropwise to 688 mL of 1-propynyl magnesium bromide (THF solution, 0.5 mol / L) at -20°C and stirred for 1 hour. Then, a solution of 17.9 g of methacrylic acid chloride dissolved in 36.0 g of THF was added dropwise. After stirring for another hour in an ice bath, 300 g of pure water was added dropwise to the reaction mixture, followed by extraction with 300 g of heptane. The solvent of the organic layer was distilled off, and the mixture was then purified by distillation to obtain compound (m-a0-2).

[0428]

[0429] The obtained compound (m-a0-2) was subjected to NMR (CDCl3) determination, and its structure was identified by the following results: δ (ppm) = 6.00-6.03 (s, C=CH, 1H), 5.50-5.45 (m, C=CH, 1H), 2.18-2.22 (s, CH2, 2H), 1.91-1.94 (s, CH3, 3H), 1.82-1.85 (s, CH3, 3H), 1.60-1.80 (m, CH2, 6H)

[0430] [Synthesis Example of Compound (m-a0-3)] 10 g of isopropylacetylene was dissolved in 40 g of THF, cooled to -78 °C, and 70 mL of n-BuLi (hexane solution, 2.4 mol / L) was added dropwise. The temperature was raised to -20 °C and stirred for 1 hour. Then, 12.8 g of cyclopentanone was added dropwise and stirred for 5 hours. Then, a solution of 19.2 g of methacrylic acid chloride dissolved in 38.0 g of THF was added dropwise. After stirring in an ice bath for 1 hour, 300 g of pure water was added dropwise to the reaction solution, followed by extraction with 300 g of heptane. The solvent of the organic layer was distilled off, and the solution was purified by distillation to obtain compound (m-a0-3).

[0431]

[0432] The obtained compound (m-a0-3) was subjected to NMR (CDCl3) determination, and its structure was identified by the following results: δ (ppm) = 6.00-6.03 (s, C=CH, 1H), 5.50-5.45 (m, C=CH, 1H), 2.50-2.54 (m, CH, 1H), 2.18-2.22 (s, CH2, 2H), 1.91-1.94 (s, CH3, 3H), 1.60-1.80 (m, CH2, 6H), 1.32-1.26 (d, CH3, 6H)

[0433] [Synthesis example of compound (m-a0-4)] Except for replacing isopropyl acetylene with 10g of cyclopropyl acetylene, compound (m-a0-4) was obtained by the same method as that used in the synthesis example of compound (m-a0-3).

[0434]

[0435] The obtained compound (m-a0-4) was subjected to NMR (CDCl3) determination, and its structure was identified by the following results: δ (ppm) = 6.00-6.03 (s, C=CH, 1H), 5.50-5.45 (m, C=CH, 1H), 2.50-2.54 (m, CH, 1H), 2.18-2.22 (s, CH2, 2H), 1.91-1.94 (s, CH3, 3H), 1.60-1.80 (m, CH2, 6H), 1.22-1.24 (m, CH2, 2H), 0.65-0.69 (m, CH2, 2H), 0.73-0.76 (m, CH2, 2H)

[0436] [Synthesis example of compound (m-a0-5)] Except for replacing cyclobutanone with 34g of cyclohexanone, compound (m-a0-5) was obtained by the same method as that used in the synthesis example of compound (m-a0-1).

[0437]

[0438] The obtained compound (m-a0-5) was subjected to NMR (CDCl3) determination, and its structure was identified by the following results: δ (ppm) = 6.00-6.03 (s, C=CH, 1H), 5.50-5.45 (m, C=CH, 1H), 2.13-2.16 (s, CH2, 2H), 1.91-1.94 (s, CH3, 3H), 1.82-1.85 (s, CH3, 3H), 1.10-1.50 (m, CH2, 8H)

[0439] [Synthesis example of compound (m-a0-6)] Except that cyclobutanone was replaced with 34.5g of 4-oxytetrahydropiperanone, compound (m-a0-6) was obtained by the same method as that used in the synthesis example of compound (m-a0-1).

[0440]

[0441] The obtained compound (m-a0-6) was subjected to NMR (CDCl3) determination, and its structure was identified by the following results: δ (ppm) = 6.00-6.03 (s, C=CH, 1H), 5.50-5.45 (m, C=CH, 1H), 3.65-3.75 (t, CH2O, 4H), 2.18-2.20 (m, CH2, 2H), 1.91-1.94 (s, CH3, 3H), 1.82-1.85 (s, CH3, 3H), 1.73-1.76 (m, CH2, 2H)

[0442] <Synthesis Example 1 of Polymer Compound> [Synthesis Example of Polymer Compound (A-1)] A dropwise solution was prepared by dissolving 18.9 g of monomer (m-a0-1), 10.0 g of monomer (m-a10-1pre), and 3.86 g of dimethyl azobis(isobutyrate) (V-601) as a polymerization initiator in 43.6 g of MEK (methyl ethyl ketone). 11.6 g of MEK was added to a three-necked flask connected to a thermometer, a return flow tube, and a nitrogen inlet tube. The flask was heated to 85°C under nitrogen, and the aforementioned dropwise solution was added dropwise over 4 hours. After the dropwise addition was complete, the reaction mixture was stirred at 85°C for 1 hour. The reaction mixture was then cooled to room temperature. Next, 12.2 g of acetic acid and 175 g of methanol were added to the resulting polymerization solution, and a deprotection reaction was carried out at 30°C for 8 hours. After the reaction was complete, the resulting reaction mixture was precipitated in 2600 g of heptane and washed. The resulting white solid was filtered and dried under reduced pressure overnight to obtain the target polymer compound (A-1).

[0443]

[0444] Regarding the obtained polymer compound (A-1), the weight-average molecular weight (Mw) of standard polystyrene, determined by GPC, is 5700, and the molecular weight dispersion (Mw / Mn) is 1.72. The copolymer composition ratio (the ratio of constituent units derived from each monomer (molar ratio)) determined by 13C-NMR is 1 / m = 50 / 50.

[0445] <Synthesis Examples 2-25 of Polymer Compounds> Using the same method as in Synthesis Example 1 of Polymer Compounds, the compounds (m-a0-1) to (m-a0-6) shown above, and the compounds (m-a10-1pre), (m-a10-2pre), (m-a10-3pre), (m-a1-1) to (m-a1-3), (m-a8), (m-a2) and (m-a3) shown below, polymer compounds (A-2) to (A-25) with the composition ratios shown in Table 1 were synthesized. Regarding the obtained polymer compounds, the copolymerization composition ratio (the proportion of constituent units derived from each monomer (molar ratio)) of the polymer compounds was determined by 13C-NMR, and the weight average molecular weight (Mw) and molecular weight dispersion (Mw / Mn) converted from standard polystyrene were determined by GPC and recorded in Table 1.

[0446]

[0447]

[0448]

[0449]

[0450]

[0451]

[0452] Furthermore, the constituent units constituting the above copolymer and each represented by the following chemical formulas (a10-1-1), (a10-1-2) and (a10-1-3) are constituent units derived from the monomers represented by the above chemical formulas (m-a10-1pre), (m-a10-2pre) and (m-a10-3pre).

[0453]

[0454]

[0455] <Preparation of inhibitor composition> (Examples 1-21, Comparative Examples 1-10) Mix and dissolve the components shown in Tables 2 and 3 to prepare the inhibitor composition for each example.

[0456]

[0457]

[0458] (A)-1~(A)-25: The above-mentioned polymeric compounds (A-1)~(A-25). (B)-1~(B)-3: Acid generating agents containing compounds represented by the following chemical formulas (B-1)~(B-3). (D)-1: Acid diffusion inhibitors containing compounds represented by the following chemical formula (D-1). (S)-1: A mixed solvent of propylene glycol monomethyl ether acetate / propylene glycol monomethyl ether = 60 / 40 (mass ratio).

[0459]

[0460] <Formation of Resistant Pattern> On an 8-inch silicate substrate treated with hexamethyldisilazane (HMDS), each resist composition was coated using a spinner. A pre-baking (PAB) process was performed on a hot plate at 110°C for 60 seconds to form a resist film with a thickness of 50 nm. Next, the resist film was subjected to electron beam lithography using a JEOL-JBX-9300FS (manufactured by Nippon Electron Ltd.) at an accelerating voltage of 100 kV to create a contact hole pattern (hereinafter referred to as "CH pattern") with 32 nm diameter holes spaced at equal intervals (64 nm spacing). Afterward, a post-exposure heating (PEB) process was performed at 110°C for 60 seconds. Next, alkaline development was performed for 60 seconds at 23°C using a 2.38% by mass tetramethylammonium hydroxyl (TMAH) aqueous solution "NMD-3" (trade name, manufactured by Tokyo Ohka Kogyo Co., Ltd.). Afterwards, a 15-second water rinse was performed using pure water. As a result, in all examples, a CH pattern with 32 nm diameter holes arranged at equal intervals (64 nm spacing) was formed. Furthermore, regarding the resist compositions of Comparative Examples 3, 4, 9, and 10, poor resolution occurred, and the target CH pattern with 32 nm diameter holes arranged at equal intervals (64 nm spacing) could not be formed.

[0461] [Evaluation of Optimal Exposure (Eop)] Based on the above <Formation of Resistant Pattern>, the optimal exposure Eop (μC / cm2) for forming the CH pattern of the target size is determined. This is represented as "Eop (μC / cm2)" in Tables 4 and 5.

[0462] [Evaluation of In-Plane Uniformity (CDU) of Pattern Size] Regarding the CH pattern formed by the aforementioned <Formation of Resistant Pattern>, the CH pattern was observed from above using a length-measuring SEM (scanning electron microscope, accelerating voltage 300V, trade name: S-9380, manufactured by Hitachi High-Techs Co., Ltd.), and the pore diameter (nm) of 40 pores in the CH pattern was measured. The standard deviation (σ) calculated from the measurement results was calculated as 3 times the value (3σ). This is taken as "CDU (nm)" and is shown in Table 3. The smaller the 3σ value, the higher the uniformity of pore size (CD) formed in the resistant film.

[0463] [Evaluation of Limiting Resolution] Using the above-described <Formation of Resistant Pattern>, the exposure was gradually reduced slightly from the optimal exposure Eop (μC / cm2) for forming the CH pattern of the target size. The aperture diameter (nm) of the resolution pattern was determined using a scanning electron microscope S-9380 (manufactured by Hitachi High-Techs). This is taken as the "Limiting Resolution (nm)" and is shown in Tables 4 and 5.

[0464]

[0465]

[0466] As shown in Tables 4 and 5, the resist composition of the Examples, compared with the resist composition of the Comparative Examples, was found to be able to form a resist pattern that is intended to achieve high sensitivity and has good CDU and resolution.

[0467] The inhibitor compositions of Comparative Examples 1 to 10, which contain polymeric compounds (A-4), (A-5), (A-9), (A-10), (A-13), (A-16), (A-19), (A-20), (A-23), and (A-25) having constituent units derived from any one of compounds (m-a1-1) to (m-a1-3), exhibit lower sensitivity compared to the inhibitor compositions of the Examples. This is presumably because in compounds (m-a1-1) to (m-a1-3), the C≡C terminus is a hydrogen atom, thus the acid reactivity of any constituent unit derived from each of compounds (m-a1-1) to (m-a1-3) is lower.

Claims

1. A resist 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 an acid-generating agent component (B) that generates acid upon exposure, wherein the resin component (A1) has a constituent unit (a01) derived from a compound represented by the following general formula (a0-1), and the acid-generating agent component (B) comprises a compound represented by the following general formula (b-1), a compound represented by the following general formula (b-2), or a compound represented by the following general formula (b-3), wherein the content of the acid-generating agent component (B) is 20 to 50 parts by mass relative to 100 parts by mass of the resin component (A1), [wherein, W01 is a polymerizable group, Ct is a tertiary carbon atom, Xt is a group with C...]. The groups t together form a monocyclic or polycyclic hydrocarbon group. Part or all of the hydrogen atoms in this monocyclic or polycyclic hydrocarbon group may be substituted, and part of the carbon atoms constituting the substituted ring may be substituted by heteroatoms. Ra 01 is a straight-chain, branched-chain, or cyclic aliphatic hydrocarbon group. [In the formula, R 101 and R 104~R 108 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. R 104 and R 105 can also bond together to form a ring structure. R 102 is a fluorinated alkyl group or a fluorine atom with 1~5 carbon atoms. Y 101 is a divalent linker group or a single bond containing an oxygen atom. V 101~V 103 are each independently a single bond, an alkyl group, or a fluorinated alkyl group. L 101~L 102 are each independently a single bond or an oxygen atom. L 103~L 105 are each independently a single bond, -CO- or -SO 2-, M m+ represents an organic cation with a valence of m, where m is an integer greater than or equal to 1).

2. The inhibitor composition as claimed in claim 1, wherein, The aforementioned acid-generating agent component (B) comprises a compound represented by the following general formula (b-1-0), [wherein, R 101 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, Yb 0 is a divalent linker containing an oxygen atom, V 101 is a single bond, an alkyl group or a fluorinated alkyl group, R 102 is a fluorinated alkyl group or a fluorine atom with 1 to 5 carbon atoms, M m+ represents an m-valent organic cation, where m is an integer greater than or equal to 1].

3. The inhibitor composition as claimed in claim 1, wherein, The aforementioned acid-generating agent component (B) comprises a compound represented by the following general formula (b-1-1), [wherein, R 101 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; Yb 0 is a divalent linker containing an oxygen atom; V 101 is a single bond, an alkyl group, or a fluorinated alkyl group; R 102 is a fluorinated alkyl group or a fluorine atom with 1 to 5 carbon atoms; R b1 is an aryl group with a fluorine atom, or an aryl group with a fluorinated alkyl group; R b2 and R b3 are each independently an aryl group that may have substituents, or they are bonded together with the sulfur atom in the formula to form a ring].

4. The inhibitor composition as claimed in claim 1, wherein, The aforementioned constituent unit (a01) is a constituent unit represented by the following general formula (a01-1), [where R 01 is a hydrogen atom, an alkyl group with 1 to 5 carbon atoms, or a haloalkyl group with 1 to 5 carbon atoms, Va 01 is a divalent linker, na 01 is an integer from 0 to 2, C t is a tertiary carbon atom, Xa t is a group that forms a monocyclic aliphatic hydrocarbon group together with C t, and some or all of the hydrogen atoms in this monocyclic aliphatic hydrocarbon group may also be substituted by substituents, and some of the carbon atoms constituting the ring may also be substituted by heteroatoms, Ra 01 is a straight-chain, branched-chain, or cyclic aliphatic hydrocarbon group].

5. The inhibitor composition as claimed in claim 1, wherein, The aforementioned constituent unit (a01) is a constituent unit represented by any of the following chemical formulas (a01-1a-1) to (a01-1a-27), [where Rα represents a hydrogen atom, methyl group, or trifluoromethyl group].

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