Inhibitor composition, inhibitor pattern formation method, compound, acid generating agent, acid diffusion control agent, and polymer compound

Abstract

An inhibitor composition is a resist composition that generates acid upon exposure and whose solubility in a developer changes due to the action of the acid, and contains a compound comprising a cation (CO) of the general formula (CO). X01 is an electron-withdrawing group, X02 is an electron-withdrawing group different from X01, and R01 is an electron-donating group. R02 and R03 are each independently substituents. nx1 and nx2 are each independently integers from 1 to 4, n1 is an integer from 0 to 3, and nx1 + nx2 + n1 ≤ 5. n2 and n3 are each independently integers from 0 to 4.

Description

[Technical Field]

[0001] This invention relates to inhibitor compositions, inhibitor pattern forming methods, compounds, acid generating agents, acid diffusion control agents, and polymeric compounds. This application is based on priority to Japanese Patent Application No. 2021-138091, filed on August 26, 2021, the contents of which are incorporated herein by reference. [Previous Technology]

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

[0003] Resistant materials are required to have photolithography properties such as sensitivity to exposure light sources and resolution in reproducing fine-sized patterns. Conventionally, chemically amplified resist compositions have been used to meet these requirements. These compositions 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 upon exposure.

[0004] In chemically amplified resist compositions, resins with multiple constituent units are generally used to improve lithography properties. Furthermore, in the formation of resist patterns, the behavior of acids generated from the acid-generating agent components due to exposure is considered a factor that significantly affects lithography properties. Various types of acid-generating agents have been proposed for use in chemically amplified resist compositions. Examples include, for instance, onium salt-based acid-generating agents such as monazite or strontium salts, oxime sulfonate ester-based acid-generating agents, diazomethane-based acid-generating agents, nitrobenzyl sulfonate-based acid-generating agents, imino sulfonate-based acid-generating agents, and disulfonate-based acid-generating agents.

[0005] For example, Patent Document 1 discloses an inhibitor composition that uses a compound that introduces an electron-withdrawing group to a strontium cation as an acid generator. [Prior Art Documents] [Patent Documents]

[0006] [Patent Document 1] Japanese Patent Application Publication No. 2019-207404 [Summary of the Invention]

[0007] [The problem the invention aims to solve]

[0008] In the pursuit of miniaturization of resist patterns, for example, using EUV or EB lithography, the goal is to form micro-patterns of tens of nanometers. Along with this miniaturization of resist patterns, improving sensitivity and reducing defects become key issues.

[0009] This invention was made in view of the above circumstances, and its objective is to provide a resist composition with high sensitivity and good photolithographic properties such as those for defects, a resist pattern forming method using the aforementioned resist composition, and the compounds, acid generating agents, acid diffusion control agents, and polymeric compounds used in the aforementioned resist composition. [Means for solving the problem]

[0010] In order to solve the above-mentioned problems, the present invention adopts the following structure. That is, the first state sample of the present invention is a resist composition, which is a resist composition that generates acid due to exposure and changes the solubility of the developer due to the action of the acid, wherein it contains: a compound comprising a cation (CO) represented by the following general formula (CO).

[0011] [In the formula, X01 is an electron-withdrawing group, X02 is an electron-withdrawing group different from X01, and R01 is an electron-donating group. R02 and R03 are each independent substituents. nx1 and nx2 are each independent integers from 1 to 4, n1 is an integer from 0 to 3, and nx1 + nx2 + n1 ≦ 5. n2 and n3 are each independent integers from 0 to 4. When nx1 is 2 or more, the complex X01 groups can be the same or different. When nx2 is 2 or more, the complex X02 groups can be the same or different. When n1 is 2 or more, the complex R01 groups can be the same or different. When n2 is 2 or more, the complex R02 groups can be the same or different. When n3 is 2 or more, the complex R03 groups can be the same or different.] ]

[0012] The second state of the present invention is a method for forming a resist pattern, which includes the steps of forming a resist film by using the resist composition of the first state on a support, exposing the resist film, and developing the exposed resist film to form a resist pattern.

[0013] The third state of the present invention is a compound represented by the following general formula (M0).

[0014] [In the formula, X01 is an electron-withdrawing group, X02 is an electron-withdrawing group different from X01, and R01 is an electron-donating group. R02 and R03 are each independent substituents. nx1 and nx2 are each independent integers from 1 to 4, n1 is an integer from 0 to 3, and nx1 + nx2 + n1 ≦ 5. n2 and n3 are each independent integers from 0 to 4. When nx1 is 2 or more, the complex X01 groups can be the same or different. When nx2 is 2 or more, the complex X02 groups can be the same or different. When n1 is 2 or more, the complex R01 groups can be the same or different. When n2 is 2 or more, the complex R02 groups can be the same or different. When n3 is 2 or more, the complex R03 groups can be the same or different.] ]

[0015] The third embodiment of the present invention is an acid generating agent comprising a compound represented by the following general formula (B0).

[0016] [In the formula, X01 is an electron-withdrawing group, X02 is an electron-withdrawing group different from X01, and R01 is an electron-donating group. R02 and R03 are each independent substituents. nx1 and nx2 are each independent integers from 1 to 4, n1 is an integer from 0 to 3, and nx1 + nx2 + n1 ≦ 5. n2 and n3 are each independent integers from 0 to 4. When nx1 is 2 or more, the complex X01 groups can be the same or different. When nx2 is 2 or more, the complex X02 groups can be the same or different. When n1 is 2 or more, the complex R01 groups can be the same or different. When n2 is 2 or more, the complex R02 groups can be the same or different. When n3 is 2 or more, the complex R03 groups can be the same or different.] Xb- is a relative anion.

[0017] The fourth state of the present invention is an acid diffusion control agent, which comprises a compound represented by the following general formula (DO).

[0018] [In the formula, X01 is an electron-withdrawing group, X02 is an electron-withdrawing group different from X01, and R01 is an electron-donating group. R02 and R03 are each independent substituents. nx1 and nx2 are each independent integers from 1 to 4, n1 is an integer from 0 to 3, and nx1 + nx2 + n1 ≦ 5. n2 and n3 are each independent integers from 0 to 4. When nx1 is 2 or more, the complex X01 groups can be the same or different. When nx2 is 2 or more, the complex X02 groups can be the same or different. When n1 is 2 or more, the complex R01 groups can be the same or different. When n2 is 2 or more, the complex R02 groups can be the same or different. When n3 is 2 or more, the complex R03 groups can be the same or different.] Xd- is a relative anion.

[0019] The fifth state of the present invention is a polymer compound having the constituent unit (a0) shown in the following general formula (A0-1).

[0020] [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. Rx0 is a group containing an anion. X01 is an electron-withdrawing group, X02 is an electron-withdrawing group different from X01, and R01 is an electron-donating group. R02 and R03 are each independently substituents. nx1 and nx2 are each independently integers from 1 to 4, n1 is an integer from 0 to 3, and nx1 + nx2 + n1 ≦ 5. n2 and n3 are each independently integers from 0 to 4. When nx1 is 2 or more, the multiple X01 groups can be the same or different. When nx2 is 2 or more, the multiple X02 groups can be the same or different. When n1 is 2 or more, the multiple R01 groups can be the same or different.] When n2 is 2 or more, the complex R02 systems can be identical or distinct. When n3 is 2 or more, the complex R03 systems can be identical or distinct. [Effects of the Invention]

[0021] According to the present invention, a resist composition with high sensitivity and good photolithography properties such as defects can be provided, a resist pattern forming method using the aforementioned resist composition, a compound used in the aforementioned resist composition, an acid generator, an acid diffusion control agent, and a polymer compound.

Implementation Method

[0022] In this specification and the scope of this application, "aliphatic" is a relative concept compared to aromatic, and is defined as a group, compound, etc., that does not possess aromaticity. "Alkyl" unless specifically defined, is considered to include monovalent saturated hydrocarbon groups that are linear, branched, or cyclic. The same applies to alkyl groups in alkoxy groups. "Decanyl" unless specifically defined, is considered to include divalent saturated hydrocarbon groups that are linear, branched, or cyclic. "Halogen atom" can be exemplified by fluorine, chlorine, bromine, and iodine atoms. "Constituent unit" refers to the monomer unit (monomer unit) that constitutes a polymer compound (resin, polymer, copolymer). When stated as "may have substituents," this includes both cases where hydrogen atoms (-H) are replaced by monovalent groups and cases where methylene (-CH2-) is replaced by divalent groups. "Exposure" is considered to include irradiation with various types of radiation.

[0023] An "acid-decomposable group" is a group that has acid-decomposability, meaning that at least a portion of the bonds in its structure can be broken by the action of an acid. Examples of acid-decomposable groups whose polarity increases due to the action of an acid include groups that decompose to produce polar groups by the action of an acid. 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-dissociative groups (e.g., groups in which the hydrogen atoms of a polar group containing OH are protected by an acid-dissociative group).

[0024] "Acid-dissociable group" refers to (i) a group whose bonds between the acid-dissociable group and the adjacent atoms can be broken by the action of an acid, or (ii) a group whose bonds can be broken by a partial bond breakage by the action of an acid, and further broken by a decarbonation reaction. The acid-dissociable group constituting the acid-dissociable group must be a group with lower polarity than the polar group generated by the dissociation of the acid-dissociable group. In this way, when the acid-dissociable group dissociates by the action of an acid, a polar group with higher polarity than the acid-dissociable group is generated, thereby increasing the polarity. The result is an increase in the overall polarity of (A1) component. By increasing polarity, the solubility of the developer changes relatively. The solubility increases when the developer is alkaline, and decreases when the developer is organic.

[0025] "Substrate component" refers to an organic compound with film-forming ability. Organic compounds used as substrate components are broadly classified into non-polymers and polymers. Non-polymers typically use compounds with a molecular weight of 500 or more but less than 4000. Hereinafter, when referred to as "low molecular weight compounds," this indicates non-polymers with a molecular weight of 500 or more but less than 4000. Polymers typically use compounds with a molecular weight of 1000 or more. Hereinafter, when referred to as "resin," "high molecular weight compound," or "polymer," this indicates polymers with a molecular weight of 1000 or more. The molecular weight of a polymer is considered to be the weight-average molecular weight converted to polystyrene using GPC (gel permeation chromatography).

[0026] "Derived constituent units" refers to multiple bonds between carbon atoms, such as the constituent units formed by the cleavage of vinyl double bonds. The hydrogen atom bonded to the α-carbon atom in "acrylate" can also be replaced by a substituent. The substituent (Rαx) that replaces the hydrogen atom bonded to the α-carbon atom is an atom or group other than the hydrogen atom. Furthermore, this also includes isoconic acid diesters substituted with a substituent (Rαx) containing an ester bond, or α-hydroxy acrylates substituted with a hydroxyalkyl group or a group modified with that hydroxyl group. Moreover, when not specifically defined, the α-carbon atom in acrylate 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 replaced by a substituent are referred to as α-substituted acrylates.

[0027] "Derivative" is considered to include compounds in which the α-hydrogen atom of the target compound is replaced by other substituents such as alkyl groups or halogenated alkyl groups, and such derivatives. Examples of such derivatives include, for instance, compounds in which the α-hydrogen atom of the target compound is replaced by a substituent and the hydrogen atom of the hydroxyl group is replaced by an organogroup; and compounds in which a substituent other than a hydroxyl group is bonded to the target compound in which the α-hydrogen atom is replaced by a substituent. Furthermore, when not specifically defined, the α-position refers to the first carbon atom adjacent to the functional group. Examples of substituents that replace the α-hydrogen atom of hydroxystyrene include those identical to Rαx.

[0028] In this specification and the claims, based on the structure represented by the chemical formula, there may be asymmetric carbon, and there may be enantiomers or diastereomers. In this case, a single chemical formula is used to represent such isomers. Such isomers can be used alone or as mixtures.

[0029] (Resistant Composition) The resistant composition of the first embodiment of the present invention is one that generates acid due to exposure and changes the solubility of the developer due to the action of the acid. The resistant composition contains a compound comprising a cation (CO) of the general formula (CO) (hereinafter also referred to as "Compound C"). Compound (C) may also be a substrate component (A) whose solubility of the developer changes due to the action of the acid (hereinafter also referred to as "(A) component"). Compound (C) may also be an acid generating agent component (B) that generates acid due to exposure (hereinafter also referred to as "(B) component"). Compound (C) may also be an acid diffusion control agent component (D) that traps the acid generated due to exposure (i.e., controls the diffusion of acid) (hereinafter also referred to as "(D) component").

[0030] The resist composition of this embodiment is capable of generating acid due to exposure. It can be component (A) or component (B) that generates acid due to exposure. Specifically, the resist composition of this embodiment is (1) that may contain component (B) as a component that generates acid due to exposure, (2) component (A) that may generate acid due to exposure, and (3) component (A) that may generate acid due to exposure, and may also contain component (B). That is, in the cases of (2) and (3) above, component (A) becomes "a substrate component that generates acid due to exposure and whose solubility in the developer changes due to the action of the acid". In the case where component (A) is a substrate component that generates acid due to exposure and whose solubility in the developer changes due to the action of the acid, component (A1) described later is preferably a polymer compound that generates acid due to exposure and whose solubility in the developer changes due to the action of the acid. As such a polymer compound, a resin having constituent units that generate acid upon exposure can be used. Known constituent units that generate acid upon exposure can be used.

[0031] When a resist film is formed using the resist composition of this embodiment and the resist film is selectively exposed, acid is generated from component (A) or component (B) in the exposed portion of the resist film. This acid causes a change in the solubility of component (A) in the developer. Conversely, the solubility of component (A) in the developer does not change in the unexposed portion of the resist film. Therefore, a difference in solubility in the developer occurs between the exposed and unexposed portions. Thus, when developing the resist film, if the resist composition is positive, the exposed portion of the resist film is dissolved and removed to form a positive resist pattern; if the resist composition is negative, the unexposed portion of the resist film is dissolved and removed to form a negative resist pattern.

[0032] In this specification, a resist composition in which the exposed portion of the resist film is dissolved and removed to form a positive resist pattern is called a positive resist composition, and a resist composition in which the unexposed portion of the resist film is dissolved and removed to form a negative resist pattern is called a negative resist composition. The resist composition of this embodiment can be either a positive or a negative resist composition. Furthermore, the resist composition of this embodiment can be used in an alkaline development process where an alkaline developer is used in the development process during resist pattern formation, or in a solvent development process where a developer containing an organic solvent (organic developer) is used in the development process.

[0033] <Compound (C) containing a cation (CO)> The inhibitor composition of this embodiment contains: a compound (C) containing a cation (CO) as shown in the following general formula (CO).

[0034] [In the formula, X01 is an electron-withdrawing group, X02 is an electron-withdrawing group different from X01, and R01 is an electron-donating group. R02 and R03 are each independent substituents. nx1 and nx2 are each independent integers from 1 to 4, n1 is an integer from 0 to 3, and nx1 + nx2 + n1 ≦ 5. n2 and n3 are each independent integers from 0 to 4. When nx1 is 2 or more, the complex X01 groups can be the same or different. When nx2 is 2 or more, the complex X02 groups can be the same or different. When n1 is 2 or more, the complex R01 groups can be the same or different. When n2 is 2 or more, the complex R02 groups can be the same or different. When n3 is 2 or more, the complex R03 groups can be the same or different.] ]

[0035] In the aforementioned formula (c0), X01 is an electron-withdrawing group. Examples of electron-withdrawing groups include acetyl, methanesulfonyl, halogen atom, alkyl halide, alkoxy halide, alkylamine halide, alkylthio halide, cyano, nitro, dialkylphosphinyl, alkylsulfonyl, sulfonoxy, acylthio, sulfamoyl, thiocyanate, and thiocarbonyl. Examples of halogen atoms among the aforementioned halogen atoms, alkyl halide, alkoxy halide, aryloxy halide, alkylamine, and alkylthio halide include fluorine, bromine, and iodine atoms, with fluorine atoms being preferred. The alkyl group among the aforementioned halogenated alkyl, halogenated alkoxy, halogenated alkylamine, halogenated alkylthio, dialkylphosphinyl, and alkylsulfonyl groups preferably has 1 to 5 carbon atoms, more preferably 1 to 3 carbon atoms, and even more preferably 1 or 2 carbon atoms. Among these, electron-withdrawing groups are preferably fluorine atoms or fluorinated alkyl groups, more preferably fluorine atoms or fluorinated alkyl groups with 1 to 3 carbon atoms, and even more preferably fluorine atoms or trifluoromethyl groups. Specific examples of electron-withdrawing groups are shown below.

[0036]

[0037] In the aforementioned formula (c0), X02 is an electron-withdrawing group that is different from X01. As an electron-withdrawing group in X02, examples can be given that are the same as those exemplified as electron-withdrawing groups in X01. However, the electron-withdrawing group of X02 is different from the electron-withdrawing group of X01. That is, X01 and X02 cannot be the same electron-withdrawing group.

[0038] Examples of combinations of X01 and X02 include combinations of halogen atoms and alkyl halides, combinations of halogen atoms and methanesulfonyl groups, combinations of alkyl halides and methanesulfonyl groups, combinations of halogen atoms and cyano groups, and combinations of alkyl halides and cyano groups. Among these, combinations of fluorine atoms and fluorinated alkyl groups are preferred as combinations of X01 and X02.

[0039] In the aforementioned formula (c0), nx1 and nx2 are each independent integers from 1 to 4. When nx1 is 2 or more, the complex numbers X01 can be the same or different. When nx2 is 2 or more, the complex numbers X02 can be the same or different. It is preferable for nx1 and nx2 to be integers from 1 to 3, more preferable for nx1 or nx2, and even more preferable for nx1 to nx2. From the viewpoint that the hydrophobicity will not become too high, it is preferable for nx1 and nx2 to be 1.

[0040] The cation (CO) disrupts the symmetry of the electron density of the phenyl group by having two or more electron-withdrawing groups, as shown in X01 and X02, bonded to the sulfur atom of the dibenzothiophene skeleton. In the cation (CO), the phenyl group bonded to the sulfur atom of the dibenzothiophene skeleton has a high degree of rotational freedom. It is believed that by disrupting the electron density of this phenyl group with a high degree of rotational freedom, its solubility in solvents is improved. Therefore, compounds (C) containing cations (CO) have improved solubility in organic solvents used in modulating resist compositions. Furthermore, it is believed that the cations (CO) that decompose upon exposure have improved solubility in developer. This results in a reduction of defects.

[0041] The bonding positions of X01 and X02 on the phenyl group are not particularly limited. From the viewpoint of disrupting the symmetry of the electron density in the phenyl group, it is preferable that X01 and X02 are bonded to the phenyl group in a way that makes the balance of electron-withdrawing groups on the phenyl group asymmetric. For example, it is preferable that no similar electron-withdrawing group is bonded to the ortho position at position 2 of the phenyl group. It is preferable that no similar electron-withdrawing group is bonded to the meta position at position 2 of the phenyl group. Examples of combinations of bonding positions of X01 and X02 on the phenyl group include, for example, meta-meta combinations; para-meta combinations; meta-ortho combinations; and ortho-para combinations. Examples of meta-ortho combinations include, for example, 1-2-1; 1-4-1; 2-5-1; and 4-5-1. As for combinations of intermediate and adjacent positions, combinations of 1 and 4 positions, or combinations of 2 and 5 positions, are preferred.

[0042] In the aforementioned formula (c0), R01 is an electron-donating group. There is no particular limitation on the electron-donating group of R01. Examples of electron-donating groups include alkyl groups and alkoxy groups. Preferably, the aforementioned alkyl and alkoxy groups have 1 to 5 carbon atoms, more preferably 1 to 3 carbon atoms, and even more preferably 1 or 2 carbon atoms. Specific examples of electron-donating groups include methyl, ethyl, tert-butyl, n-butyl, methoxy, etc.

[0043] In the aforementioned (c0), n1 is an integer from 0 to 3. It is preferable for n1 to be 0 to 2, and even better if it is 0 or 1. When n1 is 2 or more, the complex numbers R01 can be the same or different. nx1+nx2+n1≦5.

[0044] In the aforementioned formula (c0), R02 and R03 are each independently a substituent. The substituents of R02 and R03 can be electron-withdrawing groups or electron-donating groups. Examples of substituents for R02 and R03 that are the same as those exemplified as the aforementioned electron-withdrawing and electron-donating groups can be given.

[0045] In the aforementioned formula (c0), n2 and n3 are each independent integers from 0 to 4. It is preferable for n2 to be between 0 and 3, even better for n2 to be between 0 and 2, and even more preferable for n2 to be 0 or 1. When n2 is 2 or more, the complex R02 series can be identical or distinct. When n3 is 2 or more, the complex R03 series can be identical or distinct.

[0046] The following shows specific examples of cations (CO), but are not limited to them.

[0047]

[0048]

[0049] [First Embodiment] The resist composition of the first embodiment contains compound (C) as component (B). The resist composition of the first embodiment contains: component (A) which generates acid upon exposure and changes the solubility of the developer due to the action of the acid, and acid-generating agent component (B) which generates acid upon exposure. The aforementioned acid-generating agent component (B) includes a compound represented by the following general formula (b0).

[0050] [Where, Mb+ is the aforementioned cation (CO). Xb- is the relative anion.]

[0051] <(A) Component> In the resist composition of this embodiment, the (A) component is preferably a resin component (A1) (hereinafter also referred to as "(A1) component") that changes its solubility in the developer due to the action of acid. By using the (A1) component, since the polarity of the substrate composition changes before and after exposure, good development contrast can be obtained not only in alkaline development processes but also in solvent development processes. As the (A) component, at least the (A1) component is used, and the (A1) component can also be used in combination with other polymeric compounds and / or low-molecular-weight compounds.

[0052] In the case of an alkaline development process, the substrate component containing the (A1) component is poorly soluble in the alkaline developer before exposure. When acid is generated from the (B) component by exposure, for example, the polarity increases due to the action of the acid, thereby increasing the solubility in the alkaline developer. Therefore, in the formation of the resist pattern, when selectively exposing the resist film obtained by coating the resist composition onto the support, the exposed portion of the resist film changes from being poorly soluble in the alkaline developer to being soluble, while the unexposed portion of the resist film does not change and remains poorly soluble in the alkaline developer. Thus, a positive resist pattern is formed by alkaline development.

[0053] On the other hand, in the case of a solvent-based development process, the substrate component containing the (A1) component has high solubility in the organic developer before exposure. When, for example, acid is generated from the (B) component by exposure, the polarity increases due to the action of the acid, thereby reducing the solubility in the organic developer. Therefore, in the formation of the resist pattern, when selectively exposing the resist film obtained by coating the resist composition onto the support, the exposed portion of the resist film changes from being soluble in the organic developer to being insoluble, while the unexposed portion of the resist film does not change and remains soluble. Therefore, by developing with an organic developer, a contrast can be formed between the exposed and unexposed portions, thus forming a negative resist pattern.

[0054] In the inhibitor composition of this embodiment, component (A) can be used alone or in combination with two or more components.

[0055] ・Regarding component (A1): Component (A1) is a resin component whose solubility in the developer changes due to the action of acid. Component (A1) is preferably a constituent unit (a1) containing an acid-decomposing group whose polarity increases due to the action of acid. Component (A1) may also be a component containing a constituent unit (a1) and other constituent units as necessary.

[0056] ≪Constituent Unit (a1)≫ Constituent Unit (a1) is a constituent unit containing acid-decomposing groups whose polarity increases due to the action of acid.

[0057] Examples of acid-dissociating groups include those proposed so far as to be used as components of chemically amplifying inhibitors, such as the acid-dissociating groups of matrix resins. Specific examples of acid-dissociating groups proposed as components of matrix resins for use as chemically amplifying inhibitors include "acetal-type acid-dissociating groups," "third-order alkyl ester-type acid-dissociating groups," and "third-order alkoxycarbonyl acid-dissociating groups," as described below.

[0058] Acetal type acid dissociation group: As an acid dissociation group that protects the carboxyl or hydroxyl group among the aforementioned polar groups, examples include the acid dissociation group shown in the following general formula (a1-r-1) (hereinafter referred to as "acetal type acid dissociation group").

[0059] [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 combine with either Ra'1 or Ra'2 to form a ring.]

[0060] In formula (a1-r-1), it is preferable that at least one of Ra'1 and Ra'2 is a hydrogen atom, and it is more preferable that both are hydrogen atoms. If Ra'1 or Ra'2 is an alkyl group, examples of such alkyl groups, as described above regarding α-substituted acrylates, are those alkyl groups exemplified as substituents that can bond to the α-carbon atom, and preferably alkyl groups with 1 to 5 carbon atoms. Specifically, linear or branched alkyl groups are preferred. More specifically, examples include methyl, ethyl, propyl, isopropyl, n-butyl, isobutyl, tert-butyl, pentyl, isopentyl, neopentyl, etc., with methyl or ethyl being preferred, and methyl being more preferred.

[0061] In formula (a1-r-1), the hydrocarbon group of Ra'3 can be a straight-chain or branched 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. Specific examples include methyl, ethyl, n-propyl, n-butyl, and n-pentyl. Among these, methyl, ethyl, or n-butyl are preferred, with methyl or ethyl being more preferred.

[0062] The branched alkyl group is preferably composed of 3 to 10 carbon atoms, and more preferably 3 to 5 carbon atoms. Examples of such compounds include isopropyl, isobutyl, tert-butyl, isopentyl, neopentyl, 1,1-diethylpropyl, and 2,2-dimethylbutyl, with isopropyl being the most preferred.

[0063] When Ra'3 is a cyclic hydrocarbon group, the hydrocarbon group can be an aliphatic hydrocarbon group or an aromatic hydrocarbon group, and it can be a polycyclic group or a monocyclic group. As a monocyclic aliphatic hydrocarbon group, it is preferable to be a group in which one hydrogen atom has been removed from a monocyclic alkane. As for the monocyclic alkane, it is preferable to have 3 to 6 carbon atoms, and specific examples include cyclopentane and cyclohexane. As a polycyclic aliphatic hydrocarbon group, it is preferable to be a group in which one hydrogen atom has been removed from a polycyclic alkane, and as for the polycyclic alkane, it is preferable to have 7 to 12 carbon atoms, and specific examples include adamantane, norcamphene, isocamphene, tricyclodecane, tetracyclododecane, etc.

[0064] In the case where the cyclic hydrocarbon group of Ra'3 is an aromatic hydrocarbon group, the aromatic hydrocarbon group is a hydrocarbon group having at least one aromatic ring. There are no particular limitations as long as the aromatic ring is a cyclic conjugated system with 4n+2 π electrons; it can be monocyclic or polycyclic. The number of carbon atoms in the aromatic ring is preferably 5 to 30, more preferably 5 to 20, even more preferably 6 to 15, and particularly preferably 6 to 12. Specific examples of aromatic rings include aromatic hydrocarbon rings of benzene, naphthalene, anthracene, and phenanthrene; and aromatic heterocycles in which part of the carbon atoms constituting the aforementioned aromatic hydrocarbon rings are replaced by heteroatoms. Examples of heteroatoms in aromatic heterocycles include oxygen atoms, sulfur atoms, and nitrogen atoms. Specific examples of aromatic heterocycles include pyridine rings and thiophene rings. Specifically, the aromatic hydrocarbon group in Ra'3 can be exemplified by a group (aryl or heteroaryl) in which one hydrogen atom is removed from the aforementioned aromatic hydrocarbon ring or aromatic heterocycle; a group in which one hydrogen atom is removed from an aromatic compound containing two or more aromatic rings (e.g., biphenyl, benzoylene, etc.); or a group in which one hydrogen atom of the aforementioned aromatic hydrocarbon ring or aromatic heterocycle is replaced by an alkyl group (e.g., arylalkyl groups such as benzyl, phenethyl, 1-naphthylmethyl, 2-naphthylmethyl, 1-naphthylethyl, 2-naphthylethyl, etc.). The number of carbon atoms in the alkyl group bonded to the aforementioned aromatic hydrocarbon ring or aromatic heterocycle is preferably 1 to 4, more preferably 1 to 2, and particularly preferably 1.

[0065] The cyclic hydrocarbon group in Ra'3 may also have substituents. Examples of such substituents include -RP1, -RP2-O-RP1, -RP2-CO-RP1, -RP2-CO-ORP1, -RP2-O-CO-RP1, -RP2-OH, -RP2-CN, or -RP2-COOH (hereinafter, these substituents are collectively referred to as "Rax5"). Here, RP1 is a monovalent chain saturated hydrocarbon group with 1 to 10 carbon atoms, a monovalent aliphatic cyclic saturated hydrocarbon group with 3 to 20 carbon atoms, or a monovalent aromatic hydrocarbon group with 6 to 30 carbon atoms. RP2 is a single bond, a divalent chain saturated hydrocarbon group with 1 to 10 carbon atoms, a divalent aliphatic cyclic saturated hydrocarbon group with 3 to 20 carbon atoms, or a divalent aromatic hydrocarbon group with 6 to 30 carbon atoms. However, some or all of the hydrogen atoms in the chain saturated hydrocarbon group, aliphatic cyclic saturated hydrocarbon group, and aromatic hydrocarbon group of RP1 and RP2 may be replaced by fluorine atoms. The aforementioned aliphatic cyclic hydrocarbon group may have one or more of the above-mentioned substituents, or may have one or more of each 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 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 monocyclic 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.

[0066] When Ra'3 combines with either Ra'1 or Ra'2 to form a ring, the cyclic group is preferably a 4-7 member ring, and more preferably a 4-6 member ring. Specific examples of this cyclic group include tetrahydropyranyl and tetrahydrofuranyl.

[0067] Third-order alkyl ester type acid-dissociative group: As an acid-dissociative group protecting the carboxyl group among the above-mentioned polar groups, examples include the acid-dissociative group shown in the following general formula (a1-r-2). Furthermore, there are cases where the acid-dissociative group shown in the following formula (a1-r-2) is composed of an alkyl group, which are conveniently referred to below as "third-order alkyl ester type acid-dissociative group".

[0068] [In the formula, Ra'4~Ra'6 are each a hydrocarbon group, and Ra'5 and Ra'6 can also combine with each other to form a ring.]

[0069] Examples of hydrocarbon groups in Ra'4 include linear or branched alkyl groups, chain or cyclic alkenyl groups, or cyclic hydrocarbon groups. The linear or branched alkyl groups and cyclic hydrocarbon groups (monocyclic aliphatic hydrocarbon groups, polycyclic aliphatic hydrocarbon groups, aromatic hydrocarbon groups) in Ra'4 can be the same as those described in Ra'3. The chain or cyclic alkenyl groups in Ra'4 are preferably alkenyl groups with 2 to 10 carbon atoms. Examples of hydrocarbon groups in Ra'5 and Ra'6 can be the same as those described in Ra'3.

[0070] When Ra'5 and Ra'6 combine to form a ring, the following general formulas (a1-r2-1, a1-r2-2, and a1-r2-3) are suitable examples. On the other hand, when Ra'4 to Ra'6 are independent hydrocarbon groups without combining, the following general formula (a1-r2-4) is suitable.

[0071] [In formula (a1-r2-1), Ra'10 represents a linear or branched alkyl group with 1 to 12 carbon atoms, which can be partially replaced by a halogen atom or a heteroatom-containing group. Ra'11 represents a group that forms an aliphatic cyclic group together with the carbon atom bonded to Ra'10. In formula (a1-r2-2), Ya is a carbon atom. Xa is a group that forms a cyclic hydrocarbon group together with Ya. Some or all of the hydrogen atoms in the cyclic hydrocarbon group can also be replaced. Ra101 to Ra103 are each independently a 1-valent chain saturated hydrocarbon group with 1 to 10 carbon atoms or a 1-valent aliphatic cyclic saturated hydrocarbon group with 3 to 20 carbon atoms. Some or all of the hydrogen atoms in the chain saturated hydrocarbon group and the aliphatic cyclic saturated hydrocarbon group can also be replaced. Two or more of Ra101 to Ra103 can also be combined to form a cyclic structure.] In formula (a1-r2-3), Yaa is a carbon atom. Xaa forms an aliphatic cyclic group together with Yaa. Ra104 is an aromatic hydrocarbon group that may have substituents. In formula (a1-r2-4), Ra'12 and Ra'13 are each independently a monovalent chain saturated hydrocarbon group 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 is a hydrocarbon group that may have substituents. * indicates a bond.

[0072] In the above formula (a1-r2-1), Ra'10 is a linear or branched alkyl group with 1 to 12 carbon atoms that can be replaced by halogen atoms or heteroatom-containing groups.

[0073] As a straight-chain alkyl group in Ra'10, it is preferably composed of 1 to 12 carbon atoms, with 1 to 10 carbon atoms being more preferred, and 1 to 5 carbon atoms being particularly preferred. As a branched alkyl group in Ra'10, examples such as those similar to those described above in Ra'3 can be cited.

[0074] One portion of the alkyl group in Ra'10 may also be replaced by a halogen atom or a heteroatom-containing group. For example, one portion of the hydrogen atom constituting the alkyl group may be replaced by a halogen atom or a heteroatom-containing group. Furthermore, one portion of the carbon atom constituting the alkyl group (such as a methylene group) may also be replaced by a heteroatom-containing group. Examples of heteroatoms referred to here include oxygen atoms, sulfur atoms, and nitrogen atoms. Examples of heteroatom-containing groups include (-O-), -C(=O)-O-, -OC(=O)-, -C(=O)-, -OC(=O)-O-, -C(=O)-NH-, -NH-, -S-, -S(=O)2-, -S(=O)2-O-, etc.

[0075] 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) exemplified as a monocyclic or polycyclic group of Ra'3 in formula (a1-r-1). Among them, monocyclic alicyclic hydrocarbon groups are preferred, and specifically, cyclopentyl and cyclohexyl are more preferred, with cyclopentyl being even more preferred.

[0076] In formula (a1-r2-2), the cyclic hydrocarbon group formed by Xa and Ya together can be, for example, a group from which one or more hydrogen atoms are removed from the cyclic monovalent hydrocarbon group (aliphatic hydrocarbon group) in Ra'3 of the aforementioned formula (a1-r-1). The cyclic hydrocarbon group formed by Xa and Ya together may also have substituents. As such substituents, there may be substituents that are the same as those that may be present in the cyclic hydrocarbon group in Ra'3 mentioned above. In formula (a1-r2-2), the monovalent chain saturated hydrocarbon group with 1 to 10 carbon atoms in Ra101 to Ra103 can be, for example, methyl, ethyl, propyl, butyl, pentyl, hexyl, heptyl, octyl, decyl, etc. Examples of monocyclic aliphatic saturated hydrocarbon groups with 3 to 20 carbon atoms in Ra101 to Ra103 include monocyclic aliphatic saturated hydrocarbon groups such as cyclopropyl, cyclobutyl, cyclopentyl, cyclohexyl, cycloheptyl, cyclooctyl, cyclodecyl, and cyclododecyl; and polycyclic aliphatic saturated hydrocarbon groups such as bicyclic [2.2.2]octyl, tricyclic [5.2.1.02,6]decyl, tricyclic [3.3.1.13,7]decyl, tetracyclic [6.2.1.13,6.02,7]dodecyl, and adamantyl. From the viewpoint of ease of synthesis, monocyclic chain saturated hydrocarbon groups with 1 to 10 carbon atoms are preferred in Ra101 to Ra103, with hydrogen atoms, methyl, and ethyl atoms being more preferred, and hydrogen atoms being particularly preferred.

[0077] Examples of substituents in the chain-like saturated hydrocarbon groups or aliphatic cyclic saturated hydrocarbon groups shown in Ra101 to Ra103 above include, for example, groups identical to those in Rax5 above.

[0078] Examples of groups containing carbon-carbon double bonds formed by the combination of two or more Ra101 to Ra103 to create a cyclic structure include cyclopentenyl, cyclohexenyl, methylcyclopentenyl, methylcyclohexenyl, cyclopentylenevinyl, and cyclohexylenevinyl. Among these, cyclopentenyl, cyclohexenyl, and cyclopentylenevinyl are preferred from the viewpoint of ease of synthesis.

[0079] In formula (a1-r2-3), the aliphatic cyclic group formed by Xaa and Yaa together is preferably an aliphatic hydrocarbon group exemplified as a monocyclic or polycyclic group of Ra'3 in formula (a1-r-1). In formula (a1-r2-3), the aromatic hydrocarbon group in Ra104 can be a group in which one or more hydrogen atoms have been removed from an aromatic hydrocarbon ring having 5 to 30 carbon atoms. Among them, Ra104 is preferably a group in which one or more hydrogen atoms have been removed from an aromatic hydrocarbon ring having 6 to 15 carbon atoms, more preferably a group in which one or more hydrogen atoms have been removed from benzene, naphthalene, anthracene or phenanthrene, even more preferably a group in which one or more hydrogen atoms have been removed from benzene, naphthalene or anthracene, particularly preferably a group in which one or more hydrogen atoms have been removed from benzene or naphthalene, and most preferably a group in which one or more hydrogen atoms have been removed from benzene.

[0080] As a substituent that Ra104 in formula (a1-r2-3) may have, examples include methyl, ethyl, propyl, hydroxyl, carboxyl, halogen atom, alkoxy (methoxy, ethoxy, propoxy, butoxy, etc.), alkoxy carbonyl, etc.

[0081] In formula (a1-r2-4), Ra'12 and Ra'13 are each independently a monovalent chain saturated hydrocarbon group having 1 to 10 carbon atoms. Examples of monovalent chain saturated hydrocarbon groups having 1 to 10 carbon atoms in Ra'12 and Ra'13 include those identical to the monovalent chain saturated hydrocarbon groups having 1 to 10 carbon atoms in Ra101 to Ra103 described above. Some or all of the hydrogen atoms in this chain saturated hydrocarbon group may also be substituted. Preferably, Ra'12 and Ra'13 are alkyl groups having 1 to 5 carbon atoms, more preferably alkyl groups having 1 to 5 carbon atoms, methyl or ethyl is more preferred, and methyl is particularly preferred. In cases where the chain saturated hydrocarbon groups shown in Ra'12 and Ra'13 are substituted, examples of substituents include groups identical to those in Rax5 described above.

[0082] In formula (a1-r2-4), Ra'14 is a hydrocarbon group that may have substituents. Examples of hydrocarbon groups in Ra'14 include linear or branched alkyl groups or cyclic hydrocarbon groups.

[0083] The linear alkyl group in Ra'14 is preferably composed of 1 to 5 carbon atoms, more preferably 1 to 4, and even more preferably 1 or 2. Specific examples include methyl, ethyl, n-propyl, n-butyl, and n-pentyl. Among these, methyl, ethyl, or n-butyl is preferred, with methyl or ethyl being more preferred.

[0084] The branched alkyl group in Ra'14 is preferably composed of 3 to 10 carbon atoms, with 3 to 5 being more preferred. Specific examples include isopropyl, isobutyl, tert-butyl, isopentyl, neopentyl, 1,1-diethylpropyl, 2,2-dimethylbutyl, etc., with isopropyl being the most preferred.

[0085] When Ra'14 is a cyclic hydrocarbon group, the hydrocarbon group can be an aliphatic hydrocarbon group or an aromatic hydrocarbon group, and it can 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, and specific examples include cyclopentane and cyclohexane. As a polycyclic aliphatic hydrocarbon group, it is preferable to be a group that has removed one hydrogen atom from a polycyclic alkane, and as for the polycyclic alkane, it is preferable to have 7 to 12 carbon atoms, and specific examples include adamantane, norcamphene, isocamphene, tricyclic decane, tetracyclic dodecane, etc.

[0086] Examples of aromatic hydrocarbon groups in Ra'14 that are the same as those in Ra104 can be cited. Among these, Ra'14 preferably has a group from which one or more hydrogen atoms have been removed from an aromatic hydrocarbon ring having 6 to 15 carbon atoms; a group from which one hydrogen atom has been removed from benzene, naphthalene, anthracene, or phenanthrene is more preferred; a group from which one or more hydrogen atoms have been removed from benzene, naphthalene, or anthracene is even more preferred; a group from which one or more hydrogen atoms have been removed from naphthalene or anthracene is particularly preferred; and a group from which one or more hydrogen atoms have been removed from naphthalene is best. Examples of substituents that Ra'14 may have are the same as those that Ra104 may have.

[0087] In the case where Ra'14 in formula (a1-r2-4) is a naphthyl group, the position of the bond between Ra'14 and the third-order carbon atom in the aforementioned formula (a1-r2-4) can be either the 1st or 2nd position of the naphthyl group. In the case where Ra'14 in formula (a1-r2-4) is an anthracene group, the position of the bond between Ra'14 and the third-order carbon atom in the aforementioned formula (a1-r2-4) can be either the 1st, 2nd, or 9th position of the anthracene group.

[0088] The following are specific examples of the basis shown in the aforementioned formula (a1-r2-1).

[0089]

[0090]

[0091]

[0092] The following are specific examples of the basis shown in the aforementioned formula (a1-r2-2).

[0093]

[0094]

[0095]

[0096] The following are specific examples of the basis shown in the aforementioned formula (a1-r2-3).

[0097]

[0098] The following are specific examples of the basis shown in the aforementioned formula (a1-r2-4).

[0099]

[0100] Third-order alkoxycarbonyl acid dissociation group: As an acid dissociation group that protects the hydroxyl group in the aforementioned polar group, examples can be the acid dissociation group shown in the following general formula (a1-r-3) (hereinafter referred to as "third-order alkoxycarbonyl acid dissociation group" for convenience).

[0101] [In the formula, Ra'7~Ra'9 are each alkyl groups.]

[0102] In formula (a1-r-3), Ra'7 to Ra'9 are preferably alkyl groups with 1 to 5 carbon atoms, and more preferably alkyl groups with 1 to 3 carbon atoms. Furthermore, the total number of carbon atoms of each alkyl group is preferably 3 to 7, more preferably 3 to 5, and most preferably 3 to 4.

[0103] As a constituent unit (a1), examples include: a constituent unit derived from an acrylate in which the hydrogen atom bonded to the carbon atom at the α-position can be replaced by a substituent; a constituent unit derived from acrylamide; a constituent unit in which at least a portion of the hydrogen atom in the hydroxyl group of a constituent unit derived from hydroxystyrene or a hydroxystyrene derivative is protected by a substituent containing the aforementioned acid-degrading group; and a constituent unit in which at least a portion of the hydrogen atom in the -C(=O)-OH of a constituent unit derived from vinyl benzoic acid or a vinyl benzoic acid derivative is protected by a substituent containing the aforementioned acid-degrading group, etc.

[0104] As a constituent unit (a1), it is preferable to use a constituent unit derived from an acrylate in which the hydrogen atom bonded to the carbon atom at the α-position can be replaced by a substituent. As a preferred specific example of such a constituent unit (a1), the constituent unit shown in the following general formula (a1-1) or (a1-2) can be given.

[0105] [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. Va1 is a divalent hydrocarbon group that may have an ether bond. na1 is an integer from 0 to 2. Ra1 is an acid-dissociable group shown in 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 shown in the above general formula (a1-r-1) or (a1-r-3).]

[0106] In the aforementioned formula (a1-1), the alkyl group of R having 1 to 5 carbon atoms is preferably a straight-chain or branched alkyl group having 1 to 5 carbon atoms, specifically including methyl, ethyl, propyl, isopropyl, n-butyl, isobutyl, tert-butyl, pentyl, isopentyl, neopentyl, etc. The halogenated alkyl group having 1 to 5 carbon atoms is a group in which one or all of the hydrogen atoms of the aforementioned alkyl group having 1 to 5 carbon atoms are substituted with halogen atoms. As the halogen atom, a fluorine atom is particularly preferred. As R, a hydrogen atom, an alkyl group having 1 to 5 carbon atoms, or a fluorinated alkyl group having 1 to 5 carbon atoms is preferred, and from the viewpoint of ease of industrial acquisition, a hydrogen atom or a methyl group is best.

[0107] In the aforementioned formula (a1-1), the divalent hydrocarbon group in Va1 can be an aliphatic hydrocarbon group or an aromatic hydrocarbon group.

[0108] The aliphatic hydrocarbon group that is a divalent hydrocarbon group in Va1 can be saturated or unsaturated, but saturation is generally preferred. More specifically, examples of such aliphatic hydrocarbon groups include linear or branched aliphatic hydrocarbon groups, or aliphatic hydrocarbon groups whose structure contains a ring.

[0109] 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 best 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 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 best preferably 3 carbon atoms. As a branched aliphatic hydrocarbon group, branched alkyl groups are preferred. Specific 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, a straight-chain alkyl group with 1 to 5 carbon atoms is preferred.

[0110] Examples of alicyclic hydrocarbon groups containing a ring in the aforementioned structure include, for example, alicyclic hydrocarbon groups (groups with two hydrogen atoms removed from an alicyclic hydrocarbon ring), alicyclic hydrocarbon groups bonded to the end of a straight-chain or branched alicyclic hydrocarbon group, and alicyclic hydrocarbon groups present in the middle of a straight-chain or branched alicyclic hydrocarbon group. Examples of straight-chain or branched alicyclic hydrocarbon groups include those identical to the aforementioned straight-chain or branched alicyclic hydrocarbon groups. The aforementioned alicyclic hydrocarbon group preferably has 3 to 20 carbon atoms, and more preferably 3 to 12 carbon atoms. The aforementioned alicyclic hydrocarbon group can be polycyclic or monocyclic. As a monocyclic alicyclic hydrocarbon group, it is preferable to have two hydrogen atoms removed from a monocyclic alkane. As for the monocyclic alkane, it is preferable to have 3 to 6 carbon atoms, specifically examples include cyclopentane and cyclohexane. As a polycyclic alicyclic hydrocarbon group, it is preferable to have a group that removes two hydrogen atoms from the polycyclic alkane. As for the polycyclic alkane, it is preferable to have 7 to 12 carbon atoms. Specific examples include adamantane, norcamphene, isocamphene, tricyclic decane, tetracyclic dodecane, etc.

[0111] The aromatic hydrocarbon group that is the divalent hydrocarbon group in Va1 is a hydrocarbon group having an aromatic ring. This 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 is considered to exclude the number of carbon atoms in the substituents. Specific examples of the aromatic ring possessed by the aromatic hydrocarbon group include aromatic hydrocarbon rings of benzene, biphenyl, fentanyl, naphthalene, anthracene, phenanthrene, etc.; and aromatic heterocycles in which part of the carbon atoms constituting the aforementioned aromatic hydrocarbon rings are replaced by heteroatoms. Examples of heteroatoms in aromatic heterocycles include oxygen atoms, sulfur atoms, nitrogen atoms, etc. Specifically, examples of such aromatic hydrocarbon groups include groups (aryl groups) from which two hydrogen atoms have been removed from the aforementioned aromatic hydrocarbon ring; and groups (aryl groups) from which one hydrogen atom has been removed from the aforementioned aromatic hydrocarbon ring and one hydrogen atom is replaced by an alkyl group (e.g., aryl groups from which one hydrogen atom is further removed from an aryl group of benzyl, phenethyl, 1-naphthylmethyl, 2-naphthylmethyl, 1-naphthylethyl, 2-naphthylethyl, etc.). The number of carbon atoms in the aforementioned alkyl group (alkyl chain in an aryl alkyl group) is preferably 1 to 4, more preferably 1 to 2, and particularly preferably 1.

[0112] In the aforementioned formula (a1-1), Ra1 is the acid dissociative group shown in the above formula (a1-r-1) or (a1-r-2).

[0113] In the aforementioned formula (a1-2), the na2+1 valence hydrocarbon group 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; it can be saturated or unsaturated, but saturation is generally preferred. Examples of the aforementioned aliphatic hydrocarbon group include straight-chain or branched aliphatic hydrocarbon groups, aliphatic hydrocarbon groups containing rings in their structure, or groups formed by combining straight-chain or branched aliphatic hydrocarbon groups with aliphatic hydrocarbon groups containing rings in their structure. The aforementioned na2+1 valence is preferably 2 to 4, with 2 or 3 being more preferred.

[0114] In the aforementioned formula (a1-2), Ra2 is the acid dissociative group shown in the above general formula (a1-r-1) or (a1-r-3).

[0115] The following shows specific examples of the constituent units shown in the aforementioned formula (a1-1). In the following formulas, Rα represents a hydrogen atom, a methyl group, or a trifluoromethyl group.

[0116]

[0117]

[0118]

[0119]

[0120]

[0121]

[0122]

[0123]

[0124] (A1) The constituent unit (a1) of the component may be one or more types. As a constituent unit (a1), since it is easier to improve the characteristics (sensitivity, shape, etc.) in lithography using electron beams or EUV, the constituent unit shown in the aforementioned formula (a1-1) is preferred. Among them, it is particularly preferred that the constituent unit (a1) includes the constituent unit shown in the following general formula (a1-1-1).

[0125] [In the formula, Ra1” is an acid dissociative group represented by the general formula (a1-r2-1), (a1-r2-3) or (a1-r2-4).]

[0126] 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 description of the acid-dissociating groups shown in the general formulas (a1-r2-1), (a1-r2-3), or (a1-r2-4) is the same as above. Among them, since it is more suitable for use in EB or EUV applications due to increased reactivity, it is preferable to choose those with cyclic acid-dissociating groups.

[0127] In the aforementioned formula (a1-1-1), Ra1” is preferably an acid-dissociable group as shown in the general formula (a1-r2-1).

[0128] Relative to the total (100 mol%) of all constituent units constituting the (A1) component, the proportion of constituent unit (a1) in the (A1) component is preferably 5-80 mol%, preferably 10-75 mol%, even better 30-70 mol%, and particularly preferably 40-70 mol%. By making the proportion of constituent unit (a1) above or above the lower limit of the aforementioned preferred range, lithography properties such as sensitivity, resolution, and roughness are improved. On the other hand, when it is below the upper limit of the aforementioned preferred range, a balance can be achieved with other constituent units, and various lithography properties become good.

[0129] ≪Other Constituents≫ (A1) The component may also have the above-mentioned constituents (a1), as well as other constituents as necessary. Examples of other constituents include, for example, constituents containing a cyclic group containing lactone, a cyclic group containing -SO2-, or a cyclic group containing carbonate (a2); constituents containing an aliphatic hydrocarbon group containing a polar group (a3); constituents containing an aliphatic cyclic group that is not acid-dissociable (a4); constituents shown in the general formula (a10-1) described later (a10); constituents derived from styrene or styrene derivatives (st); constituents derived from hydroxystyrene or hydroxystyrene derivatives, etc.

[0130] Regarding the constituent unit (a2): The component (A1) may also have: the constituent unit (a1), and the constituent unit (a2) containing a cyclic group containing lactone, a cyclic group containing -SO2-, or a cyclic group containing carbonate (except for those equivalent to the constituent unit (a1)). When the cyclic group containing lactone, the cyclic group containing -SO2-, or the cyclic group containing carbonate of the constituent unit (a2) is used in the formation of the resist film, it is effective in improving the adhesion of the resist film to the substrate. Furthermore, by having the constituent unit (a2), for example, the acid diffusion length can be appropriately adjusted, thus improving the adhesion of the resist film to the substrate and appropriately adjusting the solubility during development, thereby improving the lithography properties.

[0131] "Lactone-containing cyclic group" refers to a cyclic group whose ring skeleton contains a ring (lactone ring) including -OC (=O)-. The lactone ring is counted as the first ring. If there is only a lactone ring, it is a monocyclic group. If there are other ring structures, regardless of their structure, it is called a polycyclic group. The lactone-containing cyclic group can be either a monocyclic group or a polycyclic group. There is no particular limitation on the lactone-containing cyclic group in the constitutive unit (a2), and any can be used. Specifically, groups represented by the following general formulas (a2-r-1) to (a2-r-7) can be given as examples.

[0132] [In the formula, Ra'21 are each independently a hydrogen atom, alkyl group, alkoxy group, halogen atom, haloalkyl group, hydroxyl group, -COOR", -OC(=O)R", hydroxyalkyl group or cyano group; R" is a hydrogen atom, alkyl group, cyclic group containing lactone, cyclic group containing carbonate, or cyclic group containing -SO2-; A" is an alkyl group, oxygen atom or sulfur atom with 1 to 5 carbon atoms that may contain oxygen atom (-O-) or sulfur atom (-S-); n' is an integer from 0 to 2; m' is 0 or 1.]

[0133] In the aforementioned general formulas (a2-r-1) to (a2-r-7), the alkyl group in Ra'21 is preferably an alkyl group having 1 to 6 carbon atoms. The alkyl group is preferably linear or branched. Examples include methyl, ethyl, propyl, isopropyl, n-butyl, isobutyl, tert-butyl, pentyl, isopentyl, neopentyl, and hexyl. Methyl or ethyl is preferred among these, with methyl being particularly preferred. The alkoxy group in Ra'21 is preferably an alkoxy group having 1 to 6 carbon atoms. The alkoxy group is preferably linear or branched. Examples include groups formed by linking an alkyl group (as exemplified in Ra'21) with an oxygen atom (-O-). The halogen atom in Ra'21 is preferably a fluorine atom. Examples of alkyl halides in Ra'21 include groups in which one or all of the hydrogen atoms of the alkyl group in Ra'21 are replaced by the aforementioned halogen atoms. Fluorinated alkyl groups are preferred as alkyl halides, and perfluoroalkyl groups are particularly preferred.

[0134] In Ra'21, in "-COOR" and "-OC(=O)R", R" is a hydrogen atom, an alkyl group, a cyclic group containing lactone, a cyclic group containing carbonate, or a cyclic group containing -SO2-. The alkyl group in "R" can be linear, branched, or cyclic, and the number of carbon atoms is preferably 1 to 15. When "R" is a linear or branched alkyl group, the number of carbon atoms is preferably 1 to 10, more preferably 1 to 5, and methyl or ethyl is particularly preferred. When "R" is a cyclic alkyl group, the number of carbon atoms is preferably 3 to 15, more preferably 4 to 12, and best of all is 5 to 10. Specifically, examples include groups from monocyclic alkanes that can or cannot be replaced by fluorine atoms or fluorinated alkyl groups, by removing one or more hydrogen atoms; and groups from polycyclic alkanes such as bicyclic alkanes, tricyclic alkanes, and tetracyclic alkanes, by removing one or more hydrogen atoms. More specifically, examples include groups that have removed one or more hydrogen atoms from monocyclic alkanes such as cyclopentane and cyclohexane; and groups that have removed one or more hydrogen atoms from polycyclic alkanes such as adamantane, norcamphene, isocamphene, tricyclic decane, and tetracyclic dodecane. As for the lactone-containing cyclic group in "R", examples include those identical to the groups represented by the aforementioned general formulas (a2-r-1) to (a2-r-7). As for the carbonate-containing cyclic group in "R", examples are identical to the carbonate-containing cyclic groups described later, specifically those represented by the general formulas (ax3-r-1) to (ax3-r-3). As for the cyclic group containing -SO2- in R”, it is the same as the cyclic group containing -SO2- described later, and specifically, the groups represented by the general formulas (a5-r-1) to (a5-r-4) can be given examples. As for the hydroxyalkyl group in Ra’21, it is preferred to have 1 to 6 carbon atoms, and specifically, groups in the aforementioned alkyl group in Ra’21 in which at least one hydrogen atom is replaced by a hydroxyl group can be given examples.

[0135] As Ra'21, each of the above-mentioned independent systems is preferably a hydrogen atom or a cyano group.

[0136] In the aforementioned general formulas (a2-r-2), (a2-r-3), and (a2-r-5), the alkyl group having 1 to 5 carbon atoms in A” is preferably a straight-chain or branched alkyl group, such as methylene, ethyl alkyl, n-propyl alkyl, and isopropyl alkyl. When the alkyl group contains oxygen or sulfur atoms, examples include the presence of -O- or -S- groups 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”, an alkyl group having 1 to 5 carbon atoms or -O- is preferred, an alkyl group having 1 to 5 carbon atoms is more preferred, and methylene is the most desirable.

[0137] The following are specific examples of the bases represented by the general formulas (a2-r-1) to (a2-r-7).

[0138]

[0139]

[0140] "Cyclic group containing -SO2-" refers to a cyclic group whose ring skeleton contains a ring containing -SO2-. Specifically, it is a cyclic group in which the sulfur atom (S) in -SO2- forms part of the ring skeleton of the cyclic group. The ring containing -SO2- in the ring skeleton is counted as the first ring. If there is only this ring, it is a monocyclic group. If there are other ring structures, it is called a polycyclic group regardless of its structure. Cyclic groups containing -SO2- can be monocyclic or polycyclic. Cyclic groups containing -SO2- are particularly preferred to contain a cyclic group in its ring skeleton containing -O-SO2-, that is, a cyclic group in which -OS- in -O-SO2- forms a sultone ring that forms part of the ring skeleton. More specifically, examples of cyclic bases containing -SO2- can be found in the general formulas (a5-r-1) to (a5-r-4) below.

[0141] [In the formula, Ra'51 are each independently a hydrogen atom, alkyl group, alkoxy group, halogen atom, haloalkyl group, hydroxyl group, -COOR", -OC(=O)R", hydroxyalkyl group or cyano group; R" is a hydrogen atom, alkyl group, cyclic group containing lactone, cyclic group containing carbonate, or cyclic group containing -SO2-; A" is an alkyl group, oxygen atom or sulfur atom with 1 to 5 carbon atoms that may contain oxygen atom or sulfur atom, and n' is an integer from 0 to 2.]

[0142] In the aforementioned general formulas (a5-r-1) to (a5-r-2), A” is the same as A” in the aforementioned general formulas (a2-r-2), (a2-r-3), and (a2-r-5). Examples of alkyl, alkoxy, halogen atom, haloalkyl, -COOR”, -OC(=O)R”, and hydroxyalkyl groups in Ra'51 are those that are the same as those exemplified in the description of Ra'21 in the aforementioned general formulas (a2-r-1) to (a2-r-7). Specific examples of the groups represented by the general formulas (a5-r-1) to (a5-r-4) are given below. In the formula, “Ac” represents acetyl.

[0143]

[0144]

[0145]

[0146] "Cyclic groups containing carbonates" refers to cyclic groups whose ring skeleton contains a ring (carbonate ring) including -OC (=O)-O-. The carbonate ring is counted as the first ring. In the case of having only a carbonate ring, it is a monocyclic group. In the case of having other ring structures, regardless of the structure, it is called a polycyclic group. Cyclic groups containing carbonates can be monocyclic or polycyclic. There are no particular limitations on the use of any type of cyclic group containing carbonates. Specifically, groups represented by the following general formulas (ax3-r-1) to (ax3-r-3) can be given as examples.

[0147] [In the formula, Ra'x31 are each independently a hydrogen atom, alkyl group, alkoxy group, halogen atom, haloalkyl group, hydroxyl group, -COOR", -OC(=O)R", hydroxyalkyl group or cyano group; R" is a hydrogen atom, alkyl group, cyclic group containing lactone, cyclic group containing carbonate, or cyclic group containing -SO2-; A" is an alkyl group, oxygen atom or sulfur atom with 1 to 5 carbon atoms that may contain oxygen atom or sulfur atom, p' is an integer from 0 to 3, and q' is 0 or 1.]

[0148] 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). Examples of alkyl groups, alkoxy groups, halogen atoms, alkyl halides, -COOR”, -OC(=O)R”, and hydroxyalkyl groups in Ra'31 are those exemplified in the descriptions of Ra'21 in the aforementioned general formulas (a2-r-1) to (a2-r-7). Specific examples of the groups represented by the general formulas (ax3-r-1) to (ax3-r-3) are given below.

[0149]

[0150] As a constituent unit (a2), it is preferably a constituent unit derived from an acrylate in which the hydrogen atom bonded to the carbon atom at the α-position can be replaced by a substituent. The constituent unit (a2) is preferably a constituent unit shown in the following general formula (a2-1).

[0151] [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. Ya21 is a single bond or a divalent linked group. La21 is -O-, -COO-, -CON(R')-, -OCO-, -CONHCO-, or -CONHCS-, where R' represents a hydrogen atom or a methyl group. However, when La21 is -O-, Ya21 does not become -CO-. Ra21 is a cyclic group containing lactones, a cyclic group containing carbonates, or a cyclic group containing -SO2-.]

[0152] In the aforementioned formula (a2-1), R is the same as described above. As R, hydrogen atom, alkyl group with 1 to 5 carbon atoms or fluorinated alkyl group with 1 to 5 carbon atoms are preferred, and hydrogen atom or methyl group is particularly preferred from the viewpoint of ease of industrial acquisition.

[0153] In the aforementioned formula (a2-1), there is no particular limitation on the divalent linking group in Ya21. Suitable examples include divalent hydrocarbon groups with substituents, divalent linking groups containing heteroatoms, etc.

[0154] ・Divalent hydrocarbon group that may have substituents: Ya21 is a case where a divalent hydrocarbon group that may have substituents can be an aliphatic hydrocarbon group or an aromatic hydrocarbon group.

[0155] ・・Ya21 The aliphatic hydrocarbon group refers to a hydrocarbon group that does not have aromaticity. The aliphatic hydrocarbon group can be saturated or unsaturated, but saturation is generally preferred. Examples of the aforementioned aliphatic hydrocarbon groups include linear or branched aliphatic hydrocarbon groups, or aliphatic hydrocarbon groups whose structure contains rings.

[0156] ・・・Straight-chain or branched 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 including methylene [-CH2-], ethyl [-(CH2)2-], trimethylene [-(CH2)3-], tetramethylene [-(CH2)4-], pentamethylene [-(CH2)5-], etc. The branched aliphatic hydrocarbon group preferably has 2 to 10 carbon atoms, more preferably 3 to 6 carbon atoms, even more preferably 3 or 4 carbon atoms, and most preferably 3 carbon atoms. As a branched aliphatic hydrocarbon group, branched alkyl groups are preferred. Specific 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, a straight-chain alkyl group with 1 to 5 carbon atoms is preferred.

[0157] The aforementioned straight-chain or branched 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.

[0158] ・・・Aliphatic hydrocarbon groups containing rings in the structure Examples of aliphatic hydrocarbon groups containing rings in the structure include cyclic aliphatic hydrocarbon groups containing heteroatom substituents (groups with two hydrogen atoms removed from the aliphatic hydrocarbon ring), groups where the aforementioned cyclic aliphatic hydrocarbon group is bonded to the end of a straight-chain or branched aliphatic hydrocarbon group, and groups where the aforementioned cyclic aliphatic hydrocarbon group exists in the middle of a straight-chain or branched aliphatic hydrocarbon group. Examples of straight-chain or branched aliphatic hydrocarbon groups are as described above. Cyclic aliphatic hydrocarbon groups preferably have 3 to 20 carbon atoms, and more preferably 3 to 12 carbon atoms. Cyclic aliphatic hydrocarbon groups can be polycyclic or monocyclic. For monocyclic alicyclic hydrocarbon groups, groups with two hydrogen atoms removed from a monocyclic alkane are preferred. As for the monocyclic alkane, those with 3 to 6 carbon atoms are preferred, and specific examples include cyclopentane and cyclohexane. As for the polycyclic alicyclic hydrocarbon group, those with two hydrogen atoms removed from the polycyclic alkane are preferred, and those with 7 to 12 carbon atoms are preferred, and specific examples include adamantane, norcamphene, isocamphene, tricyclic decane, tetracyclic dodecane, etc.

[0159] 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 alkyl groups used as substituents, alkyl groups having 1 to 5 carbon atoms are preferred, with methyl, ethyl, propyl, n-butyl, and tert-butyl being more preferred. Among the alkoxy groups used as substituents, alkoxy groups having 1 to 5 carbon atoms are preferred, with methoxy, ethoxy, n-propoxy, iso-propoxy, n-butoxy, and tert-butoxy being more preferred, and methoxy and ethoxy being the most desirable. Among the halogen atom used as substituents, fluorine atoms are preferred. Among the alkyl halide used as substituents, groups in which one or all of the hydrogen atoms of the aforementioned alkyl group are replaced by the aforementioned halogen atom can be examples. A portion of the carbon atoms constituting the ring structure of the cyclic aliphatic hydrocarbon group may also be replaced by substituents containing heteroatoms. The preferred substituents for the heteroatom-containing substituents are -O-, -C(=O)-O-, -S-, -S(=O)2-, and -S(=O)2-O-.

[0160] ・・Ya21 The aromatic hydrocarbon group is a hydrocarbon group having at least one aromatic ring. There are no particular limitations as long as the aromatic ring is a cyclic conjugated system with 4n+2 π electrons; it can be monocyclic or polycyclic. The number of carbon atoms in the aromatic ring is preferably 5 to 30, more preferably 5 to 20, even more preferably 6 to 15, and particularly preferably 6 to 12. However, this number of carbon atoms is considered to exclude the number of carbon atoms in the substituents. Specific examples of aromatic rings include aromatic hydrocarbon rings of benzene, naphthalene, anthracene, phenanthrene, etc.; and aromatic heterocycles in which a portion of the carbon atoms constituting the aforementioned aromatic hydrocarbon rings are replaced by heteroatoms. Examples of heteroatoms in aromatic heterocycles include oxygen atoms, sulfur atoms, nitrogen atoms, etc. Specific examples of aromatic heterocycles include pyridine rings, thiophene rings, etc. Specifically, examples of aromatic hydrocarbon groups include groups (aryl or heteroaryl) that have had two hydrogen atoms removed from the aforementioned aromatic hydrocarbon ring or aromatic heterocycle; groups (e.g., biphenyl, benzo[a], etc.) that have had two hydrogen atoms removed from the aromatic compound containing two or more aromatic rings; and groups (aryl or heteroaryl) in which one hydrogen atom of the group (aryl or heteroaryl) has been replaced by an alkyl group (e.g., removing one hydrogen atom from an aryl group in arylalkyl groups such as benzyl, phenethyl, 1-naphthylmethyl, 2-naphthylmethyl, 1-naphthylethyl, 2-naphthylethyl, etc.). The number of carbon atoms in the alkyl group bonded to the aforementioned aryl or heteroaryl group is preferably 1 to 4, more preferably 1 to 2, and particularly preferably 1.

[0161] The hydrogen atoms of the aforementioned aromatic hydrocarbon group can also be replaced by substituents. For example, the hydrogen atoms on the aromatic ring bonded to the aromatic hydrocarbon group can also be replaced by substituents. Examples of such substituents include alkyl groups, alkoxy groups, halogen atoms, alkyl halides, and hydroxyl groups. Among the alkyl groups used as the aforementioned substituents, alkyl groups with 1 to 5 carbon atoms are preferred, and methyl, ethyl, propyl, n-butyl, and tert-butyl are more preferred. Examples of alkoxy groups, halogen atoms, and alkyl halides used as the aforementioned substituents include substituents that replace the hydrogen atoms of the aforementioned cyclic aliphatic hydrocarbon group.

[0162] ・Divalent linker containing heteroatoms: Ya21 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)- (H can also be replaced by alkyl, acetylated, or other 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 group represented by -Y21-OC(=O)-Y22- or -Y21-S(=O)2-O-Y22- [where Y21 and Y22 are each independently divalent hydrocarbon groups that can have substituents, O is an oxygen atom, and m” is an integer from 0 to 3], etc. In the case of the aforementioned divalent linking group containing heteroatoms being -C(=O)-NH-, -C(=O)-NH-C(=O)-, -NH-, or -NH-C(=NH)-, the H atoms can also be replaced by substituents such as alkyl or acetyl groups. These substituents (alkyl, acetyl, etc.) are preferably composed of 1 to 10 carbon atoms, 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 that can have substituents. Examples of such divalent hydrocarbon groups include those exemplified in the description of Ya21 as a divalent linking group (divalent hydrocarbon groups that can have substituents). For Y21, a straight-chain aliphatic hydrocarbon group is preferred, a straight-chain alkyl group is more preferred, a straight-chain alkyl group with 1 to 5 carbon atoms is even more preferred, and methylene or ethyl groups are particularly preferred. Y22 is preferably a straight-chain or branched aliphatic hydrocarbon group, with methylene, ethyl, or alkylmethylene being more preferred. The alkyl group in this 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 methyl is the most desirable. In the group represented by formula -[Y21-C(=O)-O]m”-Y22-, m” is an integer from 0 to 3, preferably an integer from 0 to 2, more preferably 0 or 1, and especially preferably 1. That is, the group represented by formula -Y21-C(=O)-O-Y22- is particularly preferred. Among them, the group represented by formula -(CH2)a'-C(=O)-O-(CH2)b'- is also preferred.In this formula, a' is 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. b' is 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.

[0163] Among the above, Ya21 is preferably a single bond, an ester bond [-C(=O)-O-], an ether bond (-O-), a straight-chain or branched alkyl group, or a combination thereof.

[0164] In the aforementioned formula (a2-1), Ra21 is a cyclic group containing lactone, a cyclic group containing -SO2-, or a cyclic group containing carbonate. As the cyclic group containing lactone, the cyclic group containing -SO2-, and the cyclic group containing carbonate in Ra21, suitable examples can be the groups represented by the aforementioned general formulas (a2-r-1) to (a2-r-7), the groups represented by the general formulas (a5-r-1) to (a5-r-4), and the groups represented by the general formulas (ax3-r-1) to (ax3-r-3). Among them, the cyclic group containing lactone or -SO2- containing cyclic group is preferred, and the group represented by the aforementioned general formula (a2-r-1), (a2-r-2), (a2-r-6) or (a5-r-1) is more preferred, and the group represented by the aforementioned general formula (a2-r-2) or (a5-r-1) is even more preferred. Specifically, the 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), and (r-sl-1-18) is preferred, the base represented by any of the aforementioned chemical formulas (r-lc-2-1)~(r-lc-2-18) and (r-sl-1-1) is even more preferred, and the base represented by any of the aforementioned chemical formulas (r-lc-2-1), (r-lc-2-12), and (r-sl-1-1) is even more preferred.

[0165] (A1) The constituent unit (a2) may be one type or two or more types. When (A1) has a constituent unit (a2), the proportion of the constituent unit (a2) relative to the total (100 mol%) of all constituent units constituting the (A1) component is preferably 5-60 mol%, preferably 10-60 mol%, preferably 20-60 mol%, and preferably 30-60 mol%. When the proportion of the constituent unit (a2) is made above the lower limit of the optimum, the effects of containing the constituent unit (a2) can be fully obtained through the aforementioned effects. When it is below the upper limit, a balance with other constituent units can be achieved, and various photolithography properties become good.

[0166] Regarding the constituent unit (a3): Component (A1) may also have a constituent unit (a1), and a constituent unit (a3) ​​containing a polar aliphatic hydrocarbon group (except for those equivalent to constituent unit (a1) or constituent unit (a2)). By having a constituent unit (a3), the hydrophilicity of component (A) is enhanced, and resolution is improved. Furthermore, the acid diffusion length can be appropriately adjusted.

[0167] Examples of polar groups include hydroxyl, cyano, carboxyl, and alkyl groups in which one hydrogen atom is partially replaced by a fluorine atom, with hydroxyl being particularly preferred. Examples of aliphatic hydrocarbon groups include linear or branched hydrocarbon groups (preferably alkyl groups) having 1 to 10 carbon atoms, or cyclic aliphatic hydrocarbon groups (cyclic groups). The cyclic group can be monocyclic or polycyclic, and for example, it is appropriate to select from the majority of resins proposed for use in ArF excimer laser resist compositions.

[0168] When the cyclic group is a monocyclic group, the number of carbon atoms is preferably 3 to 10. Among these, it is preferable to use a unit derived from an acrylate containing a hydroxyl alkyl group in which one of the hydrogen atoms of a hydroxyl, cyano, carboxyl, or alkyl group is partially replaced by a fluorine atom. Examples of such a 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. Of 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.

[0169] In the case where the cyclic group is a polycyclic group, the number of carbon atoms in the polycyclic group is preferably 7 to 30. Among these, it is preferable to use a constituent unit derived from an acrylate of an aliphatic polycyclic group containing a hydroxyl alkyl group, in which one of the hydrogen atoms of a hydroxyl, cyano, carboxyl, or alkyl group is partially replaced by a fluorine atom. Examples of such polycyclic groups include those with two or more hydrogen atoms removed from bicyclic alkanes, tricyclic alkanes, tetracyclic alkanes, etc. Specifically, examples include groups with two or more hydrogen atoms removed from polycyclic alkanes such as adamantane, norcamphene, isocamphene, tricyclic decane, and tetracyclic dodecane. Among these polycyclic groups, those with two or more hydrogen atoms removed from adamantane, those with two or more hydrogen atoms removed from norcamphene, and those with two or more hydrogen atoms removed from tetracyclic dodecane are industrially preferred.

[0170] As a constituent unit (a3), any unit may be used as long as it contains an aliphatic hydrocarbon group with a polar group, without particular limitation. As a constituent unit (a3), it is preferable to be a constituent unit derived from an acrylate in which the hydrogen atom bonded to the α-carbon atom can be replaced by a substituent, and to be a constituent unit containing an aliphatic hydrocarbon group with a polar group. As a constituent unit (a3), when the hydrocarbon group in the aliphatic hydrocarbon group containing the polar group is a straight-chain or branched hydrocarbon group with 1 to 10 carbon atoms, it is preferable to be a constituent unit derived from a hydroxyethyl ester of acrylic acid. Furthermore, as a constituent unit (a3), when the aliphatic hydrocarbon group containing a polar group is a polycyclic group, the constituent units shown in formula (a3-1), formula (a3-2), and formula (a3-3) are preferred; when it is a monocyclic group, the constituent unit shown in formula (a3-4) is preferred.

[0171] [In the formula, R is the same as above, j is an integer from 1 to 3, k is an integer from 1 to 3, t' is an integer from 1 to 3, l is an integer from 0 to 5, and s is an integer from 1 to 3.]

[0172] In formula (a3-1), j is preferably 1 or 2, with 1 being more preferred. When j is 2, it is preferred that the hydroxyl group is bonded to the 3-position or the 5-position of the adamantyl group. When j is 1, it is preferred that the hydroxyl group is bonded to the 3-position of the adamantyl group. j is preferably 1, with the hydroxyl group bonded to the 3-position of the adamantyl group being particularly preferred.

[0173] 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 norcamphene group.

[0174] In formula (a3-3), t' is preferably 1. l is preferably 1. s is preferably 1. These systems are preferably bonded to the carboxyl terminus of acrylic acid with a 2-norcamphenicol or 3-norcamphenicol. Fluorinated alkyl alcohols are preferably bonded to the 5 or 6 position of the norcamphenicol.

[0175] In formula (a3-4), t' is preferably 1 or 2. l is preferably 0 or 1. s is preferably 1. Fluorinated alkyl alcohols are preferably bonded to the 3 or 5 position of the cyclohexyl group.

[0176] (A1) The constituent unit (a3) ​​may be one type or two or more types. When (A1) contains a constituent unit (a3), the proportion of the constituent unit (a3) ​​relative to the total (100 mol%) of all constituent units constituting the (A1) component is preferably 1 to 30 mol%, more preferably 2 to 25 mol%, and even more preferably 5 to 20 mol%. By making the proportion of the constituent unit (a3) ​​above the lower limit of the optimum, the effects of containing the constituent unit (a3) ​​can be fully obtained through the aforementioned effects. When it is below the upper limit of the optimum, a balance with other constituent units can be achieved, and various photolithography properties become good.

[0177] Regarding the constituent unit (a4): In addition to the constituent unit (a1), component (A1) may also have a constituent unit (a4) containing a non-acid-dissociable aliphatic cyclic group. By having the constituent unit (a4), the dry etching resistance of the resist pattern formed by component (A1) is improved. Furthermore, the hydrophobicity of component (A) is improved. The improvement in hydrophobicity is particularly helpful in solvent development processes, as it contributes to improvements in resolution, resist pattern shape, etc. The "non-acid-dissociable cyclic group" in the constituent unit (a4) refers to the 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 by the constituent unit or component (B) due to exposure).

[0178] As a constituent unit (a4), it is preferable to use a constituent unit derived from an acrylate containing a non-acid-dissociable aliphatic cyclic group, for example. The cyclic group can be one of the most commonly known resin components used as resist compositions for ArF excimer lasers, KrF excimer lasers (preferably ArF excimer lasers), etc. From the viewpoint of easy industrial availability, it is particularly preferable to use at least one selected from tricyclodecyl, adamantyl, tetracyclododecyl, isocamphenyl, and norcamphenyl. These polycyclic groups may also have a straight-chain or branched alkyl group having 1 to 5 carbon atoms as a substituent. Specifically, the constituent units (a4) can be exemplified by the constituent units represented by the following general formulas (a4-1) to (a4-7).

[0179] [In the formula, Rα is the same as described above.]

[0180] (A1) The constituent unit (a4) may be one type or two or more types. When (A1) contains a constituent unit (a4), the proportion of the constituent unit (a4) relative to the total number of all constituent units constituting (A1) (100 mol%) is preferably 1 to 40 mol%, and more preferably 5 to 20 mol%. By setting the proportion of the constituent unit (a4) to a lower limit or above the preferred value, the effects of containing the constituent unit (a4) can be fully obtained. On the other hand, by setting it to a lower limit or below the preferred value, it becomes easier to achieve a balance with other constituent units.

[0181] Regarding the constituent unit (a10): The constituent unit (a10) is the constituent unit shown in the following general formula (a10-1).

[0182] [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 have substituents. nax1 is an integer of 1 or more.]

[0183] In the aforementioned formula (a10-1), R is a hydrogen atom, an alkyl group having 1 to 5 carbon atoms, or a haloalkyl group having 1 to 5 carbon atoms. R is the same as R in the aforementioned formula (a0-1-1).

[0184] In the aforementioned formula (a10-1), Yax1 is a single bond or a divalent linked group. In the aforementioned chemical formula, there is no particular limitation on the divalent linked group in Yax1; suitable examples include divalent hydrocarbon groups that may have substituents, divalent linked groups containing heteroatoms, etc. As for the divalent linked group in Yax1, examples such as the divalent linked group in Ya21 of the aforementioned formula (a2-1) are also suitable. Among these, as Yax1, single bonds, ester bonds [-C(=O)-O-, -OC(=O)-], ether bonds (-O-), straight-chain or branched alkyl groups, or combinations thereof are preferred, with single bonds or ester bonds [-C(=O)-O-, -OC(=O)-] being more preferred.

[0185] In the aforementioned formula (a10-1), Wax1 is an aromatic hydrocarbon group that may have substituents. Examples of aromatic hydrocarbon groups in Wax1 include groups that have (nax1+1) hydrogen atoms removed from an aromatic ring that may have substituents. The aforementioned aromatic ring is not particularly limited as long as it is a cyclic conjugated system with 4n+2 π electrons; it can be monocyclic or polycyclic. The number of carbon atoms in the aromatic ring is preferably 5 to 30, more preferably 5 to 20, even more preferably 6 to 15, and particularly preferably 6 to 12. Specific examples of such aromatic rings include aromatic hydrocarbon rings of benzene, naphthalene, anthracene, phenanthrene, etc.; and aromatic heterocycles in which a portion of the carbon atoms constituting the aforementioned aromatic hydrocarbon ring is replaced by heteroatoms. Examples of heteroatoms in aromatic heterocycles include oxygen atoms, sulfur atoms, nitrogen atoms, etc. Examples of aromatic heterocycles include pyridine rings and thiophene rings. Examples of aromatic hydrocarbon groups in Wax1 include groups formed by removing (nax1+1) hydrogen atoms from aromatic compounds containing aromatic rings that may have two or more substituents (e.g., biphenyl, naphthalene, etc.). Preferably, Wax1 is formed by removing (nax1+1) hydrogen atoms from benzene, naphthalene, anthracene, or biphenyl; more preferably, from benzene or naphthalene; and even more preferably, from benzene.

[0186] The aromatic hydrocarbon group in Wax1 may or may not have substituents. Examples of substituents include alkyl groups, alkoxy groups, halogen atoms, and alkyl halides. Examples of alkyl groups, alkoxy groups, halogen atoms, and alkyl halides that serve as the aforementioned substituents are those similar to those exemplified as substituents for cyclic aliphatic hydrocarbon groups in Wax1. The aforementioned substituents are preferably straight-chain or branched alkyl groups having 1 to 5 carbon atoms, more preferably straight-chain or branched alkyl groups having 1 to 3 carbon atoms, and even more preferably ethyl or methyl, with methyl being particularly preferred. The aromatic hydrocarbon group in Wax1 is preferably unsubstituented.

[0187] In the aforementioned formula (a10-1), nax1 is an integer greater than or equal to 1, preferably an integer from 1 to 10, more preferably an integer from 1 to 5, even more preferably 1, 2 or 3, and especially preferably 1 or 2.

[0188] The following shows specific examples of the constituent unit (a10) shown in the aforementioned formula (a10-1). In the following formulas, Rα represents a hydrogen atom, a methyl group, or a trifluoromethyl group.

[0189]

[0190]

[0191]

[0192] The constituent unit (a10) of component (A1) may be one type or two or more types. When component (A1) has a constituent unit (a10), the proportion of the constituent unit (a10) in component (A1) is preferably 10-80 mol%, more preferably 20-70 mol%, more preferably 30-60 mol%, and especially preferably 30-50 mol%, relative to the total of all constituent units constituting component (A1). By setting the proportion of the constituent unit (a10) above or above the aforementioned preferred lower limit, it becomes easier to improve sensitivity. On the other hand, by setting the proportion of the constituent unit (a10) below or above the aforementioned preferred upper limit, it becomes easier to achieve a balance with other constituent units.

[0193] Regarding the constituent unit (st): The constituent unit (st) is a constituent unit derived from styrene or styrene derivatives. "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 derivatives" means a constituent unit formed by the cleavage of the vinyl double bond of styrene derivatives (but excluding those equivalent to constituent unit (a10)).

[0194] "Styrene derivatives" means compounds in which at least some of the hydrogen atoms of styrene are replaced by substituents. Examples of styrene derivatives include those in which the α-hydrogen atom of styrene is replaced by a substituent, those in which one or more hydrogen atoms of the benzene ring of styrene are replaced by a substituent, and those in which the α-hydrogen atom of styrene and one or more hydrogen atoms of the benzene ring are replaced by substituents.

[0195] 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, straight-chain or branched alkyl groups having 1 to 5 carbon atoms are preferred, specifically including methyl, ethyl, propyl, isopropyl, n-butyl, isobutyl, tert-butyl, pentyl, isopentyl, neopentyl, etc. The aforementioned alkyl halides having 1 to 5 carbon atoms are groups in which one or all of the hydrogen atoms of the aforementioned alkyl groups having 1 to 5 carbon atoms are replaced by halogen atoms. Fluorine atoms are particularly preferred as the halogen atom. As a substituent for the α-hydrogen atom of styrene, an alkyl group with 1 to 5 carbon atoms or a fluorinated alkyl group with 1 to 5 carbon atoms is preferred, and an alkyl group with 1 to 3 carbon atoms or a fluorinated alkyl group with 1 to 3 carbon atoms is even more preferred. From the point of view of ease of industrial availability, methyl is even more preferred.

[0196] Examples of substituents that replace the hydrogen atoms on the benzene ring of styrene include alkyl groups, alkoxy groups, halogen atoms, and alkyl halides. Among the alkyl groups used as the aforementioned substituents, alkyl groups having 1 to 5 carbon atoms are preferred, with methyl, ethyl, propyl, n-butyl, and tert-butyl being more preferred. Among the alkoxy groups used as 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 more preferred, and methoxy and ethoxy being even more preferred. Among the halogen atoms used as the aforementioned substituents, fluorine atoms are preferred. Among the alkyl halides used as the aforementioned substituents, examples include groups in which one or all of the hydrogen atoms of the aforementioned alkyl group are replaced by the aforementioned halogen atom. Among the substituents that replace the hydrogen atoms on the benzene ring of styrene, alkyl groups having 1 to 5 carbon atoms are preferred, with methyl or ethyl being more preferred, and methyl being even more preferred.

[0197] 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 of 1 to 5 carbon atoms or a halogenated alkyl group of 1 to 5 carbon atoms. 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. It is even more preferable to be a constituent unit derived from styrene.

[0198] (A1) The constituent unit (st) may be one type or two or more types. When the (A1) component has a constituent unit (st), the proportion of the constituent unit (st) relative to the total (100 mol%) of all constituent units constituting the (A1) component is preferably 1 to 30 mol%, and more preferably 3 to 20 mol%.

[0199] The (A1) component contained in the inhibitor composition can be used alone or in combination with two or more. In the inhibitor composition of this embodiment, the (A1) component can be a polymer compound having a repeating structure of constituent unit (a1), and preferably a polymer compound having a repeating structure of constituent unit (a1) and constituent unit (a10). As the (A1) component, suitable examples above include polymer compounds composed of repeating structures of constituent unit (a1) and constituent unit (a10); and polymer compounds composed of repeating structures of constituent unit (a1), constituent unit (a10), and constituent unit (a3).

[0200] In a polymer compound having a repeating structure of constituent units (a1) and constituent units (a10), the proportion of constituent unit (a1) relative to the total number of constituent units constituting the polymer compound (100 mol%) is preferably 10-90 mol%, more preferably 20-80 mol%, even more preferably 30-70 mol%, and particularly preferably 40-70 mol%. In a polymer compound having a repeating structure of constituent units (a1) and constituent units (a10), the proportion of constituent unit (a10) relative to the total number of constituent units constituting the polymer compound (100 mol%) is preferably 10-90 mol%, more preferably 20-80 mol%, even more preferably 30-70 mol%, and particularly preferably 30-60 mol%.

[0201] In a polymer compound having a repeating structure of constituent units (a1), (a10), and (a3), the proportion of constituent unit (a1) relative to the total number of constituent units constituting the polymer compound (100 mol%) is preferably 20-80 mol%, more preferably 30-70 mol%, even more preferably 40-70 mol%, and particularly preferably 45-65 mol%. In a polymer compound having a repeating structure of constituent units (a1), (a10), and (a3), the proportion of constituent unit (a10) relative to the total number of constituent units constituting the polymer compound (100 mol%) is preferably 10-70 mol%, more preferably 20-60 mol%, even more preferably 20-50 mol%, and particularly preferably 25-45 mol%. Furthermore, in a polymer compound having a repeating structure of constituent units (a1), (a10), and (a3), the proportion of constituent unit (a3) ​​relative to the total number of constituent units constituting the polymer compound (100 mol%) is preferably 1 to 30 mol%, more preferably 5 to 25 mol%, even more preferably 5 to 20 mol%, and particularly preferably 5 to 15 mol%.

[0202] The molar ratio (constituent unit (a1): constituent unit (a10)) of the polymer compound is preferably 2:8 to 8:2, preferably 3:7 to 7:3, and even more preferably 4:6 to 6:4.

[0203] The (A1) component can be manufactured by dissolving the monomers from which each constituent unit is derived in a polymerization solvent and adding a free radical polymerization initiator such as azobisisobutyronitrile (AIBN) or dimethyl azobisisobutyrate (e.g., V-601) to the solvent. Alternatively, the (A1) component can be manufactured by dissolving the monomers from which the constituent unit (a1) is derived, along with monomers from other constituent units (e.g., constituent unit (a10)) as necessary, in a polymerization solvent and adding a free radical polymerization initiator as described above to the solvent. Furthermore, during polymerization, a -C(CF3)2-OH group can be introduced at the end by using a chain transfer agent such as HS-CH2-CH2-CH2-C(CF3)2-OH. Thus, copolymers in which hydroxyalkyl groups, in which one of the hydrogen atoms of an alkyl group is partially replaced by fluorine atoms, effectively reduce development defects or LER (line edge roughness: unevenness of the line sidewalls).

[0204] The weight-average molecular weight (Mw) of component (based on polystyrene using gel permeation chromatography (GPC)) is not particularly limited, but is preferably 1,000 to 50,000, more preferably 2,000 to 30,000, and even more preferably 3,000 to 20,000. When the Mw of component (A1) is below the upper limit of this range, it has sufficient solubility in the inhibitor solvent required for use as an inhibitor; when it is above the lower limit of this range, it has good resistance to dry etching or good inhibitor pattern profile shape. 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 particularly preferably 1.0 to 2.0. Furthermore, Mn represents the number-average molecular weight.

[0205] ・Regarding component (A2), the resist composition of this embodiment may also be used in conjunction with a substrate component (hereinafter referred to as "component (A2)") that does not affect the solubility of the developer due to the action of acid, unlike component (A1). There are no particular limitations on component (A2), and it may be selected from most of the previously known substrate components used as chemically amplifying resist compositions. Component (A2) may be a single polymeric compound or a low-molecular-weight compound, or two or more may be used in combination.

[0206] The proportion of (A1) component in (A) component 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. When the proportion is 25% by mass or more, it becomes easier to form a resist pattern with excellent resist properties such as high sensitivity and improved resolution and roughness.

[0207] In the resist composition of this embodiment, the content of component (A) can be adjusted according to the desired resist film thickness, etc.

[0208] <Acid Generator Component (B)> The inhibitor composition of this embodiment contains: an acid generator component (B) that generates acid upon exposure. Component (B) comprises a compound (B0) shown in the following general formula (b0) (hereinafter also referred to as "(B0) component").

[0209] ≪(B0)Component≫ (B0)Component is a compound represented by the following general formula (b0).

[0210] [Where, Mb+ is the aforementioned cation (CO). Xb- is the relative anion.]

[0211] {Cation part} In the aforementioned general formula (b0), Mb+ is the aforementioned cation (CO).

[0212] {Anionic part} In the aforementioned general formula (b0), Xb- is a relative anion. There are no particular restrictions on Xb-, and the anionic part of an acid generating agent proposed for use as a chemical amplification inhibitor component can be used.

[0213] As Xb-, examples include the anions shown in the following general formulas (b-1-an), (b-2-an), or (b-3-an).

[0214] [In the formula, R101 and R104~R108 are each independently a cyclic group that may have substituents, a chain-like alkyl group that may have substituents, or a chain-like 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-.]

[0215] ・In the anionic formula (b-1-an) shown in formula (b-1-an), 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.

[0216] Cyclic groups that may have substituents: The cyclic group is preferably a cyclic hydrocarbon group, which can 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 can be saturated or unsaturated, but saturated is generally preferred.

[0217] 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 refers to the number of carbon atoms excluding those in the substituents. Specific examples of the aromatic ring possessed by the aromatic hydrocarbon group in R101 include benzene, benzo[a], naphthalene, anthracene, phenanthrene, biphenyl, or aromatic heterocycles in which a portion of the carbon atoms constituting such aromatic rings is replaced by heteroatoms. Examples of heteroatoms in aromatic heterocycles include oxygen atoms, sulfur atoms, and nitrogen atoms. Specifically, the aromatic hydrocarbon group in R101 can be exemplified by groups in which one hydrogen atom has been removed from the aforementioned aromatic ring (aryl: for example, phenyl, naphthyl, etc.), or groups in which one hydrogen atom of the aforementioned aromatic ring is replaced by an alkyl group (for example, arylalkyl groups such as benzyl, phenethyl, 1-naphthylmethyl, 2-naphthylmethyl, 1-naphthylethyl, 2-naphthylethyl, etc.). The aforementioned alkyl group (the alkyl chain in the arylalkyl group) preferably has 1 to 4 carbon atoms, more preferably 1 to 2, and particularly preferably 1.

[0218] The cyclic aliphatic hydrocarbon group in R101 can be exemplified by an aliphatic hydrocarbon group whose structure contains a ring. The cyclic aliphatic hydrocarbon group in R101 preferably has 3 to 50 carbon atoms, preferably 4 to 45 carbon atoms, and more preferably 5 to 40 carbon atoms. Examples of aliphatic hydrocarbon groups containing a ring in this structure include alicyclic hydrocarbon groups (groups with one hydrogen atom removed from an aliphatic hydrocarbon ring), alicyclic hydrocarbon groups bonded to the end of a straight-chain or branched aliphatic hydrocarbon group, and alicyclic hydrocarbon groups present in the middle of a straight-chain or branched 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 be a polycyclic group or a monocyclic group. As a monocyclic alicyclic hydrocarbon group, it is preferable to have one or more hydrogen atoms removed from a monocyclic alkane. The monocyclic alkane is preferably composed of 3 to 6 carbon atoms, such as cyclopentane and cyclohexane. The polycyclic alicyclic hydrocarbon group is preferably composed of a group from which one or more hydrogen atoms have been removed from the polycyclic alkane, and the polycyclic alkane is preferably composed of 7 to 30 carbon atoms. Among these, polycyclic alkanes with a cross-linked ring system, such as adamantane, norcamphene, isocamphene, tricyclodecane, and tetracyclododecane, and polycyclic alkanes with a condensed ring system, such as cyclic groups with a steroid skeleton, are also preferred.

[0219] 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 a polycyclic alkane, and is more preferably a group that has removed one hydrogen atom from a polycyclic alkane. It is more preferably adamantyl or norbornel, and is especially preferred to be adamantyl.

[0220] The linear aliphatic hydrocarbon group that can be bonded to an 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 an 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 aliphatic hydrocarbon group, branched alkyl groups are preferred. Specific 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, a straight-chain alkyl group with 1 to 5 carbon atoms is preferred.

[0221] Furthermore, the cyclic hydrocarbon group in R101 may also contain heteroatoms, such as heterocycles. Specifically, examples include the lactone-containing cyclic groups represented by the aforementioned general formulas (a2-r-1) to (a2-r-7), the -SO2- containing cyclic groups represented by the aforementioned general formulas (a5-r-1) to (a5-r-4), and other heterocyclic groups represented by the following chemical formulas (r-hr-1) to (r-hr-16). In the formulas, * indicates a bond at the Y101 in formula (b-1-an).

[0222]

[0223] Examples of substituents in the cyclic group of R101 include alkyl, alkoxy, halogen atom, alkyl halide, hydroxyl, carbonyl, and nitro groups. Among the alkyl groups used as 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 groups used as substituents, alkoxy groups with 1 to 5 carbon atoms are preferred, with methoxy, ethoxy, n-propoxy, iso-propoxy, n-butoxy, and tert-butoxy being more preferred, and methoxy and ethoxy being the most desirable. Among the halogen atom used as substituents are fluorine, chlorine, bromine, and iodine atoms, with fluorine being the most desirable. Among the alkyl halide used as substituents are alkyl groups with 1 to 5 carbon atoms, such as methyl, ethyl, propyl, n-butyl, and tert-butyl groups, where one or all of the hydrogen atoms are replaced by the aforementioned halogen atom. The carbonyl group, as a substituent, is a group that replaces the methylene (-CH2-) that constitutes the cyclic hydrocarbon group.

[0224] The cyclic hydrocarbon group in R101 may also be a condensed cyclic group comprising a condensed ring of an aliphatic hydrocarbon ring and an aromatic ring. Examples of the aforementioned condensed ring include, for example, a polycyclic alkane having one or more aromatic rings condensed on it. Specific examples of the aforementioned cross-linked polycyclic alkane include bicyclic alkanes such as bicyclic [2.2.1]heptane (norbornene) and bicyclic [2.2.2]octane. As for the aforementioned condensed cyclic group, a group comprising a condensed ring of two or three aromatic rings condensed on it is preferred, and a group comprising a condensed cyclic group of two or three aromatic rings condensed on it is even more preferred. Specific examples of the condensed cyclic group in R101 include those shown in the following formulas (r-br-1) to (r-br-2). In this case, * indicates the bonding point with Y101 in equation (b-1-an).

[0225]

[0226] Substituents that may be present in the condensed cyclic group of R101 include, for example, alkyl, alkoxy, halogen atom, halogenated alkyl, hydroxyl, carbonyl, nitro, aromatic hydrocarbon group, alicyclic hydrocarbon group, etc. Examples of alkyl, alkoxy, halogen atom, and halogenated alkyl groups that serve as substituents for the aforementioned condensed cyclic group are those that are the same as those used as substituents for the cyclic group in R101. Examples of aromatic hydrocarbon groups that serve as substituents for the aforementioned condensed cyclic group include, for example, 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 represented by the formulas (r-hr-1) to (r-hr-6) above. Examples of alicyclic hydrocarbon groups that can be used as substituents for the aforementioned condensed cyclic groups include: groups that remove one hydrogen atom from monocyclic alkanes such as cyclopentane and cyclohexane; groups that remove one hydrogen atom from polycyclic alkanes such as adamantane, norcamphene, isocamphene, tricyclic decane, and tetracyclic dodecane; cyclic groups containing lactones represented by the aforementioned general formulas (a2-r-1) to (a2-r-7); cyclic groups containing -SO2- represented by the aforementioned general formulas (a5-r-1) to (a5-r-4); and heterocyclic groups represented by the aforementioned formulas (r-hr-7) to (r-hr-16).

[0227] The cyclic hydrocarbon group in R101 may also be a group consisting of two or more aliphatic rings and / or aromatic rings linked by straight-chain or branched aliphatic hydrocarbon groups that may have substituents. The methylene (-CH2-) constituting the aliphatic hydrocarbon chain of the straight-chain or branched aliphatic hydrocarbon group linking the aliphatic hydrocarbon group may also be replaced by a divalent group containing a heteroatom. Examples of divalent groups containing heteroatoms 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.

[0228] A chain alkyl group having substituents: The chain alkyl group of R101 can be either straight-chain or branched. As a straight-chain alkyl group, 1 to 20 carbon atoms are preferred, 1 to 15 are more preferred, and 1 to 10 are most preferred. As a branched alkyl group, 3 to 20 carbon atoms are preferred, 3 to 15 are more preferred, and 3 to 10 are most preferred. Specific 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.

[0229] The alkenyl group may 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 especially preferably with 3 carbon atoms. Examples of linear alkenyl groups include vinyl, allyl, and butynyl. Examples of branched alkenyl groups include 1-methylvinyl, 2-methylvinyl, 1-methylpropenyl, and 2-methylpropenyl. Among the above-mentioned linear alkenyl groups, linear alkenyl groups are preferred, with vinyl and allyl groups being more preferred, and vinyl groups being especially preferred.

[0230] As a substituent in the chain-like alkyl or alkenyl group of R101, examples include alkoxy, halogen atom, haloalkyl, hydroxyl, carbonyl, nitro, amino, and cyclic group in R101.

[0231] Of the above, R101 is preferably a cyclic group that can have substituents, and is more preferably a cyclic hydrocarbon group that can have substituents. More specifically, as a cyclic hydrocarbon group, it is preferably phenyl, naphthyl, or a group that has removed one or more hydrogen atoms from a polycyclic alkane; a cyclic group containing lactones represented by the aforementioned general formulas (a2-r-1) to (a2-r-7); or a cyclic group containing -SO2- represented by the aforementioned general formulas (a5-r-1) to (a5-r-4). It is more preferably a group that has removed one or more hydrogen atoms from a polycyclic alkane or a cyclic group containing -SO2- represented by the aforementioned general formulas (a5-r-1) to (a5-r-4). It is even more preferably adamantyl or a cyclic group containing -SO2- represented by the aforementioned general formula (a5-r-1).

[0232] When the cyclic hydrocarbon group has a substituent, the substituent is preferably a hydroxyl group.

[0233] In formula (b-1-an), 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. Examples of atoms other than oxygen include carbon, hydrogen, sulfur, and nitrogen. Examples of divalent groups containing oxygen include non-hydrocarbon oxygen-containing groups such as oxygen atom (ether bond: -O-), ester bond (-C(=O)-O-), oxycarbonyl (-OC(=O)-), amide bond (-C(=O)-NH-), carbonyl (-C(=O)-), carbonate bond (-OC(=O)-O-), etc.; combinations of these non-hydrocarbon oxygen-containing groups with alkyl groups, etc. These combinations may also be further linked with a sulfonyl group (-SO2-). As a divalent linker containing an oxygen atom, examples include the linkers represented by the following general formulas (y-al-1) to (y-al-7). Furthermore, in this case, the linker in the following general formulas (y-al-1) to (y-al-7) that is bonded to R101 in the above formula (b-1-an) is V'101 in the following general formulas (y-al-1) to (y-al-7).

[0234] [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.]

[0235] The divalent saturated hydrocarbon group in V'102 is preferably an alkyl group with 1 to 30 carbon atoms, more preferably an alkyl group with 1 to 10 carbon atoms, and even more preferably an alkyl group with 1 to 5 carbon atoms.

[0236] The alkyl group in V'101 and V'102 can be a straight-chain alkyl group or a branched alkyl group, with a straight-chain alkyl group being preferred. Specific examples of alkyl groups in V'101 and V'102 include methylene [-CH2-]; alkyl methylene groups such as -CH(CH3)-, -CH(CH2CH3)-, -C(CH3)2-, -C(CH3)(CH2CH3)-, -C(CH3)(CH2CH2CH3)-, and -C(CH2CH3)2-; alkyl ethyl groups such as ethyl group [-CH2CH2-]; alkyl ethyl groups such as -CH(CH3)CH2-, -CH(CH3)CH(CH3)-, -C(CH3)2CH2-, and -CH(CH2CH3)CH2-; and trimethylene (n-propyl) [-CH2CH2CH2-]. Alkyltrimethylbenzenes such as -CH(CH3)CH2CH2- and -CH2CH(CH3)CH2-; tetramethylene [-CH2CH2CH2CH2-]; alkyltetramethylenes such as -CH(CH3)CH2CH2CH2- and -CH2CH(CH3)CH2CH2-; pentamethylene [-CH2CH2CH2CH2CH2-], etc. Furthermore, some of the methylene groups in the aforementioned alkyl groups in V'101 or V'102 can also be replaced by a divalent aliphatic cyclic group with 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 aliphatic hydrocarbon group, polycyclic aliphatic hydrocarbon group) of Ra'3 in the aforementioned formula (a1-r-1), with cyclohexyl, 1,5-adamantyl, or 2,6-adamantyl being more preferred.

[0237] As Y101, it is preferred to have a divalent linker containing an ester bond or a divalent linker containing an ether bond, and it is more preferred to have a linker represented by the formulas (y-al-1) to (y-al-5) above.

[0238] In formula (b-1-an), V101 is a single bond, an alkyl group, or a fluorinated alkyl group. The alkyl group or fluorinated alkyl group in V101 is preferably composed of 1 to 4 carbon atoms. Examples of fluorinated alkyl groups in V101 include groups in which one or all of the hydrogen atoms of the alkyl group in V101 are replaced by fluorine atoms. V101 is also preferably a single bond or a fluorinated alkyl group with 1 to 4 carbon atoms.

[0239] In formula (b-1-an), R102 is a fluorine atom or a fluorinated alkyl group having 1 to 5 carbon atoms. R102 is preferably a fluorine atom or a perfluoroalkyl group having 1 to 5 carbon atoms, with fluorine atoms being more preferred.

[0240] As a specific example of the anionic part shown in the aforementioned formula (b-1-an), for example, when Y101 is a single bond, fluorinated alkyl sulfonate anions such as trifluoromethane sulfonate anion or perfluorobutane sulfonate anion can be cited; when Y101 is a divalent linker containing an oxygen atom, anions shown in any of the following formulas (an-1) to (an-3) can be cited.

[0241] [In the formula, R”101 is an aliphatic cyclic group that may have substituents, a monovalent heterocyclic group represented by the above chemical formulas (r-hr-1) to (r-hr-6) respectively, a condensed cyclic group represented by the above formulas (r-br-1) or (r-br-2), a chain alkyl group that may have substituents, or an aromatic cyclic group that may have substituents. R”102 is an aliphatic cyclic group that may have substituents, a condensed cyclic group represented by the above formulas (r-br-1) and (r-br-2), a cyclic group containing lactone represented by the above general formulas (a2-r-1), (a2-r-3) to (a2-r-7) respectively, or a cyclic group containing SO2- represented by the above general formulas (a5-r-1) to (a5-r-4) respectively. R”103 is an aromatic cyclic group that may have substituents, an aliphatic cyclic group that may have substituents, or a chain-like 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 independent integer from 0 to 3, q” is an independent integer from 0 to 20, and n” is 0 or 1.

[0242] The aliphatic cyclic groups of R”101, R”102 and R”103 that may have substituents are preferably the groups exemplified by the cyclic aliphatic hydrocarbon group of R101 in the aforementioned formula (b-1-an). As the aforementioned substituents, examples may be those that are the same as the substituents that can replace the cyclic aliphatic hydrocarbon group of R101 in the aforementioned formula (b-1-an).

[0243] The aromatic cyclic groups that may have substituents in R”101 and R”103 are preferably the groups exemplified as the aromatic hydrocarbon groups in the cyclic hydrocarbon groups of R101 in the aforementioned formula (b-1-an). As the aforementioned substituents, examples may be those that are the same as the substituents that can replace the aromatic hydrocarbon groups of R101 in the aforementioned formula (b-1-an).

[0244] The chain alkyl group that may have substituents in R”101 is preferably the group exemplified by the chain alkyl group of R101 in the aforementioned formula (b-1-an). The chain alkenyl group that may have substituents in R”103 is preferably the group exemplified by the chain alkenyl group of R101 in the aforementioned formula (b-1-an).

[0245] The following shows a specific example of the anion section shown in formula (b-1-an), but is not limited to such examples.

[0246]

[0247] ・In the anionic formula (b-2-an) shown in formula (b-2-an), R104 and R105 are each independently a cyclic group that may have substituents, a chain alkyl group that may have substituents, or a chain alkenyl group that may have substituents, and examples such as those identical to R101 in formula (b-1-an) can be given. However, R104 and R105 may also be combined with each other to form a ring. R104 and R105 are preferably chain alkyl groups that may have substituents, and are preferably straight-chain or branched alkyl groups, or straight-chain or branched fluorinated alkyl groups. The number of carbon atoms in the chain alkyl group is preferably 1 to 10, more preferably 1 to 7, and even more preferably 1 to 3. The carbon number of the chain alkyl groups in R104 and R105 is preferably lower within the aforementioned range, as it provides good solubility in solvents used for resisting agents. Furthermore, the more hydrogen atoms replaced by fluorine atoms in the chain alkyl groups of R104 and R105, 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-an), V102 and V103 are each independently a single bond, an alkyl group, or a fluorinated alkyl group, and examples of the same type as V101 in formula (b-1-an) can be cited. In formula (b-2-an), L101 and L102 are each independently a single bond or an oxygen atom.

[0248] ・In the anionic formula (b-3-an) shown in formula (b-3-an), R106 to R108 are each independently a cyclic group that may have substituents, a chain alkyl group that may have substituents, or a chain alkenyl group that may have substituents, and examples can be those that are the same as R101 in formula (b-1-an). In formula (b-3-an), L103 to L105 are each independently a single bond, -CO-, or -SO2-.

[0249] Of the above, the anion represented by formula (b-1-an) is preferred as Xb-. Among them, the anion represented by any of the above general formulas (an-1) to (an-3) is more preferred, the anion represented by any of the general formulas (an-1) or (an-2) is more preferred, and the anion represented by the general formula (an-1) is particularly preferred.

[0250] The following shows specific examples of (B0) components, but are not limited to them.

[0251]

[0252]

[0253]

[0254]

[0255] In the resist composition of this embodiment, component (B0) can be used alone or in combination with two or more components. In the resist composition of this embodiment, the content of component (B0) relative to 100 parts by mass of component (A) is preferably 5 to 45 parts by mass, more preferably 10 to 40 parts by mass, even more preferably 12 to 40 parts by mass, and particularly preferably 15 to 35 parts by mass. When the content of component (B0) is above or below the lower limit of the aforementioned preferred range, the micro-lithography properties such as sensitivity, LWR (linewidth roughness) reduction, pattern shape, and defect reduction during resist pattern formation are further improved. On the other hand, when it is below the upper limit of the preferred range, a homogeneous solution can be easily obtained when each component of the resist composition is dissolved in an organic solvent, and the storage stability of the resist composition is further improved.

[0256] In the inhibitor composition of this embodiment, the proportion of component (B0) in all components (B) is, for example, 50% by mass or more, preferably 70% by mass or more, and more preferably 95% by mass or more. The proportion of component (B0) in all components (B) may also be 100% by mass.

[0257] Component (B) of the inhibitor composition of this embodiment may also contain an acid generating agent component (B1) other than the above-mentioned component (B0) (hereinafter also referred to as "(B1) component").

[0258] ≪(B1) Component≫ As a (B1) component, examples include onium salt acid generators such as monazite or strontium salts (except those equivalent to (B0) components); oxime sulfonate acid generators; diazomethane acid generators such as dialkyl or diarylsulfonyldiazomethanes and poly(disulfonyl)diazomethanes; nitrobenzyl sulfonate acid generators, imino sulfonate acid generators, diazonate acid generators, and many other types.

[0259] As a tungsten salt acid generator, examples include the compound shown in general formula (b-1) below (hereinafter also referred to as "(b-1) component"), the compound shown in general formula (b-2) (hereinafter also referred to as "(b-2) component") or the compound shown in general formula (b-3) (hereinafter also referred to as "(b-3) component").

[0260] [In the formula, R101 and R104~R108 are each independently a cyclic group that may have substituents, a chain-like alkyl group that may have substituents, or a chain-like 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 group 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 M'm+ is an onium cation with an m valence.]

[0261] {Anion section} ・The anion in component (b-1) is the anion shown in the aforementioned formula (b-1-an).

[0262] ・(b-2) The anion in the component (b-2) is the anion shown in the aforementioned formula (b-2-an).

[0263] ・(b-3) The anion in the component (b-3) is the anion shown in the aforementioned formula (b-3-an).

[0264] Of the above, the anionic portion of component (B1) is preferably an anion represented by formula (b-1-an). Among these, an anion represented by any of the general formulas (an-1) to (an-3) is more preferred, an anion represented by any of the general formulas (an-1) or (an-2) is even more preferred, and an anion represented by the general formula (an-2) is particularly preferred.

[0265] {Cation Section} In the aforementioned formulas (b-1), (b-2), and (b-3), Mm+ represents an onium cation with a valence of m. Among them, strontium cations and monium cations are preferred. m is an integer greater than or equal to 1.

[0266] As a preferred cation portion ((Mm+)1 / m), examples include organic cations represented by the general formulas (ca-1) to (ca-5) below (except for those equivalent to cation (CO)).

[0267] [In the formula, R201~R207 and R211~R212 each independently represent an aryl, alkyl, or alkenyl group that may have substituents. R201~R203, R206~R207, and R211~R212 may also combine with each other to form a ring together with the sulfur atom in the formula. R208~R209 each independently represent a hydrogen atom or an alkyl group with 1 to 5 carbon atoms. R210 is an aryl group that may have substituents, an alkyl group that may have substituents, an alkenyl group that may have substituents, or a cyclic group containing SO2- that may have substituents. L201 represents -C(=O)- or -C(=O)-O-. Y201 each independently represents an aryl, alkyl, or alkenyl group. x is 1 or 2. W201 represents a (x+1) valence linkage group.]

[0268] In the above general formulas (ca-1) to (ca-5), aryl groups in R201 to R207 and R211 to R212 can be unsubstituted aryl groups with 6 to 20 carbon atoms, with phenyl and naphthyl groups being preferred. Alkyl groups in R201 to R207 and R211 to R212 are preferably chain-like or cyclic alkyl groups with 1 to 30 carbon atoms. Alkenyl groups in R201 to R207 and R211 to R212 are preferably alkenyl groups with 2 to 10 carbon atoms. Substituents that can be present in R201 to R207 and R210 to R212 can be, for example, alkyl groups, halogen atoms, alkyl halides, carbonyl groups, cyano groups, amino groups, aryl groups, and groups represented by the following general formulas (ca-r-1) to (ca-r-7).

[0269] [In the formula, R'201 can be a hydrogen atom, a cyclic group that may have substituents, a chain alkyl group that may have substituents, or a chain alkenyl group that may have substituents.]

[0270] Cyclic groups that may have substituents: The cyclic group is preferably a cyclic hydrocarbon group, which can 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 can be saturated or unsaturated, but saturated is generally preferred.

[0271] The aromatic hydrocarbon group in R'201 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 refers to the number of carbon atoms excluding those in the substituents. Specific examples of the aromatic ring 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 replaced by heteroatoms. Examples of heteroatoms in aromatic heterocycles include oxygen atoms, sulfur atoms, and nitrogen atoms. Specifically, the aromatic hydrocarbon group in R'201 can be exemplified by groups in which one hydrogen atom is removed from the aforementioned aromatic ring (aryl: for example, phenyl, naphthyl, etc.), or groups in which one hydrogen atom of the aforementioned aromatic ring is replaced by an alkyl group (e.g., 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.

[0272] The cyclic aliphatic hydrocarbon group in R'201 can be exemplified by an aliphatic hydrocarbon group whose structure includes a ring. Examples of such aliphatic hydrocarbon groups with a ring include alicyclic hydrocarbon groups (groups in which one hydrogen atom is removed from an aliphatic hydrocarbon ring), alicyclic hydrocarbon groups bonded to the end of a straight-chain or branched aliphatic hydrocarbon group, and alicyclic hydrocarbon groups present in the middle of a straight-chain or branched 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 be a polycyclic group or a monocyclic group. As a monocyclic alicyclic hydrocarbon group, it is preferable to have one or more hydrogen atoms removed from a monocyclic alkane. As for such a monocyclic alkane, it is preferable to have 3 to 6 carbon atoms, specifically examples include cyclopentane and cyclohexane. The alicyclic hydrocarbon group is preferably a group that has removed one or more hydrogen atoms from the polycyclic alkane, and the polycyclic alkane is preferably one with 7 to 30 carbon atoms. Among these, polycyclic alkanes with a cross-linked ring system polycyclic skeleton, such as adamantane, norcamphene, isocamphene, tricyclic decane, and tetracyclic dodecane, and polycyclic alkanes with a condensed ring system polycyclic skeleton, such as cyclic groups with a steroid skeleton, are more preferred.

[0273] 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 a polycyclic alkane, and is more preferably a group that has removed one hydrogen atom from a polycyclic alkane. Adamantyl and norbenzyl are particularly preferred, with adamantyl being the best.

[0274] The aliphatic hydrocarbon group that can be bonded to the alicyclic hydrocarbon group is preferably of 1 to 10 carbon atoms, more preferably of 1 to 6 carbon atoms, even more preferably of 1 to 4 carbon atoms, and especially preferably of 1 to 3 carbon atoms. As a straight-chain aliphatic hydrocarbon group, a straight-chain alkyl group is preferred, and specific examples include methylene [-CH2-], ethyl [-(CH2)2-], trimethylene [-(CH2)3-], tetramethylene [-(CH2)4-], pentamethylene [-(CH2)5-], etc. As a branched aliphatic hydrocarbon group, branched alkyl groups are preferred. Specific 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, a straight-chain alkyl group with 1 to 5 carbon atoms is preferred.

[0275] Furthermore, the cyclic hydrocarbon group in R'201 may contain heteroatoms, such as heterocycles. Specifically, examples include the lactone-containing cyclic groups represented by the aforementioned general formulas (a2-r-1) to (a2-r-7), the -SO2- containing cyclic groups represented by the aforementioned general formulas (a5-r-1) to (a5-r-4), and other heterocyclic groups represented by the aforementioned chemical formulas (r-hr-1) to (r-hr-16).

[0276] 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 groups used as substituents, alkyl groups having 1 to 5 carbon atoms are preferred, with methyl, ethyl, propyl, n-butyl, and tert-butyl being the most desirable. Among the alkoxy groups used as substituents, alkoxy groups having 1 to 5 carbon atoms are preferred, with methoxy, ethoxy, n-propoxy, iso-propoxy, n-butoxy, and tert-butoxy being more preferred, and methoxy and ethoxy being the most desirable. Among the halogen atom used as substituents, fluorine atoms are preferred. Among the alkyl halide groups used as substituents are alkyl groups having 1 to 5 carbon atoms, such as methyl, ethyl, propyl, n-butyl, and tert-butyl, where one or all of the hydrogen atoms are replaced by the aforementioned halogen atom. The carbonyl group, as a substituent, is a group that replaces the methylene (-CH2-) that constitutes the cyclic hydrocarbon group.

[0277] A chain alkyl group that may have substituents: The chain alkyl group of R'201 may be either straight-chain or branched. As a straight-chain alkyl group, it is preferred to have 1 to 20 carbon atoms, more preferably 1 to 15 carbon atoms, and most preferably 1 to 10 carbon atoms. As a branched 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 of specific 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.

[0278] The alkenyl group may have substituents: The alkenyl group of R'201 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 butynyl. Examples of branched alkenyl groups include 1-methylvinyl, 2-methylvinyl, 1-methylpropenyl, and 2-methylpropenyl. Among the above, linear alkenyl groups are preferred, with vinyl and allyl groups being more preferred, and vinyl being particularly preferred.

[0279] Examples of substituents in the chain-like alkyl or alkenyl groups of R'201 include alkoxy groups, halogen atoms, halogenated alkyl groups, hydroxyl groups, carbonyl groups, nitro groups, amino groups, and cyclic groups in the aforementioned R'201.

[0280] 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, other cyclic groups with substituents or chain alkyl groups with substituents may be those with the same acid dissociative group as shown in the above formula (a1-r-2).

[0281] Among them, R'201 is preferably a cyclic group that can have substituents, and is more preferably a cyclic hydrocarbon group that can have substituents. More specifically, it is preferably a phenyl, naphthyl, or a group that has removed one or more hydrogen atoms from a polycyclic alkane; a cyclic group containing lactones represented by the aforementioned general formulas (a2-r-1) to (a2-r-7); or a cyclic group containing -SO2- represented by the aforementioned general formulas (a5-r-1) to (a5-r-4).

[0282] In the above general formulas (ca-1) to (ca-5), where R201 to R203, R206 to R207, and R211 to R212 are bonded together with the sulfur atom in the formula to form a ring, the bonding can also be achieved through heteroatoms such as sulfur atoms, oxygen atoms, and nitrogen atoms, 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 the sulfur atom in the formula is included in one ring of its ring skeleton, and the ring containing the sulfur atom is a 3 to 10-membered ring, with a 5 to 7-membered ring being particularly preferred. Specific examples of the rings formed include thiophene rings, thiazole rings, benzothiophene rings, dibenzothiophene rings, 9H-thioxanthium rings, thioxanone rings, thiathrone rings, phenoxathiin rings, tetrahydrothiophenonium rings, and tetrahydrothiaranonium rings.

[0283] R208~R209 each independently represent an alkyl group having 1 to 5 hydrogen atoms or carbon atoms, preferably an alkyl group having 1 to 3 hydrogen atoms or carbon atoms. When forming an alkyl group, they can also combine with each other to form a ring.

[0284] R210 is an aryl group that may have substituents, an alkyl group that may have substituents, an alkenyl group that may have substituents, or a cyclic group containing -SO2- that may have substituents. Examples of aryl groups in R210 include unsubstituted aryl groups with 6 to 20 carbon atoms, with phenyl and naphthyl groups being preferred. Examples of alkyl groups in R210 include chain-like or cyclic alkyl groups with 1 to 30 carbon atoms. Examples of alkenyl groups in R210 include alkenyl groups with 2 to 10 carbon atoms. Examples of cyclic groups containing -SO2- that may have substituents in R210 include "polycyclic groups containing -SO2-", with the group shown in the above general formula (a5-r-1) being more preferred.

[0285] Y201 represents aryl, alkyl, or alkenyl groups, each independently. Examples of aryl groups in Y201 include those formed by removing one hydrogen atom from an aryl group exemplified as an aromatic hydrocarbon group in R101 of the above formula (b-1-an). Examples of alkyl and alkenyl groups in Y201 include those formed by removing one hydrogen atom from a chain alkyl or chain alkenyl group exemplified as a chain alkyl or chain alkenyl group in R101 of the above formula (b-1).

[0286] In the aforementioned formula (ca-4), x is 1 or 2. W201 is a (x+1) valence, i.e., a divalent or trivalent linking group. As the divalent linking group in W201, a divalent hydrocarbon group that can have substituents is preferred, such as a divalent hydrocarbon group that can have substituents, similar to Ya21 in the above general formula (a2-1). The divalent linking group in W201 can be any of straight-chain, branched, or cyclic, with cyclic being preferred. Among them, a group with two carbonyl groups combined at both ends of an aryl group is preferred. Examples of aryl groups include phenyl and naphthyl groups, with phenyl being particularly preferred. As the trivalent linking group in W201, examples include a group that removes one hydrogen atom from the divalent linking group in the aforementioned W201, or a group that has the aforementioned divalent linking group further bonded to it. As a trivalent linker in W201, it is preferable to have an aryl group bonded to two carbonyl groups.

[0287] As a suitable cation represented by the aforementioned formula (ca-1), examples can be specifically given as cations represented by the following chemical formulas (ca-1-1) to (ca-1-70).

[0288]

[0289]

[0290] [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.]

[0291]

[0292]

[0293] [In the formula, R”201 is a hydrogen atom or a substituent, and the substituent is the same as the substituents that R201~R207 and R210~R212 can have.]

[0294] Specific examples of suitable cations represented by the aforementioned formula (ca-2) include, for example, diphenyl citronium cation, bis(4-tert-butylphenyl) citronium cation, etc.

[0295] Specific examples of suitable cations represented by the aforementioned formula (ca-3) include cations represented by the following formulas (ca-3-1) to (ca-3-6).

[0296]

[0297] Specific examples of suitable cations represented by the aforementioned formula (ca-4) include cations represented by the following formulas (ca-4-1) to (ca-4-2).

[0298]

[0299] Specific examples of suitable cations represented by the aforementioned formula (ca-5) include those represented by the following general formulas (ca-5-1) to (ca-5-3).

[0300]

[0301] In the above, the cation part ((Mm+)1 / m) is preferably a cation represented by the general formula (ca-1).

[0302] In the inhibitor composition of this embodiment, component (B1) can be used alone or in combination with two or more components. When the inhibitor composition contains component (B1), the content of component (B1) relative to 100 parts by mass of component (A) is preferably less than 40 parts by mass, more preferably 1 to 30 parts by mass, and even more preferably 1 to 20 parts by mass. By making the content of component (B1) within the aforementioned preferred range, defects are easily reduced. Furthermore, when each component of the inhibitor composition is dissolved in an organic solvent, a homogeneous solution can be easily obtained, and the storage stability of the inhibitor composition becomes good. The inhibitor composition of this embodiment is preferably free of component (B1).

[0303] <Other Components> In addition to components (A) and (B) mentioned above, the inhibitor composition of this embodiment may also contain other components. Examples of other components include components (D), (E), (F), and (S) as shown below.

[0304] ≪Acid Diffusion Control Agent Component (D)≫ In addition to component (A), the resist composition of this embodiment may also contain an acid diffusion control agent component ((D) component) that captures acid generated by exposure (i.e., controls acid diffusion). Component (D) acts as a quencher (acid diffusion control agent) in the resist composition to capture acid generated by exposure. Examples of component (D) include, for example, a photodegradable base (D1) (hereinafter referred to as "(D1) component") that loses its acid diffusion control due to decomposition by exposure, and a nitrogen-containing organic compound (D2) (hereinafter referred to as "(D2) component") that is not suitable for component (D1). Among these, a photodegradable base ((D1) component) is preferred because it easily improves high sensitivity, reduces roughness, and suppresses the generation of coating defects.

[0305] ・Regarding component (D1), by creating a resist composition containing component (D1), the contrast between the exposed and unexposed areas of the resist film can be further enhanced during resist pattern formation. As for component (D1), there are no particular limitations as long as it decomposes upon exposure and loses its acid diffusion control. It is preferable to select one or more compounds from the group consisting of compounds shown in general formula (d1-1) (hereinafter referred to as "(d1-1) component"), compounds shown in general formula (d1-2) (hereinafter referred to as "(d1-2) component"), and compounds shown in general formula (d1-3) (hereinafter referred to as "(d1-3) component"). Since components (d1-1) to (d1-3) decompose and lose their acid diffusion control (alkalinity) in the exposed areas of the resist film, they do not act as quenchers, but they do act as quenchers in the unexposed areas of the resist film.

[0306] [In the formula, Rd1~Rd4 are cyclic groups that may have substituents, chain-like alkyl groups that may have substituents, or chain-like alkenyl groups that may have substituents. However, in formula (d1-2), the carbon atom adjacent to the S atom in Rd2 is a non-bonded fluorine 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.]

[0307] {(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, as can be examples of those similar to R'201 mentioned above. Among these, Rd1 is preferably an aromatic hydrocarbon group that may have substituents, an aliphatic cyclic group that may have substituents, or a chain alkyl group that may have substituents. Examples of substituents that may be present in these groups include hydroxyl groups, oxo groups, alkyl groups, aryl groups, fluorine atoms, fluorinated alkyl groups, lactone-containing cyclic groups represented by the above general formulas (a2-r-1) to (a2-r-7), ether bonds, ester bonds, or combinations thereof. When an ether or ester bond is used as a substituent, an alkyl group may be used as the substituent, preferably a linking group represented by formulas (y-al-1) to (y-al-5). Furthermore, when the aromatic hydrocarbon group, aliphatic cyclic group, or chain alkyl group in Rd1 is used as a substituent by a linking group represented by formulas (y-al-1) to (y-al-7), the carbon atom bond between the aromatic hydrocarbon group, aliphatic cyclic group, or chain alkyl group in formula (y-al-1) to Rd1 in formula (d3-1) is V'101 in formulas (y-al-1) to (y-al-7). Suitable examples of the aforementioned aromatic hydrocarbon group include phenyl, naphthyl, and polycyclic structures containing a bicyclic octane skeleton (polycyclic structures composed of a bicyclic octane skeleton and other ring structures). As the aforementioned aliphatic cyclic group, it is preferable to use a group that has removed one or more hydrogen atoms from polycyclic alkanes such as adamantane, norbornene, isobathane, tricyclic decane, and tetracyclic dodecane. As the aforementioned chain-like alkyl group, it is preferable to have 1 to 10 carbon atoms, and specific examples include 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.

[0308] When the aforementioned chain-like alkyl group is a fluorinated alkyl group having a fluorine atom or a fluorinated alkyl group, the number of carbon atoms in the fluorinated alkyl group is preferably 1 to 11, more preferably 1 to 8, and even more preferably 1 to 4. The fluorinated alkyl group may also contain atoms other than fluorine atoms. Examples of atoms other than fluorine atoms include oxygen atoms, sulfur atoms, and nitrogen atoms.

[0309] The following are preferred examples of the anionic portion of component (d1-1).

[0310]

[0311] ・・In the cation formula (d1-1), Mm+ is an organic cation with an m valence. Suitable examples of the organic cation Mm+ include those identical to those represented by the aforementioned general formulas (ca-1) to (ca-5), with the cation represented by the aforementioned general formula (ca-1) being preferred, and the cation represented by the aforementioned formulas (ca-1-1) to (ca-1-70) being even more preferred. The (d1-1) component can be used alone or in combination with two or more components.

[0312] (d1-1) Components can be used alone or in combination of two or more.

[0313] {(d1-2) Components} ・・In the anionic formula (d1-2), Rd2 can be a cyclic group that may have substituents, a chain alkyl group that may have substituents, or a chain alkenyl group that may have substituents, such as R'201 mentioned above. However, the carbon atom adjacent to the S atom in Rd2 is one that is not bonded with a fluorine atom (unsubstituted with fluorine). In this way, the anion of the (d1-2) component becomes a moderately weak acid anion, and the quenching ability of the (D) component is improved. As Rd2, a chain alkyl group that may have substituents or an aliphatic cyclic group that may have substituents is preferred. As a chain alkyl group, 1 to 10 carbon atoms are preferred, and 3 to 10 carbon atoms are more preferred. As an aliphatic cyclic group, it is preferred to have a group that has removed one or more hydrogen atoms from adamantane, norcamphene, isocamphene, tricyclodecane, tetracyclododecane, etc. (substituents may also be present); it is preferred to have a group that has removed one or more hydrogen atoms from camphor, etc. The hydrocarbon group of Rd2 may also have substituents, and examples of such substituents include those that are the same as those that may be present in the hydrocarbon group (aromatic hydrocarbon group, aliphatic cyclic group, chain alkyl group) of Rd1 in the aforementioned formula (d1-1).

[0314] The following are preferred examples of the anionic portion of the (d1-2) components.

[0315]

[0316] ・・In the cation part of formula (d1-2), Mm+ is an organic cation with an m valence, which is the same as Mm+ in the aforementioned formula (d1-1). The component (d1-2) can be used alone or in combination of two or more.

[0317] {(d1-3) Components} • In the anionic formula (d1-3), Rd3 is a cyclic group that may have substituents, a chain alkyl group that may have substituents, or a chain alkenyl group that may have substituents. Examples include those similar to R'201 mentioned above. Cyclic groups containing fluorine atoms, chain alkyl groups, or chain alkenyl groups are preferred. Fluorinated alkyl groups are also preferred, and those similar to the fluorinated alkyl groups of Rd1 mentioned above are even more preferred.

[0318] In formula (d1-3), Rd4 is a cyclic group that may have substituents, a chain alkyl group that may have substituents, or a chain alkenyl group that may have substituents, as can be the same as R'201 mentioned above. Among them, alkyl, alkoxy, alkenyl, and cyclic groups that may have substituents are preferred. The alkyl group in Rd4 is preferably a straight-chain or branched alkyl group with 1 to 5 carbon atoms, specifically such as 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 replaced by hydroxyl, cyano, etc. The alkoxy group in Rd4 is preferably an alkoxy group with 1 to 5 carbon atoms, specifically such as methoxy, ethoxy, n-propoxy, isopropoxy, n-butoxy, tert-butoxy. Among them, methoxy and ethoxy compounds are preferred.

[0319] The alkenyl group in Rd4 can be the same as that in R'201 mentioned above, preferably vinyl, propenyl (allyl), 1-methylpropenyl, or 2-methylpropenyl. These groups may also have alkyl groups with 1 to 5 carbon atoms or haloalkyl groups with 1 to 5 carbon atoms as substituents.

[0320] The cyclic group system in Rd4 can be the same as that in R'201 mentioned above, preferably an alicyclic group with one or more hydrogen atoms removed from cycloalkanes such as cyclopentane, cyclohexane, adamantane, norcamphene, isocamphene, tricyclodecane, tetracyclododecane, etc., or an aromatic group such as phenyl or naphthyl. When Rd4 is an alicyclic group, the resist composition will dissolve well in organic solvents, thus improving the lithography properties. Furthermore, when Rd4 is an aromatic group, the resist composition exhibits excellent light absorption efficiency in lithography using EUV or other light sources, resulting in good sensitivity or lithography properties.

[0321] In formula (d1-3), Yd1 is a single bond or a divalent linkage. There is no particular limitation on the divalent linkage in Yd1; examples include divalent hydrocarbon groups (aliphatic hydrocarbon groups, aromatic hydrocarbon groups) with substituents, and divalent linkages containing heteroatoms. Examples of such groups include those identical to the divalent hydrocarbon groups with substituents and divalent linkages containing heteroatoms mentioned in the description of divalent linkages in Ya21 of formula (a2-1) above. Yd1 is preferably a carbonyl group, an ester bond, an amide bond, an alkyl group, or a combination thereof. As an alkyl group, a straight-chain or branched alkyl group is preferred, and methylene or ethyl groups are even more preferred.

[0322] The following are preferred examples of the anionic portion of the (d1-3) components.

[0323]

[0324]

[0325] ・・In the cation part of formula (d1-3), Mm+ is an organic cation with an m valence, which is the same as Mm+ in the aforementioned formula (d1-1). The component (d1-3) can be used alone or in combination of two or more.

[0326] Component (D1) can be any one of the components (d1-1) to (d1-3) mentioned above, or two or more can be used in combination. When the resist composition contains component (D1), the content of component (D1) in the resist composition is preferably 0.5 to 20 parts by mass relative to 100 parts by mass of component (A1), more preferably 1 to 15 parts by mass, and even more preferably 2 to 8 parts by mass. When the content of component (D1) is above the lower limit of the preferred value, it is particularly easy to obtain good lithography characteristics and resist pattern shape. On the other hand, when it is below the upper limit value, sensitivity can be well maintained, and the yield is also excellent.

[0327] (D1) Manufacturing method: There are no particular limitations on the manufacturing methods of the aforementioned components (d1-1) and (d1-2), and they can be manufactured by known methods. Also, there are no particular limitations on the manufacturing method of component (d1-3), and it can be manufactured by operating in the same manner as the method described in US2012-0149916.

[0328] ・Regarding component (D2), as component (D), it may also contain nitrogen-containing organic compounds that are not appropriate to component (D1) (hereinafter referred to as "component (D2)"). As component (D2), there are no particular limitations as long as it can act as an acid diffusion control agent and is not appropriate to component (D1), and it may be used freely from those known. Aliphatic amines are preferred, especially secondary or tertiary aliphatic amines. Aliphatic amines refer to amines having one or more aliphatic groups, and the aliphatic group preferably has 1 to 12 carbon atoms. Examples of aliphatic amines include amines (alkylamines or alkylolamines) or cyclic amines in which at least one hydrogen atom of ammonia (NH3) is replaced by an alkyl or hydroxyalkyl group having 12 or fewer carbon atoms. Specific examples of alkylamines and alkylolamines include monoalkylamines such as n-hexylamine, n-heptylamine, n-octylamine, n-nonylamine, and n-decylamine; dialkylamines such as diethylamine, di-n-propylamine, di-n-heptylamine, di-n-octylamine, and dicyclohexylamine; trialkylamines such as trimethylamine, triethylamine, tri-n-propylamine, tri-n-butylamine, tri-n-pentylamine, tri-n-hexylamine, tri-n-heptylamine, tri-n-octylamine, tri-n-nonylamine, tri-n-decylamine, and tri-n-dodecylamine; and alkylolamines such as diethanolamine, triethanolamine, diisopropanolamine, triisopropanolamine, di-n-octanolamine, and tri-n-octanolamine. Among these, trialkylamines with 5 to 10 carbon atoms are preferred, with tri-n-pentylamine or tri-n-octylamine being particularly preferred.

[0329] As a cyclic amine, examples include heterocyclic compounds containing a nitrogen atom as a heteroatom. Such heterocyclic compounds can be monocyclic (aliphatic monocyclic amines) or polycyclic (aliphatic polycyclic amines). Examples of aliphatic monocyclic amines include piperidine and piperazine. Examples of aliphatic polycyclic amines are preferably those with 6 to 10 carbon atoms, such as 1,5-diacrylbicyclo[4.3.0]-5-nonene, 1,8-diacrylbicyclo[5.4.0]-7-undecene, hexamethylenetetramine, and 1,4-diacrylbicyclo[2.2.2]octane.

[0330] Other aliphatic amines include, for example, 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-hydroxyethoxy)ethoxy]ethyl]amine, triethanolamine triacetate, etc., with triethanolamine triacetate being preferred.

[0331] 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, 2,6-di-tert-butylpyridine, etc.

[0332] Component (D2) can be used alone or in combination with two or more components. When the inhibitor composition contains component (D2), the content of component (D2) in the inhibitor composition is typically in the range of 0.01 to 5 parts by mass relative to 100 parts by mass of component (A1). By achieving this range, the inhibitor's pattern shape and stability over time are improved.

[0333] ≪At least one compound (E) selected from organic carboxylic acids and oxyacids of phosphorus and their derivatives≫ The inhibitor composition of this embodiment may contain at least one compound (E) selected from organic carboxylic acids and oxyacids of phosphorus and their derivatives (hereinafter referred to as "(E) component") as an arbitrary component for the purpose of preventing sensitivity degradation, improving inhibitor pattern shape, and stability over standing time. Examples of organic carboxylic acids include acetic acid, malonic acid, citric acid, malic acid, succinic acid, benzoic acid, and salicylic acid, with salicylic acid being preferred. Examples of oxyacids of phosphorus include phosphoric acid, phosphonic acid, and phosphonic acid, with phosphonic acid being particularly preferred. Examples of oxyacid derivatives of phosphorus include esters in which the hydrogen atoms of the aforementioned oxyacids are replaced by hydrocarbon groups. Examples of hydrocarbon groups include alkyl groups with 1 to 5 carbon atoms and aryl groups with 6 to 15 carbon atoms. Examples of phosphoric acid derivatives include phosphate esters such as di-n-butyl phosphate and diphenyl phosphate. Examples of phosphonic acid derivatives include phosphonate esters such as dimethyl phosphonate, di-n-butyl phosphonate, phenylphosphonic acid, diphenyl phosphonate, and dibenzyl phosphonate. Examples of phosphonic acid derivatives include phosphonate esters or phenylphosphonic acid. In the inhibitor composition of this embodiment, component (E) can be used alone or in combination with two or more components. When the inhibitor composition contains component (E), the content of component (E) is preferably 0.01 to 5 parts by mass relative to 100 parts by mass of component (A), and more preferably 0.05 to 3 parts by mass. By creating the aforementioned range, sensitivity and holographic properties are improved.

[0334] ≪Fluorine Additive Component (F)≫ The inhibitor composition of this embodiment may also contain a hydrophobic resin with a fluorine additive component (hereinafter referred to as "(F) component"). The (F) component is used to impart water repellency to the inhibitor film. By using a resin that is different from the (A) component, the lithography properties can be improved. As the (F) component, for example, fluorine-containing polymer compounds disclosed 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 the constituent unit (f1) shown in the following general formula (f1-1) can be cited as the (F) component. The polymer is preferably a homopolymer composed only of the constituent unit (f1) shown in formula (f1-1) below; a copolymer of the constituent unit (f1) and the aforementioned constituent unit (a1); or a copolymer of the constituent unit (f1) and a constituent unit derived from acrylic acid or methacrylic acid and the aforementioned constituent unit (a1), with the copolymer of the constituent unit (f1) and the aforementioned constituent unit (a1) being more preferred. Here, the constituent unit (a1) used in copolymerization 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, with the constituent unit derived from 1-ethyl-1-cyclooctyl (meth)acrylate being more preferred.

[0335] [In the formula, R is the same as described 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. Rf102 and Rf103 can be the same or different. nf1 is an integer from 0 to 5, and Rf101 is an organic group containing a fluorine atom.]

[0336] In formula (f1-1), the R group bonded to the carbon atom at the α-position is the same as described above. Hydrogen atoms or methyl groups are preferred as R. In formula (f1-1), fluorine atoms are preferred as halogen atoms in Rf102 and Rf103. Examples of alkyl groups having 1 to 5 carbon atoms in Rf102 and Rf103 include those with the same alkyl group having 1 to 5 carbon atoms as the aforementioned R, preferably methyl or ethyl. Specifically, examples of alkyl halides having 1 to 5 carbon atoms in Rf102 and Rf103 include groups where one or all of the hydrogen atoms of an alkyl group having 1 to 5 carbon atoms are replaced by halogen atoms. Fluorine atoms are preferred as the halogen atom. Among these, hydrogen atoms, fluorine atoms, or alkyl groups having 1 to 5 carbon atoms are preferred as Rf102 and Rf103, with hydrogen atoms, fluorine atoms, methyl groups, or ethyl groups being more preferred, and hydrogen atoms being even more preferred. In formula (f1-1), nf1 is an integer from 0 to 5, preferably an integer from 0 to 3, and preferably 1 or 2.

[0337] 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, more preferably with 1 to 15 carbon atoms, and especially preferably with 1 to 10 carbon atoms. Furthermore, it is preferable that at least 25% of the hydrogen atoms in the hydrocarbon group are fluorinated, more preferably with at least 50%, and especially preferably with at least 60% fluorination, as this improves the hydrophobicity of the resist film during immersion exposure. Among them, as Rf101, fluorinated hydrocarbon groups with 1 to 6 carbon atoms are preferred, and trifluoromethyl, -CH2-CF3, -CH2-CF2-CF3, -CH(CF3)2, -CH2-CH2-CF3, and -CH2-CH2-CF2-CF2-CF2-CF3 are particularly preferred.

[0338] (F) The weight average molecular weight (Mw) of the component (based on polystyrene conversion using gel permeation chromatography) is preferably 1,000 to 50,000, more preferably 5,000 to 40,000, and best preferably 10,000 to 30,000. Below the upper limit of this range, there is sufficient solubility in the solvent required for use as a resisting agent; above the lower limit of this range, the water repellency of the resisting film is good. (F) The dispersibility (Mw / Mn) of the component is preferably 1.0 to 5.0, more preferably 1.0 to 3.0, and best preferably 1.0 to 2.5.

[0339] In the inhibitor composition of this embodiment, component (F) can be used alone or in combination with two or more components. When the inhibitor composition contains component (F), the content of component (F) is preferably 0.5 to 10 parts by mass relative to 100 parts by mass of component (A), and more preferably 1 to 10 parts by mass.

[0340] ≪Organic Solvent Component (S)≫ The inhibitor composition of this embodiment is manufactured by dissolving the inhibitor material in an organic solvent component (hereinafter referred to as "(S) component"). As the (S) component, any component that can dissolve all the components used to form a homogeneous solution can be appropriately selected from those known in the past as solvents for chemically amplified inhibitor compositions. As components (S), 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; polyvalent alcohols such as ethylene glycol, diethylene glycol, propylene glycol, and dipropylene glycol; compounds containing ester bonds such as ethylene glycol monoacetate, diethylene glycol monoacetate, propylene glycol monoacetate, or dipropylene glycol monoacetate; polyvalent alcohol derivatives such as monomethyl ethers, monoethyl ethers, monopropyl ethers, monobutyl ethers, etc., or monoalkyl ethers or monophenyl ethers of the aforementioned polyvalent alcohols or compounds containing ester bonds [among these...]. Preferred solvents include 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, cresolyl methyl ether, diphenyl ether, dibenzyl ether, phenethyl ether, butyl phenyl ether, ethylbenzene, diethylbenzene, pentylbenzene, isopropylbenzene, toluene, xylene, p-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. Preferred solvents include PGMEA, PGME, γ-butyrolactone, EL, and cyclohexanone.

[0341] Furthermore, as component (S), a mixed solvent consisting of PGMEA and a polar solvent is preferred. The mixing ratio (mass ratio) should be appropriately determined after considering the compatibility of PGMEA and the polar solvent, preferably in the range of 1:9 to 9:1, and more preferably in the range of 2:8 to 8:2. More specifically, when EL or cyclohexanone is used as a polar solvent, the mass ratio of PGMEA:EL or cyclohexanone is preferably 1:9 to 9:1, and more preferably 2:8 to 8:2. Also, as a polar solvent, when PGME is used as a solvent, the mass ratio of PGMEA:PGME is preferably 1:9 to 9:1, more preferably 2:8 to 8:2, and even more preferably 3:7 to 7:3. Furthermore, a mixed solvent consisting of PGMEA and PGME and cyclohexanone is also preferred. Furthermore, as component (S), it is preferable to use at least one of the solvents selected from PGMEA and EL, mixed with γ-butyrolactone. In this case, the mass ratio of the former to the latter is preferably 70:30 to 95:5. The amount of component (S) used is not particularly limited, and should be appropriately set according to the coating thickness, such as the concentration required for coating onto the substrate. Generally, component (S) is used in a manner that makes the solid content concentration of the resist composition within the range of 0.1 to 20% by mass, preferably 0.2 to 15% by mass.

[0342] The inhibitor composition of this embodiment can be further modified as needed by adding additives that are miscible, such as addition resins for improving the performance of the inhibitor film, solubility inhibitors, plasticizers, stabilizers, colorants, anti-glare agents, dyes, etc.

[0343] In this embodiment, after dissolving the aforementioned inhibitor material in component (S), the inhibitor composition is used to remove impurities by employing a polyimide porous membrane, a polyamide-imide porous membrane, or the like. For example, a filter composed of a polyimide porous membrane, a filter composed of a polyamide-imide porous membrane, or a filter composed of both polyimide porous membranes can be used to filter the inhibitor composition. Examples of the aforementioned polyimide porous membranes and polyamide-imide porous membranes include those described in Japanese Patent Application Publication No. 2016-155121.

[0344] As explained above, the resist composition of this embodiment contains a compound (B) comprising a cation (CO) as component (B). The cation (CO) is a low LUMO cation with a planar structure. By containing the cation (CO), the acid generation efficiency of the compound (B) during exposure is improved. Therefore, the sensitivity of the resist composition containing the compound (B) is improved. Furthermore, the cation (CO) has two or more electron-withdrawing groups in the phenyl group, thus improving the solubility for component (S). In addition, its solubility in the developer is improved during post-exposure development. Therefore, the resist composition containing the compound (B) can reduce defects. Based on the above, the resist composition of this embodiment achieves both high sensitivity and reduced defects.

[0345] [Second Embodiment] The resist composition of the second embodiment contains compound (C) as component (D). The resist composition of the second embodiment contains: component (A) which changes the solubility of the developer due to the action of acid, and acid diffusion control agent component (D) which controls the diffusion of acid generated due to exposure. The aforementioned acid diffusion control agent component (D) includes a compound represented by the following general formula (d0).

[0346] [Where, Md+ is the aforementioned cation (CO). Xd- is the relative anion.]

[0347] <(A) Component> The (A) component may be the same as the (A) component in the first embodiment described above. The (A) component is preferably a resin component (A1) component that changes the solubility of the developer due to the action of acid. The (A1) component may be the same as the (A1) component in the first embodiment described above. One (A1) component may be used alone, or two or more may be used together.

[0348] In the resist composition of this embodiment, the content of component (A) can be adjusted according to the desired resist film thickness, etc.

[0349] <(D) Component> The inhibitor composition of this embodiment contains an acid diffusion control component (D) that captures acid generated by exposure (i.e., controls acid diffusion). The (D) component includes a compound (D0) represented by the following general formula (d0) (hereinafter also referred to as "(D0) component"). The compound (D0) is a photodegradable base that decomposes upon exposure and loses its acid diffusion control.

[0350] ≪(D0)Component≫ (D0)Component is a compound represented by the following general formula (d0).

[0351] [Where, Md+ is the aforementioned cation (CO). Xd- is the relative anion.]

[0352] {Cation part} In the aforementioned general formula (d0), Md+ is the aforementioned cation (CO).

[0353] {Anionic part} In the aforementioned general formula (d0), Xd- is a relative anion. There are no particular restrictions on Xd-, and the anionic part of a photodegradable base proposed for use as a chemically amplifying inhibitor component can be used.

[0354] As Xd-, examples include anions represented by the following general formulas (d-1-an), (d-2-an), or (d-3-an).

[0355] [In the formula, Rd1~Rd4 are cyclic groups that may have substituents, chain-like alkyl groups that may have substituents, or chain-like alkenyl groups that may have substituents. However, in formula (d1-2), the carbon atom of Rd2 adjacent to the S atom is not bonded to a fluorine atom. Yd1 is a single bond or a divalent linkage. m is an integer greater than or equal to 1, and Mm+ are each an independent organic cation with an m valence.]

[0356] ・The anion shown in formula (d-1-an) is the same as the anion part of the aforementioned (d1-1) component.

[0357] ・The anion shown in formula (d-2-an) is the same as the anion part of the aforementioned (d1-2) component.

[0358] ・The anion shown in formula (d-3-an) is the same as the anion part of the aforementioned (d1-3) component.

[0359] Among the above, the anion represented by formula (d-1-an) is preferred as Xd-.

[0360] The following shows specific examples of (D0) components, but are not limited to them.

[0361]

[0362]

[0363]

[0364]

[0365] In the resist composition of this embodiment, the (DO) component can be used alone or in combination with two or more components. In the resist composition of this embodiment, the content of the (DO) component relative to 100 parts by mass of the (A) component is preferably 0.5 to 20 parts by mass, more preferably 1 to 15 parts by mass, and even more preferably 2 to 8 parts by mass. When the content of the (DO) component is above or below the lower limit of the aforementioned preferred range, it is easy to obtain good lithography properties and resist pattern shape. On the other hand, when it is below the upper limit, sensitivity can be well maintained, and the yield is also excellent.

[0366] In the inhibitor composition of this embodiment, the proportion of the (D) component in all (D) components is, for example, 50% by mass or more, preferably 70% by mass or more, and more preferably 95% by mass or more. The proportion of the (D) component in all (D) components may also be 100% by mass.

[0367] The (D) component in the inhibitor composition of this embodiment may also contain an acid diffusion control agent component other than the (D0) component. Examples of acid diffusion control agents other than the (D0) component include photodegradable bases (D1) that lose their acid diffusion control properties due to decomposition upon exposure (hereinafter referred to as "(D1) component") (except for those that are equivalent to the (D0) component), nitrogen-containing organic compounds (D2) that are not equivalent to the (D1) component (hereinafter referred to as "(D2) component"), etc.

[0368] ≪(D1) component≫ The (D1) component can be the same as the (D1) component in the first embodiment mentioned above.

[0369] Component (D1) can be used alone or in combination of two or more. In the case of the inhibitor composition of this embodiment containing component (D1), the content of component (D1) relative to 100 parts by mass of component (A1) is preferably less than 20 parts by mass, more preferably less than 15 parts by mass, and even more preferably less than 8 parts by mass. By making the content of component (D1) within the aforementioned preferred range, it becomes easier to reduce defects. The inhibitor composition of this embodiment is preferably free of component (D1).

[0370] ≪(D2) component≫ The (D2) component can be the same as the (D2) component in the first embodiment mentioned above.

[0371] Component (D2) can be used alone or in combination of two or more. In the case of the inhibitor composition of this embodiment containing component (D2), the content of component (D2) in the inhibitor composition is preferably less than 10 parts by mass relative to 100 parts by mass of component (A1), and more preferably less than 5 parts by mass. By making the content of component (D2) within the aforementioned preferred range, it becomes easier to reduce defects. The inhibitor composition of this embodiment is preferably free of component (D2).

[0372] <Other Ingredients> In addition to the ingredients (A) and (D) mentioned above, the inhibitor composition of this embodiment may also contain other ingredients. Examples of other ingredients include, for example, ingredients (B), (E), (F), and (S) shown below.

[0373] ≪(B) component≫ The inhibitor composition of this embodiment is preferably containing component (B). Component (B) may be the same as component (B1) in the aforementioned first embodiment.

[0374] In the inhibitor composition of this embodiment, component (B) can be used alone or in combination with two or more components. In the inhibitor composition of this embodiment, the content of component (B) relative to 100 parts by mass of component (A) is preferably 5 to 40 parts by mass, more preferably 10 to 40 parts by mass, even more preferably 12 to 40 parts by mass, and particularly preferably 15 to 35 parts by mass. By making the content of component (B) within the aforementioned preferred range, sufficient pattern formation can be achieved. Furthermore, since it is easy to obtain a homogeneous solution when each component of the inhibitor composition is dissolved in an organic solvent, and the storage stability of the inhibitor composition is good, it is preferable.

[0375] ≪(E) Component≫ The resist composition of this embodiment may also contain component (E). The (E) component may be the same as that in the first embodiment described above. In the resist composition of this embodiment, component (E) may be used alone or in combination with two or more. In the case where the resist composition of this embodiment contains component (E), the content of component (E) is preferably 0.01 to 5 parts by mass relative to 100 parts by mass of component (A), and more preferably 0.05 to 3 parts by mass. By achieving the above range, sensitivity and lithography properties are improved.

[0376] ≪(F) Component≫ The inhibitor composition of this embodiment may also contain component (F). Component (F) may be the same as component (E) in the aforementioned first embodiment. In the inhibitor composition of this embodiment, component (F) may be used alone or in combination with two or more. In the case where the inhibitor composition of this embodiment contains component (F), the content of component (F) is preferably 0.5 to 10 parts by mass relative to 100 parts by mass of component (A), and more preferably 1 to 10 parts by mass.

[0377] ≪(S) component≫ The (S) component can be the same as the (S) component in the first embodiment described above. The amount of (S) component used is not particularly limited, and the concentration that can be coated onto the substrate, etc., should be appropriately set according to the coating film thickness. Generally speaking, the (S) component is used in a manner that makes the solid component concentration of the resist composition in the range of 0.1 to 20% by mass, preferably in the range of 0.2 to 15% by mass.

[0378] The inhibitor composition of this embodiment can be further modified as needed by adding additives that are miscible, such as addition resins for improving the performance of the inhibitor film, solubility inhibitors, plasticizers, stabilizers, colorants, anti-glare agents, dyes, etc.

[0379] The inhibitor composition of this embodiment is similar to that of the inhibitor composition of the first embodiment described above. After dissolving the inhibitor material in component (S), impurities are removed using a polyimide porous membrane, a polyimide porous membrane, etc.

[0380] The resist composition of this embodiment described above contains a compound (DO) comprising a cation (CO) as component (D). The cation (CO) is a low LUMO cation with a planar structure. By containing a cation (CO), the compound (DO) becomes more susceptible to decomposition during exposure and loses its acid diffusion control ability. Therefore, the sensitivity of the resist composition containing compound (DO) is improved. Furthermore, the cation (CO) has two or more electron-withdrawing groups in the phenyl group, thus increasing the solubility for component (S). In addition, its solubility in the developer is improved during post-exposure development. Therefore, the resist composition containing compound (DO) can reduce defects. Based on the above, the resist composition of this embodiment achieves both high sensitivity and reduced defects.

[0381] [Third Embodiment] The resist composition of the third embodiment contains a compound (C) as component (A). The resist composition of the third embodiment contains component (A) which changes the solubility of the developer due to the action of acid. Component (A) includes a resin component (A0) having a constituent unit (a0) as shown in the following general formula (a0-1) (hereinafter also referred to as "(A0) component").

[0382] [In the formula, R is a hydrogen atom, an alkyl group having 1 to 5 carbon atoms, or a haloalkyl group having 1 to 5 carbon atoms. Ma+ is the aforementioned cation (CO). Rx0- is a group containing an anion.]

[0383] <(A) Component> In the inhibitor composition of this embodiment, component (A) includes component (A0).

[0384] ・(A0) Component (A0) Component is a resin component having a constituent unit (a0).

[0385] ≪Constituent Unit (a0)≫ The constituent unit (a0) is the constituent unit shown in the aforementioned general formula (a0-1). Depending on the type of Rx0-, the constituent unit (a0) may have the function of an acid generating agent or the function of an acid diffusion control agent. Hereinafter, the constituent unit (a0) with the function of an acid generating agent will also be referred to as "constituent unit (a0b). The constituent unit (a0) with the function of an acid diffusion control agent will also be referred to as "constituent unit (a0d)".

[0386] Constituent unit (a0b): {Cation part} In the aforementioned general formula (a0-1), Ma+ is the aforementioned cation (CO).

[0387] {Anion section} In the aforementioned general formula (a0-1), R is a hydrogen atom, an alkyl group having 1 to 5 carbon atoms, or a haloalkyl group having 1 to 5 carbon atoms. R is the same as R in the aforementioned formula (a1-1).

[0388] In the aforementioned general formula (a0-1), Rx0- is a radical containing an anion. In the constituent unit (a0b), Rx0- is a radical containing an anion that generates acid due to exposure. Examples of anions contained in Rx0- include those shown in the aforementioned formulas (b-1-an), (b-2-an), or (b-3-an).

[0389] An anion portion, which is a constituent unit (a0b), can be exemplified by the anion portion shown in the following general formula (a0-1-b).

[0390] [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. Ya01 is a single bond or a divalent linked group. La01 is a single bond, -O-, -COO-, -CON(R')-, -OCO-, -CONHCO-, or -CONHCS-, where R' represents a hydrogen atom or a methyl group. However, when La01 is -O-, Ya01 will not be -CO-. Rx0b is a group represented by the following general formula (b1-an), general formula (b2-an), or general formula (b3-an).]

[0391] [In the formula, Rx101, Rx104, and Rx107 are each independently a cyclic group that may have substituents, a chain-like alkyl group that may have substituents, or a chain-like alkenyl group that may have substituents. R105, R106, and R108 are each independently a cyclic group that may have substituents, a chain-like alkyl group that may have substituents, or a chain-like alkenyl group that may have substituents. Rx104 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 group or a single bond containing an oxygen atom. V101 to V103 are each independently a single bond, an alkyl group, or a fluorinated alkyl group. L101 to L102 are each independently a single bond or an oxygen atom. L103 to L105 are each independently a single bond, -CO-, or -SO2-.] * indicates the bond location with the La01 bond in equation (a0-1-b).

[0392] In the aforementioned formula (a0-1-b), R is a hydrogen atom, an alkyl group having 1 to 5 carbon atoms, or a haloalkyl group having 1 to 5 carbon atoms. R is the same as R in the aforementioned formula (a1-1).

[0393] In the aforementioned formula (a0-1-b), Ya01 is a single bond or a divalent linkage. There is no particular limitation on the divalent linkage; examples include divalent hydrocarbon groups having substituents, divalent linkage groups containing heteroatoms, etc. Examples of divalent hydrocarbon groups having substituents include those identical to those mentioned in the aforementioned formula (a2-1) for Ya21. Examples of divalent linkage groups containing heteroatoms include those identical to those mentioned in the aforementioned formula (a2-1) for Ya21. Ya01 is preferably a single bond, an ester bond [-C(=O)-O-], an ether bond (-O-), a straight-chain or branched alkyl group, or a combination thereof, with a single bond being more preferred.

[0394] In the aforementioned formula (a0-1-b), La01 is -O-, -COO-, -CON(R')-, -OCO-, -CONHCO-, or -CONHCS-. R' represents a hydrogen atom or a methyl group. However, when La01 is -O-, Ya01 will not become -CO-. As La01, -COO- is preferred.

[0395] In the aforementioned formula (a0-1-b), Rx0b is a base shown in the aforementioned general formula (b1-an), general formula (b2-an), or (b3-an).

[0396] ・The base shown in formula (b1-an) In the aforementioned formula (b1-an), Rx101 is a cyclic group that may have substituents, a chain-like alkyl group that may have substituents, or a chain-like alkylene group that may have substituents. Rx101 is a base from which one hydrogen atom is removed from R101 in the aforementioned formula (b-1-an). As Rx101, a cyclic group that may have substituents is preferred, and an alicyclic hydrocarbon group that may have substituents is more preferred. As Rx101, a base from which two hydrogen atoms are removed from a monocyclic alkane or a polycyclic alkane is preferred. As a monocyclic alkane, a group with 3 to 6 carbon atoms is preferred, and specific examples include cyclopentane and cyclohexane. As polycyclic alkanes, those with 7 to 30 carbon atoms are preferred. Specific examples include adamantane, norcamphene, isocamphene, tricyclic decane, and tetracyclic dodecane.

[0397] R102, Y101, and V101 are the same as R102, Y101, and V101 in the aforementioned formula (b-1-an).

[0398] As a basis represented by the formula (b1-an), any of the following general formulas (b1-an1) to (b1-an3) can be cited as a basis.

[0399] [In the formula, Rx”101 is an aliphatic cyclic group that may have substituents, a group that removes one hydrogen atom from the monovalent heterocyclic group represented by the above chemical formulas (r-hr-1) to (r-hr-6), a group that removes one hydrogen atom from the condensed cyclic group represented by the aforementioned formula (r-br-1) or (r-br-2), or a chain-like alkyl group that may have substituents. Rx”102 is an aliphatic group that may have substituents. The following are possible meanings: a cyclic group, a group formed by removing one hydrogen atom from a condensed cyclic group represented by formula (r-br-1) or (r-br-2), a group formed by removing one hydrogen atom from a lactone-containing cyclic group represented by the aforementioned general formulas (a2-r-1), (a2-r-3) to (a2-r-7), or a group formed by removing one hydrogen atom from a -SO2- containing cyclic group represented by the aforementioned general formulas (a5-r-1) to (a5-r-4). Rx”103 is an aromatic cyclic group that may have substituents, an aliphatic cyclic group that may have substituents, or a chain-like alkylene group that may have substituents. V”101 is a single bond, an alkylene group having 1 to 4 carbon atoms, or a fluorinated alkylene group having 1 to 4 carbon atoms. R102 is a fluorine atom or a fluorinated alkylene group having 1 to 5 carbon atoms. v” represents an independent integer from 0 to 3, q” represents an independent integer from 0 to 20, and n” represents 0 or 1.

[0400] In the aforementioned formula (a-1-an1), Rx”101 is a base obtained by removing one hydrogen atom from R”101 in the aforementioned formula (an-1). In the aforementioned formula (a-1-an2), Rx”102 is a base obtained by removing one hydrogen atom from R”102 in the aforementioned formula (an-2). In the aforementioned formula (a-1-an3), Rx”103 is a base obtained by removing one hydrogen atom from R”103 in the aforementioned formula (an-3).

[0401] V”10, R102, v”, q”, and n” are the same as V”10, R102, v”, q”, and n” in the aforementioned formulas (an-1), (an-2), and (an-3), respectively.

[0402] ・The base shown in formula (b2-an) In the aforementioned formula (b2-an), Rx104 is a cyclic group that may have substituents, a chain-like alkyl group that may have substituents, or a chain-like alkylene group that may have substituents. Rx104 is a base from which one hydrogen atom is removed from R104 in the aforementioned formula (b-2-an). Examples of Rx104 include bases from which one hydrogen atom is removed from R104 in the aforementioned formula (b-2-an).

[0403] R105, L101, L102, V102, and V103 are the same as R105, L101, L102, V102, and V103 in the aforementioned formula (b-2-an).

[0404] ・The base shown in formula (b3-an) In the aforementioned formula (b3-an), Rx107 is a cyclic group that may have substituents, a chain-like alkyl group that may have substituents, or a chain-like alkylene group that may have substituents. Rx107 is a base from which one hydrogen atom is removed from R107 in the aforementioned formula (b-3-an). Examples of Rx107 include bases from which one hydrogen atom is removed from R107 in the aforementioned formula (b-3-an).

[0405] R106, R108, L103, L104, and L105 are the same as R106, R108, L103, L104, and L105 in the aforementioned formula (b-3-an).

[0406] Rx0b is preferably based on the basis shown in equation (b1-an). Among them, Rx0b is preferably based on any one of the aforementioned equations (b1-an1) to (b1-an3), more preferably on the basis shown in either equation (b1-an1) or (b-an2), and especially preferably on the basis shown in equation (b1-an1).

[0407] The following shows specific examples of the anionic portion of the constituent unit (a0) when Rx0b is the base shown in the aforementioned formula (b1-an), but is not limited to such examples. In the formula, Rα represents a hydrogen atom, a methyl group, or a trifluoromethyl group.

[0408]

[0409]

[0410] The following shows specific examples of the anionic portion of the constituent unit (a0) when Rx0b is the base shown in the aforementioned formula (b2-an), but is not limited to such examples. In the formula, Rα represents a hydrogen atom, a methyl group, or a trifluoromethyl group.

[0411]

[0412] The following shows specific examples of the anionic portion of the constituent unit (a0) when Rx0b is the base shown in the aforementioned formula (b3-an), but is not limited to such examples. In the formula, Rα represents a hydrogen atom, a methyl group, or a trifluoromethyl group.

[0413]

[0414]

[0415] ≪Constituted Unit (a0d)≫ {Cation Part} In the aforementioned general formula (a0-1), Ma+ is the aforementioned cation (C0).

[0416] {Anion Section} In the aforementioned general formula (a0-1), Rx0- is a base containing an anion. In the constituent unit (a0d), Rx0- is a base containing anion that captures acid generated by exposure. Examples of anions contained in Rx0- include those shown in the aforementioned formulas (d-1-an), (d-2-an), or (d-3-an).

[0417] As a constituent unit (a0d), an anion portion can be exemplified by the following general formula (a0-1-d).

[0418] [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. Ya01 is a single bond or a divalent linked group. La01 is a single bond, -O-, -COO-, -CON(R')-, -OCO-, -CONHCO-, or -CONHCS-, where R' represents a hydrogen atom or a methyl group. However, when La01 is -O-, Ya01 will not be -CO-. Rx0d is a group shown in the following general formula (d1-an), general formula (d2-an), or general formula (d3-an). * indicates the bond position with La01 in the aforementioned formula (a0-1-d).]

[0419] [In the formula, Rd01~Rd03 are single bonds, cyclic groups that may have substituents, chain-like alkyl groups that may have substituents, or chain-like alkenyl groups that may have substituents. However, in formula (d1-2), the carbon atom adjacent to the S atom in Rd02 is a non-bonded fluorine atom. Rd4 is a cyclic group that may have substituents, a chain-like alkyl group that may have substituents, or a chain-like alkenyl group that may have substituents. Yd1 is a single bond or a divalent linked group.]

[0420] In the aforementioned formula (a0-1-d), R, Ya01, and La01 are the same as R, Ya01, and La01 in the aforementioned formula (a0-1-b).

[0421] In the aforementioned formula (a0-1-d), Rx0d is the basis shown in the aforementioned general formula (d1-an), general formula (d2-an), or (d3-an).

[0422] ・The group shown in formula (d1-an) In the aforementioned formula (d1-an), Rd01 is a single bond, a cyclic group that may have substituents, a chain-like alkyl group that may have substituents, or a chain-like alkylene group that may have substituents. Rd01 is preferably a group in which one hydrogen atom is removed from Rd1 in the aforementioned formula (d-1-an). Examples of Rd01 include groups in which one hydrogen atom is removed from Rd1 in the aforementioned formula (d-1-an). As Rd01, a cyclic group that may have substituents is preferred. As Rx101, an aromatic hydrocarbon group (e.g., an aryl group) in which two hydrogen atoms are removed from a monocyclic alkane or polycyclic alkane is preferred. As a monocyclic alkane, a group with 3 to 6 carbon atoms is preferred; specific examples include cyclopentane and cyclohexane. As polycyclic alkanes, those with 7 to 30 carbon atoms are preferred. Specific examples include adamantane, norcamphene, isocamphene, tricyclic decane, and tetracyclic dodecane. As aromatic hydrocarbon groups, examples include pentylene, pentylenaphthalene, and polycyclic structures containing a bicyclic octane skeleton (polycyclic structures composed of a bicyclic octane skeleton and other ring structures).

[0423] ・The group represented by formula (d2-an) In the aforementioned formula (d2-an), Rd02 is a single bond, a cyclic group that may have substituents, a chain-like alkyl group that may have substituents, or a chain-like alkylene group that may have substituents. Rd02 is preferably a group in which one hydrogen atom is removed from Rd2 in the aforementioned formula (d-2-an). Examples of Rd02 include groups in which one hydrogen atom is removed from Rd2 in the aforementioned formula (d-2-an).

[0424] ・The group represented by formula (d3-an) In the aforementioned formula (d3-an), Rd03 is a single bond, a cyclic group that may have substituents, a chain-like alkyl group that may have substituents, or a chain-like alkylene group that may have substituents. Rd03 is preferably a group in which one hydrogen atom is removed from Rd2 in the aforementioned formula (d-3-an). Examples of Rd03 include groups in which one hydrogen atom is removed from Rd2 in the aforementioned formula (d-3-an).

[0425] Rd4 and Yd1 are the same as Rd4 and Yd1 in the aforementioned formula (d-3-an).

[0426] Rx0d is preferably based on the basis shown in formula (d1-an) or formula (d2-an), with the basis shown in formula (d1-an) being more preferred.

[0427] The following shows specific examples of the anionic portion of the constituent unit (a0) when Rx0d is the base shown in the aforementioned formula (d1-an), but is not limited to such examples. In the formula, Rα represents a hydrogen atom, a methyl group, or a trifluoromethyl group. m” is an integer from 0 to 3.

[0428]

[0429] The following shows specific examples of the anionic portion of the constituent unit (a0) when Rx0d is the base shown in the aforementioned formula (d2-an), but is not limited to such examples. In the formula, Rα represents a hydrogen atom, a methyl group, or a trifluoromethyl group.

[0430]

[0431] The following shows specific examples of the anionic portion of the constituent unit (a0) when Rx0d is the base shown in the aforementioned formula (d2-an), but is not limited to such examples. In the formula, Rα represents a hydrogen atom, a methyl group, or a trifluoromethyl group.

[0432]

[0433] The following shows specific examples of constituent units (a0), but are not limited to them.

[0434]

[0435] The constituent unit (a0) of component (A0) may be one type or two or more types. The proportion of constituent unit (a0) in component (A0) is preferably 3-90 mol%, more preferably 5-75 mol%, even more preferably 10-70 mol%, and particularly preferably 10-60 mol%. The proportion of constituent unit (a0) in component (A0) may also be 100 mol%.

[0436] (A0) The ingredient can be used alone or in combination with two or more ingredients.

[0437] The weight average molecular weight (Mw) of component (A0) (based on polystyrene using gel permeation chromatography (GPC)) is not particularly limited, but is preferably 1,000 to 50,000, more preferably 2,000 to 30,000, and even more preferably 3,000 to 20,000. When the Mw of component (A0) is below the upper limit of this range, it has sufficient solubility in the inhibitor solvent required for use as an inhibitor; when it is above the lower limit of this range, it has good dry etching resistance or inhibitor pattern profile shape. The dispersibility (Mw / Mn) of component (A0) is not particularly limited, but is preferably 1.0 to 4.0, more preferably 1.0 to 3.0, and particularly preferably 1.0 to 2.0.

[0438] ・(A1) Component The resist composition of this embodiment is preferably a resin component (A1) ((A1) component) that changes the solubility of the developer due to the action of acid. As the (A1) component, the same (A1) component as in the first embodiment described above can be used. One (A1) component can be used alone, or two or more can be used together.

[0439] ・・A1 component having a constituent unit (a0) ((A1-0) component) A1 component may also have a constituent unit (a0). In this case, the (A1) component becomes the (A0) component. Hereinafter, the (A1) component having a constituent unit (a0) will also be referred to as the "(A1-0) component".

[0440] The (A1-0) component may contain one or more constituent units (a0). When the (A1-0) component contains constituent units (a0), the proportion of constituent units (a0) in the (A1-0) component is preferably 3-50 mol%, more preferably 5-40 mol%, more preferably 10-30 mol%, and especially preferably 15-20 mol%. When the proportion of constituent units (a0) is above the lower limit of the aforementioned preferred range, lithography properties such as sensitivity and reduction of defects are improved. On the other hand, when the proportion of constituent units (a0) is below the upper limit of the aforementioned preferred range, a balance can be achieved with other constituent units, and various lithography properties become better.

[0441] ≪Constituent Unit (a1)≫ (A1-0) is preferably composed of an acid-decomposing group that increases polarity due to the action of an acid. As the constituent unit (a1), it may be the same as the constituent unit (a1) in the first embodiment described above.

[0442] The (A1-0) component may contain one or more constituent units (a1). The proportion of constituent units (a1) in the (A1-0) component is preferably 5-80 mol%, more preferably 10-75 mol%, even better 20-70 mol%, and particularly preferably 25-60 mol%. When the proportion of constituent units (a1) is above the lower limit of the aforementioned preferred range, lithography properties such as sensitivity, resolution, and improved roughness are enhanced. On the other hand, when the proportion of constituent units (a1) is below the upper limit of the aforementioned preferred range, a balance with other constituent units can be achieved, and various lithography properties become better.

[0443] ≪Other Constituent Units≫ (A1-0) Components may also be those that, in addition to constituent units (a0) and constituent units (a1), have other constituent units as necessary. Examples of other constituent units include constituent units (a2), constituent units (a3), constituent units (a4), constituent units (a10), and constituent units (st).

[0444] Constituent (a2): The (A1-0) component may also have constituent unit (a2). The constituent unit (a2) may be the same as the constituent unit (a2) in the first embodiment described above.

[0445] The (A1-0) component may contain one or more constituent units (a2). When the (A1-0) component contains constituent units (a2), the proportion of constituent units (a2) relative to the total (100 mol%) of all constituent units constituting the (A1) component is preferably 5-60 mol%, more preferably 10-60 mol%, even better 20-60 mol%, and particularly preferably 30-60 mol%. When the proportion of constituent units (a2) is above the aforementioned lower limit of the preferred values, the effects achieved by containing constituent units (a2) can be fully obtained. On the other hand, when the proportion of constituent units (a2) is below the aforementioned upper limit of the preferred values, a balance with other constituent units can be achieved, and various photolithography properties become better.

[0446] Constituent (a3): The (A1-0) component may also have constituent unit (a3). The constituent unit (a3) ​​may be the same as the constituent unit (a3) ​​in the first embodiment described above.

[0447] The (A1-0) component may contain one or more constituent units (a3). When the (A1-0) component contains constituent units (a3), the proportion of constituent units (a3) ​​relative to the total (100 mol%) of all constituent units constituting the (A1-0) component is preferably 1-30 mol%, more preferably 2-25 mol%, and even more preferably 5-20 mol%. When the proportion of constituent units (a3) ​​is above the aforementioned lower limit, the effects achieved by containing constituent units (a3) ​​can be fully obtained. On the other hand, when the proportion of constituent units (a3) ​​is below the aforementioned upper limit, a balance with other constituent units can be achieved, and various photolithography properties become better.

[0448] Constituent Unit (a4): The (A1-0) component may also have constituent unit (a4). The constituent unit (a4) may be the same as the constituent unit (a4) in the first embodiment described above.

[0449] The (A1-0) component may contain one or more constituent units (a4). When the (A1-0) component contains constituent units (a4), the proportion of constituent units (a4) relative to the total number of constituent units (100 mol%) constituting the (A1-0) component is preferably 1 to 40 mol%, and more preferably 5 to 20 mol%. When the proportion of constituent units (a4) is above the aforementioned lower limit, the effects achieved by the constituent units (a4) can be fully obtained. On the other hand, when the proportion of constituent units (a4) is below the aforementioned upper limit, a balance with other constituent units can be achieved, and various photolithography properties become better.

[0450] Constituent Unit (a10): The (A1-0) component is preferably composed of constituent unit (a10). The constituent unit (a10) may be the same as that in the first embodiment described above.

[0451] The (A1-0) component may contain one or more constituent units (a10). When the (A1-0) component contains constituent units (a10), the proportion of constituent units (a10) relative to the total number of constituent units (100 mol%) constituting the (A1-0) component is preferably 10-80 mol%, more preferably 20-70 mol%, more preferably 30-60 mol%, and particularly preferably 30-55 mol%. When the proportion of constituent units (a10) is above the aforementioned lower limit of the preferred values, sensitivity becomes easier to improve. On the other hand, when the proportion of constituent units (a10) is below the aforementioned upper limit of the preferred values, a balance can be achieved with other constituent units, and various lithography properties become better.

[0452] Constituent unit (st): The (A1-0) component may also have a constituent unit (st). The constituent unit (st) may be the same as the constituent unit (st) in the first embodiment described above.

[0453] The (A1-0) component may contain one or more constituent units (st). When the (A1-0) component contains constituent units (st), the proportion of constituent units (st) relative to the total number of all constituent units constituting the (A1-0) component (100 mol%) is preferably 1 to 30 mol%, and more preferably 3 to 20 mol%. When the proportion of constituent units (st) is above the aforementioned lower limit, the effects achieved by containing constituent units (st) can be fully obtained. On the other hand, when the proportion of constituent units (st) is below the aforementioned upper limit, a balance with other constituent units can be achieved, and various photolithography properties become better.

[0454] (A1-0) Component can be used alone or in combination with two or more. Examples of (A1-0) component include polymeric compounds having repeating structures of constituent units (a0) and (a1), preferably polymeric compounds having repeating structures of constituent units (a0), (a1), and (a10). Among the above, suitable examples of (A1-0) component include polymeric compounds composed of repeating structures of constituent units (a0) and (a1); and polymeric compounds composed of repeating structures of constituent units (a0), (a1), and (a10).

[0455] The weight average molecular weight (Mw) of component (A1-0) (based on polystyrene using gel permeation chromatography (GPC)) is not particularly limited, but is preferably 1,000 to 50,000, more preferably 2,000 to 30,000, and even more preferably 3,000 to 20,000. When the Mw of component (A1-0) is below the upper limit of this range, it has sufficient solubility in the inhibitor solvent required for use as an inhibitor; when it is above the lower limit of this range, it has good dry etching resistance or inhibitor pattern profile shape. The dispersibility (Mw / Mn) of component (A1-0) is not particularly limited, but is preferably 1.0 to 4.0, more preferably 1.0 to 3.0, and particularly preferably 1.0 to 2.0.

[0456] ・(A2) Component The inhibitor composition of this embodiment may also contain component (A2) as component (A). As component (A2), the same component (A2) as in the first embodiment described above may be used.

[0457] The proportion of (A1-O) component 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. When the proportion is 25% by mass or more, it becomes easier to form resist patterns with excellent lithography properties such as high sensitivity or resolution, improved roughness, and reduced defects.

[0458] In the resist composition of this embodiment, the content of component (A) can be adjusted according to the desired resist film thickness, etc.

[0459] <Other Ingredients> In addition to ingredient (A) mentioned above, the inhibitor composition of this embodiment may also contain other ingredients. Examples of other ingredients include ingredients (B), (D), (E), (F), and (S) as shown below.

[0460] ≪(B) component≫ The inhibitor composition of this embodiment may also contain component (B). Component (B) may be the same as component (B1) in the first embodiment described above.

[0461] In the inhibitor composition of this embodiment, component (B) can be used alone or in combination with two or more components. In the case of the inhibitor composition containing component (B), the content of component (B) relative to 100 parts by mass of component (A) is preferably 5-40 parts by mass, more preferably 10-40 parts by mass, even more preferably 12-40 parts by mass, and particularly preferably 15-35 parts by mass. By making the content of component (B) within the aforementioned preferred range, sufficient pattern formation can be achieved. Furthermore, since it is easy to obtain a homogeneous solution when each component of the inhibitor composition is dissolved in an organic solvent, and the storage stability of the inhibitor composition is good, it is preferable.

[0462] ≪(D) component≫ The inhibitor composition of this embodiment is preferably containing component (D). The component (D) can be the same as that in the first embodiment described above.

[0463] In the resist composition of this embodiment, component (D) can be used alone or in combination with two or more components. In the resist composition of this embodiment containing component (D), the content of component (D) is preferably 0.5 to 20 parts by mass, more preferably 1 to 15 parts by mass, and even more preferably 2 to 8 parts by mass, relative to 100 parts by mass of component (A). When the content of component (D) is above the aforementioned lower limit, good photolithography properties and resist pattern shape are easily obtained. On the other hand, when the content of component (D) is below the aforementioned upper limit, sensitivity can be well maintained.

[0464] ≪(E) Component≫ The resist composition of this embodiment may also contain component (E). The (E) component may be the same as that in the first embodiment described above. In the resist composition of this embodiment, component (E) may be used alone or in combination with two or more. In the case where the resist composition of this embodiment contains component (E), the content of component (E) is preferably 0.01 to 5 parts by mass relative to 100 parts by mass of component (A), and more preferably 0.05 to 3 parts by mass. By achieving the above range, sensitivity and lithography properties are improved.

[0465] ≪(F) Component≫ The inhibitor composition of this embodiment may also contain component (F). Component (F) may be the same as component (E) in the aforementioned first embodiment. In the inhibitor composition of this embodiment, component (F) may be used alone or in combination with two or more. In the case where the inhibitor composition of this embodiment contains component (F), the content of component (F) relative to 100 parts by mass of component (A) is preferably 0.5 to 10 parts by mass, and more preferably 1 to 10 parts by mass.

[0466] ≪(S) component≫ The (S) component can be the same as the (S) component in the first embodiment described above. The amount of (S) component used is not particularly limited, and the concentration that can be coated onto the substrate, etc., should be appropriately set according to the coating film thickness. Generally speaking, the (S) component is used in a manner that makes the solid component concentration of the resist composition in the range of 0.1 to 20% by mass, preferably in the range of 0.2 to 15% by mass.

[0467] The inhibitor composition of this embodiment can be further modified as needed by adding additives that are miscible, such as addition resins for improving the performance of the inhibitor film, solubility inhibitors, plasticizers, stabilizers, colorants, anti-glare agents, dyes, etc.

[0468] The inhibitor composition of this embodiment is similar to that of the inhibitor composition of the first embodiment described above. After dissolving the inhibitor material in component (S), impurities are removed using a polyimide porous membrane, a polyimide porous membrane, etc.

[0469] The resist composition of this embodiment described above contains a resin component (A0) containing a cation (CO) as component (A). The cation (CO) is a low LUMO cation with a planar structure. The resin component (A0) has a constituent unit (a0) that generates acid upon exposure. By containing a cation (CO), the efficiency of acid generation by exposure is improved in the constituent unit (a0). Therefore, the sensitivity of the resist composition containing the resin component (A0) is improved. Furthermore, the cation (CO) has two or more electron-withdrawing groups in the phenyl group, which improves the solubility for component (S). In addition, the solubility for the developer is improved during development after exposure. Therefore, the resist composition containing the resin component (A0) can reduce defects. Based on the above, the resist composition of this embodiment can achieve both high sensitivity and reduced defects.

[0470] [Embodiments 4-7] The inhibitor composition of embodiment 4 contains compound (C) as component (B) and component (D). That is, the inhibitor composition of embodiment 4 contains component (B0) and component (D0). It is preferable that the inhibitor composition of embodiment 4 contains component (A1), component (B0), and component (D0). The inhibitor composition of embodiment 4 may also contain component (E), component (F), and component (S) as other components. In the inhibitor composition of embodiment 4, the content of each component can be made the same as in embodiments 1-3.

[0471] The inhibitor composition of the fifth embodiment contains compound (C) as component (B) and component (A). That is, the inhibitor composition of the fifth embodiment contains component (B0) and component (A0). Component (A0) may have either a constituent unit (a0b) or a constituent unit (a0d), or both, but it is preferred to have constituent unit (a0d). The inhibitor composition of the fifth embodiment is preferably composed of component (A1-0) and component (B0). The inhibitor composition of the fifth embodiment may also contain component (D), component (E), component (F), and component (S) as other components. In the inhibitor composition of the fifth embodiment, the content of each component can be made the same as in the aforementioned embodiments 1 to 3.

[0472] The inhibitor composition of the sixth embodiment contains compound (C) as component (D) and component (A). That is, the inhibitor composition of the sixth embodiment contains component (D0) and component (A0). Component (A0) may have either a constituent unit (a0b) or a constituent unit (a0d), or both, but it is preferred to have constituent unit (a0b). The inhibitor composition of the sixth embodiment is preferably composed of component (A1-0) and component (D0). The inhibitor composition of the sixth embodiment may also contain component (B), component (E), component (F), and component (S) as other components. In the inhibitor composition of the sixth embodiment, the content of each component can be made the same as in the aforementioned embodiments 1 to 3.

[0473] The inhibitor composition of the seventh embodiment contains compound (C) as component (B), component (D), and component (A). That is, the inhibitor composition of the seventh embodiment contains component (B0), component (D0), and component (A0). Component (A0) may have either a constituent unit (a0b) or a constituent unit (a0d), or both. It is preferred that the inhibitor composition of the seventh embodiment contains component (B0), component (A1-0), and component (D0). The inhibitor composition of the seventh embodiment may also contain component (E), component (F), and component (S) as other components. In the inhibitor composition of the seventh embodiment, the content of each component can be made the same as in the aforementioned embodiments 1 to 3.

[0474] (Resistant Pattern Forming Method) The resistant pattern forming method of the second aspect of the present invention is a method comprising: a step of forming a resist film on a support using a resist composition as described in the first aspect; a step of exposing the resist film; and a step of developing the exposed resist film to form a resist pattern. As one embodiment of this resistant pattern forming method, a resistant pattern forming method performed, for example, by the following operations can be cited.

[0475] First, the resist composition of the above embodiment is coated onto a support using a spinner, and a baking (post-coating baking (PAB)) treatment is performed 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 selectively exposed using an exposure apparatus such as an electron line drawing apparatus or an ArF exposure apparatus, either by exposure through a mask (mask pattern) with a pre-formed pattern or by direct irradiation of electron lines without a mask pattern. Then, a baking (post-exposure baking (PEB)) treatment is performed at a temperature of, for example, 80-150°C for 40-120 seconds, preferably 60-90 seconds. Next, the aforementioned resist film is developed. In the case of an alkaline development process, an alkaline developer is used; in the case of a solvent development process, a developer containing an organic solvent (organic developer) is used.

[0476] After development, a rinsing process is preferable. In alkaline development processes, rinsing with pure water is preferred; in solvent development processes, rinsing with a solution containing organic solvents is preferred. In solvent development processes, after the aforementioned development or rinsing process, a process to remove the developer or rinsing solution adhering to the pattern using a supercritical fluid may also be performed. Drying is then performed after development or rinsing. Alternatively, depending on the circumstances, a baking process (post-baking) may be performed after the aforementioned development process. This operation forms a resist pattern.

[0477] There are no particular limitations on the support body; conventionally known materials can be used, such as substrates for electronic components, or substrates on which a specified wiring pattern has already been formed. More specifically, examples include metal substrates such as silicon wafers, copper, chromium, iron, and aluminum, or glass substrates. Materials for the wiring pattern can include, for example, copper, aluminum, nickel, and gold. Furthermore, the support body can also be a substrate on which an inorganic and / or organic film is disposed. 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 formed on a substrate, and the resist pattern formed on the upper resist film is used as a mask to pattern the lower organic film. This method is considered capable of forming patterns with a high aspect ratio. That is, 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, thus enabling the formation of fine patterns with a high aspect ratio. The multilayer resist method is basically divided into: a method of forming a two-layer structure of an upper resist film and a lower organic film (2-layer resist method), and a method of forming a multilayer structure of three or more layers, in which one or more intermediate layers (such as metal thin films) are formed between the upper resist film and the lower organic film (3-layer resist method).

[0478] There are no particular limitations on the wavelength used for exposure; ArF excimer lasers, KrF excimer lasers, F2 excimer lasers, EUV (extreme ultraviolet), VUV (vacuum ultraviolet), EB (electron beam), X-rays, soft X-rays, and other types of radiation can be used. The aforementioned resist composition is highly useful as a KrF excimer laser, ArF excimer laser, EB, or EUV, and is particularly useful as an ArF excimer laser.

[0479] The exposure method for the resist film can be either conventional exposure (dry exposure) performed in an inert gas such as air or nitrogen, or liquid immersion lithography. Liquid immersion lithography involves filling the space between the resist film and the lens at the lowest position of the exposure apparatus with a solvent (immersion medium) having a refractive index higher than that of air, and then performing exposure (immersion exposure) under these conditions. As the immersion medium, a solvent having a refractive index higher than that of air and lower than that of the resist film being exposed is preferred. As long as the refractive index of the solvent is within the aforementioned range, there are no particular limitations. Examples of solvents having a refractive index higher than that of air and lower than that of the aforementioned resist film include, for example, water, fluorine-based inert liquids, silicon-based solvents, and hydrocarbon-based solvents. Specific examples of fluorine-based inert liquids include liquids with fluorine compounds such as C3HCl2F5, C4F9OCH3, C4F9OC2H5, and C5H3F7 as the main component, with a boiling point preferably between 70 and 180°C, and more preferably between 80 and 160°C. Fluorine-based inert liquids with boiling points within the above range are preferable because they allow for easy removal of the immersion medium after exposure. Perfluoroalkyl compounds, in particular, where all hydrogen atoms of the alkyl group are replaced by fluorine atoms, are preferred as fluorine-based inert liquids. Examples of perfluoroalkyl compounds include perfluoroalkyl ethers and perfluoroalkylamines. Specifically, examples of perfluoroalkyl ethers include perfluoro(2-butyltetrahydrofuran) (boiling point 102°C), and examples of perfluoroalkylamines include perfluorotributylamine (boiling point 174°C). From the perspectives of cost, safety, environmental issues, and versatility, water is the better choice as a liquid immersion medium.

[0480] Examples of alkaline developing solutions used in alkaline developing processes include 0.1-10% by mass tetramethylammonium hydroxide (TMAH) aqueous solutions. As for organic solvents used in solvent developing processes, any solvent capable of dissolving component (A) (the component (A) before exposure) 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 alcoholic hydroxyl groups. "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 nitrile groups. Aminoamine solvents are organic solvents whose structure contains amide groups. Ether solvents are organic solvents whose structure contains COC. Among organic solvents, there are also those containing multiple types of functional groups that impart the characteristics of the aforementioned solvents; in this case, they are considered to be any type of solvent containing the functional groups possessed by that organic solvent. For example, diethylene glycol monomethyl ethers are considered to be any of the alcohol solvents and ether solvents in the above classification. Hydrocarbon solvents are hydrocarbon solvents composed of halogenable hydrocarbons and without substituents other than halogen atoms. Fluorine atoms are preferred as halogen atoms. Among the organic solvents contained in organic developers, polar solvents are preferred, such as ketone solvents, ester solvents, and nitrile solvents.

[0481] Examples of ketone solvents include, for example, 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, acetoethyl alcohol, acetophenone, methyl naphthyl ketone, isophorone, propenyl carbonate, γ-butyrolactone, methylpentyl ketone (2-heptanone), etc. Among these, methylpentyl ketone (2-heptanone) is preferred as a ketone solvent.

[0482] Examples of ester-based solvents include methyl acetate, butyl acetate, ethyl acetate, isopropyl acetate, amyl acetate, isopentyl 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, and 4-ethoxybutyl acetate. 4-Propoxybutylacetic acid ester, 2-Methoxypentylacetic acid ester, 3-Methoxypentylacetic acid ester, 4-Methoxypentylacetic acid ester, 2-Methyl-3-Methoxypentylacetic acid ester, 3-Methyl-3-Methoxypentylacetic acid ester, 3-Methyl-4-Methoxypentylacetic acid ester, 4-Methyl-4-Methoxypentylacetic acid ester, 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.

[0483] Examples of nitrile solvents include acetonitrile, propionitrile, valerate, and butyronitrile.

[0484] Known additives may be added to organic developers as necessary. Examples of such additives include surfactants. There are no particular limitations on the surfactant, and ionic or nonionic fluorinated and / or silicone surfactants may be used. Nonionic surfactants are preferred, and nonionic fluorinated or silicone surfactants are more preferred. When surfactants are added, the amount added is usually 0.001 to 5% by mass relative to the total amount of the organic developer, preferably 0.005 to 2% by mass, and more preferably 0.01 to 0.5% by mass.

[0485] The developing process can be carried out by known developing methods, such as the method of immersing the support in the developing solution for a fixed time (immersion method), the method of making the developing solution float and remain still on the surface of the support by means of surface tension for a fixed time (liquid holding method), the method of spraying the developing solution onto the surface of the support (spraying method), and the method of scanning the developing solution ejection nozzle at a fixed speed on a support rotating at a fixed speed and continuously ejecting the developing solution at the same time (dynamic distribution method), etc.

[0486] The organic solvent contained in the rinsing solution used for rinsing after development in the solvent-based developing process may be appropriately selected from organic solvents listed above that are not easily soluble in the inhibitor pattern. Generally, at least one solvent selected from hydrocarbon solvents, ketone solvents, ester solvents, alcohol solvents, amide solvents, and ether solvents is used. Among these, at least one solvent selected from hydrocarbon solvents, ketone solvents, ester solvents, alcohol solvents, and amide solvents is preferred, at least one solvent selected from alcohol solvents and ester solvents is more preferred, and alcohol solvents are particularly preferred. The alcohol solvent used in the rinsing solution is preferably a monovalent alcohol with 6 to 8 carbon atoms, and the monovalent alcohol may be linear, branched, or cyclic. Specifically, examples include 1-hexanol, 1-heptanol, 1-octanol, 2-hexanol, 2-heptanol, 2-octanol, 3-hexanol, 3-heptanol, 3-octanol, 4-octanol, and benzyl alcohol. Among these, 1-hexanol, 2-heptanol, and 2-hexanol are preferred, with 1-hexanol and 2-hexanol being even more preferred. Each of these organic solvents can be used alone or in combination of two or more. Furthermore, it can be used in combination with organic solvents other than those mentioned above or with water. However, considering the developing characteristics, the amount of water added to the rinse solution relative to the total amount of the rinse solution is preferably 30% by mass or less, more preferably 10% by mass or less, even better 5% by mass or less, and particularly preferably 3% by mass or less. Known additives can be added to the rinse solution as necessary. Examples of such additives include surfactants. Surfactants can be categorized as described above, with nonionic surfactants being preferred, particularly nonionic fluorinated surfactants or nonionic silicone surfactants. When surfactants are incorporated, the amount incorporated relative to the total amount of the washing solution is typically 0.001–5% by mass, preferably 0.005–2% by mass, and more preferably 0.01–0.5% by mass.

[0487] The rinsing treatment (cleaning treatment) using a rinsing solution can be carried out by known rinsing methods. Examples of such rinsing treatment methods include, for instance, continuously dispensing rinsing solution onto a support rotating at a fixed speed (rotation coating method), immersing the support in the rinsing solution for a fixed time (immersion method), and spraying rinsing solution onto the surface of the support (spraying method).

[0488] According to the resist pattern forming method of this embodiment described above, since the resist composition of the first state sample mentioned above is used, a resist pattern with reduced defects can be formed.

[0489] (Compound) The third state of the compound of the present invention is the compound shown in the following general formula (M0) (hereinafter also referred to as "compound (M0)").

[0490] [In the formula, X01 is an electron-withdrawing group, X02 is an electron-withdrawing group different from X01, and R01 is an electron-donating group. R02 and R03 are each independent substituents. nx1 and nx2 are each independent integers from 1 to 4, n1 is an integer from 0 to 3, and nx1 + nx2 + n1 ≦ 5. n2 and n3 are each independent integers from 0 to 4. When nx1 is 2 or more, the complex X01 groups can be the same or different. When nx2 is 2 or more, the complex X02 groups can be the same or different. When n1 is 2 or more, the complex R01 groups can be the same or different. When n2 is 2 or more, the complex R02 groups can be the same or different. When n3 is 2 or more, the complex R03 groups can be the same or different.] X- represents a relative anion.

[0491] {Cation section} The cation section is the same as the cation (CO) shown in the aforementioned general formula (C0).

[0492] {Anion section} X- is a relative anion. Examples of X- include anion sections of compounds shown in the aforementioned general formula (b0), anion sections of compounds shown in the aforementioned general formula (d0), and anion sections of constituent units shown in the aforementioned general formula (a0-1).

[0493] <Method for Manufacturing Compound> The compound (M0) can be manufactured using known methods. Examples of methods for manufacturing the compound (M0) include, for instance, a method comprising steps 1 and 2 as shown below.

[0494] The compounds used in each step may be commercially available or synthesized. As solvents in each reaction of steps 1 and 2, solvents capable of dissolving the compounds used in each step and not reacting with them may be used. Examples of solvents include dichloromethane, dichloroethane, chloroform, tetrahydrofuran, N,N-dimethylformamide, dimethylacetamide, dimethyl sulfoxide, acetonitrile, and propionitrile.

[0495] Step 1: Step 1 involves reacting a mixture of compound (I) and compound (II) with TMS-X in a solvent to obtain compound (pre). Examples of solvents used in Step 1 include tetrahydrofuran. Examples of reaction temperatures include 0–50°C, with 10–40°C being preferred. The reaction time can be appropriately set according to the reactivity and amount of the compound used. Examples of reaction times include 10 minutes to 24 hours, with 10 minutes to 12 hours being preferred.

[0496] The reaction can be stopped by adding water to the reaction solution after any reaction time. After the reaction is complete, the compound (pre) can be purified by solvent extraction, vacuum concentration, crystallization, etc. Examples of solvents used for solvent extraction include dichloromethane. Examples of solvents used for crystallization include a mixture of dichloromethane and tert-butyl ethyl ether.

[0497] [In the formula, X01, X02, R01~R03, nx1, nx2, and n1~n3 are the same as those described in the aforementioned formula (M0). Xh represents a halogen atom. TMS represents a trimethylsilyl group. X” represents the relative anion in the compound (pre).]

[0498] In the aforementioned reaction formula, examples of halogen atoms in Xh include fluorine atoms, chlorine atoms, bromine atoms, and iodine atoms. Examples of relative anions in X”- include Br-, Cl-, and CF3SO3-. Examples of compounds represented by TMS-X” include trimethylsilyl trifluoromethanesulfonate (TMSOTf).

[0499] Step 2: Step 2 involves a salt exchange reaction in a solvent, in which the mixed compound (pre) and the salt exchange compound (III) are reacted to obtain compound (M0). Examples of solvents used in Step 2 include dichloromethane. Examples of reaction temperatures include 0–100°C, with 0–50°C being preferred. The reaction time can be appropriately set according to the reactivity and amount of the compound used. Examples of reaction times include 10 minutes to 24 hours, with 10 minutes to 12 hours being preferred.

[0500] After the salt exchange reaction is completed, the compound (M0) can also be isolated and / or purified. Known methods can be used for the isolation and / or purification of the compound (M0). Examples of methods for isolation and / or purification include concentration, solvent extraction, distillation, crystallization, recrystallization, and chromatographic analysis, and these methods can be used in combination.

[0501] [In the formula, X01, X02, R01~R03, nx1, nx2, n1~n3, and X- are the same as those described in the aforementioned formula (M0). X”- represents the relative anion in the compound (pre). M'+ represents the ammonium cation.]

[0502] In the aforementioned reaction formula, the ammonium cation in M'+ can be an organic ammonium cation, preferably a fourth-order ammonium cation. The ammonium cation in M'+ can be appropriately selected according to the relative anion in compound (III).

[0503] The structure of the compound obtained by the above operation can be identified by general organic analysis methods such as 1H-nuclear magnetic resonance (NMR) spectroscopy, 13C-NMR spectroscopy, 19F-NMR spectroscopy, infrared absorption (IR) spectroscopy, mass analysis (MS), elemental analysis, and X-ray crystallization diffraction.

[0504] As a specific example of compound (M0), one may be given as the same as that given as a specific example of the aforementioned compound (B0) or the aforementioned compound (D0).

[0505] (Acid generating agent) The acid generating agent of the fourth state of the present invention comprises a compound represented by the following general formula (B0).

[0506] [In the formula, X01 is an electron-withdrawing group, X02 is an electron-withdrawing group different from X01, and R01 is an electron-donating group. R02 and R03 are each independent substituents. nx1 and nx2 are each independent integers from 1 to 4, n1 is an integer from 0 to 3, and nx1 + nx2 + n1 ≦ 5. n2 and n3 are each independent integers from 0 to 4. When nx1 is 2 or more, the complex X01 groups can be the same or different. When nx2 is 2 or more, the complex X02 groups can be the same or different. When n1 is 2 or more, the complex R01 groups can be the same or different. When n2 is 2 or more, the complex R02 groups can be the same or different. When n3 is 2 or more, the complex R03 groups can be the same or different.] Xb- is a relative anion.

[0507] {Cation section} The cation section is the same as the cation (CO) shown in the aforementioned general formula (C0).

[0508] {Anion section} Xb- is a relative anion. Xb- is the same as Xb- in the aforementioned general formula (b0).

[0509] As a specific example of the compound shown in the general formula (B0), there are examples that are the same as those given as specific examples of the aforementioned compound (B0).

[0510] The acid generating agent of this embodiment comprises a compound shown in general formula (B0). The cationic portion of this compound is a planar low least unoccupied molecular orbital (LLUMO) cation, and the acid generating efficiency is high. Therefore, the sensitivity of the resist composition containing the acid generating agent of this embodiment is improved. Furthermore, the aforementioned compound, by having two or more electron-withdrawing groups in the phenyl group in the cationic portion, enhances the solubility of the (S) component when used in the resist composition. Moreover, the solubility in the developer is improved during post-exposure development. Thus, the resist composition containing the acid generating agent of this embodiment can reduce defects. Based on the above, the acid generating agent of this embodiment can achieve both high sensitivity and reduced defects in the resist composition.

[0511] (Acid diffusion control agent) The acid diffusion control agent of the fifth state of the present invention contains a compound represented by the following general formula (D0).

[0512] [In the formula, X01 is an electron-withdrawing group, X02 is an electron-withdrawing group different from X01, and R01 is an electron-donating group. R02 and R03 are each independent substituents. nx1 and nx2 are each independent integers from 1 to 4, n1 is an integer from 0 to 3, and nx1 + nx2 + n1 ≦ 5. n2 and n3 are each independent integers from 0 to 4. When nx1 is 2 or more, the complex X01 groups can be the same or different. When nx2 is 2 or more, the complex X02 groups can be the same or different. When n1 is 2 or more, the complex R01 groups can be the same or different. When n2 is 2 or more, the complex R02 groups can be the same or different. When n3 is 2 or more, the complex R03 groups can be the same or different.] Xd- is a relative anion.

[0513] {Cation section} The cation section is the same as the cation (CO) shown in the aforementioned general formula (C0).

[0514] {Anion section} Xd- is a relative anion. Xd- is the same as Xd- in the aforementioned general formula (d0).

[0515] As a specific example of the compound shown in the general formula (D0), there are examples that are the same as those given as specific examples of the aforementioned compound (D0).

[0516] The acid diffusion control agent of this embodiment comprises a compound shown in general formula (DO). The cationic portion of this compound is a planar low least unoccupied molecular orbital (LLUMO) cation, which loses its acid diffusion control ability due to decomposition upon exposure. Therefore, the sensitivity of the resist composition containing the acid diffusion control agent of this embodiment is improved. Furthermore, the aforementioned compound, by having two or more electron-withdrawing groups in the phenyl group in the cationic portion, enhances the solubility of the (S) component when used in the resist composition. Moreover, its solubility in the developer is enhanced during post-exposure development. Thus, the resist composition containing the acid diffusion control agent of this embodiment can reduce defects. Based on the above, the acid diffusion control agent of this embodiment achieves both high sensitivity and reduced defects in the resist composition.

[0517] (Polymer compound) The polymer compound of the sixth state of the present invention has the constituent units shown in the following general formula (A0-1).

[0518] [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. Rx0 is a group containing an anion. X01 is an electron-withdrawing group, X02 is an electron-withdrawing group different from X01, and R01 is an electron-donating group. R02 and R03 are each independently substituents. nx1 and nx2 are each independently integers from 1 to 4, n1 is an integer from 0 to 3, and nx1 + nx2 + n1 ≦ 5. n2 and n3 are each independently integers from 0 to 4. When nx1 is 2 or more, the multiple X01 groups can be the same or different. When nx2 is 2 or more, the multiple X02 groups can be the same or different. When n1 is 2 or more, the multiple R01 groups can be the same or different.] When n² is 2 or more, the complex numbers in the R₀² system can be identical or distinct. When n³ is 2 or more, the complex numbers in the R₀³ system can be identical or distinct.

[0519] {Cation section} The cation section is the same as the cation (CO) shown in the aforementioned general formula (C0).

[0520] {Anion part} Rx0 is a base containing anion. Rx0 is the same as Rx0 in the aforementioned general formula (a0-1).

[0521] As a specific example of the constituent unit shown in the general form (A0-1), there are examples that are the same as those given as specific examples of the aforementioned constituent unit (a0).

[0522] As a polymeric compound of this embodiment, examples include those that are the same as the aforementioned resin component (A-0) or resin component (A1-0).

[0523] The polymer compound of this embodiment contains a constituent unit shown in the general formula (A0-1). The cationic portion of this constituent unit is a planar low least unoccupied molecular orbital (LLUMO) cation, which is easily decomposed upon exposure. Therefore, when it has the function of an acid generator, the acid generation efficiency is high. However, when it has the function of an acid diffusion control agent, the acid diffusion control ability is easily lost upon exposure. Therefore, the sensitivity of the resist composition containing the polymer compound of this embodiment is improved. Furthermore, the aforementioned constituent unit has two or more electron-withdrawing groups in the phenyl portion, which improves the solubility of the (S) component when used in the resist composition. Moreover, the solubility in the developer is improved during development after exposure. Thus, the resist composition containing the polymer compound of this embodiment can reduce defects. Based on the above, the acid diffusion control agent of this embodiment can achieve both high sensitivity of the resist composition and reduction of defects.

[0524] <Method for manufacturing polymeric compounds> The polymeric compound of this embodiment can be obtained by polymerizing a monomer that derives a constituent unit (a0) and a monomer that derives other constituent units (constituent units (a1)~(a4), (a10), (st), etc.) as necessary, using a known free radical polymerization initiator such as azobisisobutyronitrile (AIBN).

[0525] The resist composition of the above-described embodiment, and the various materials used in the resist pattern forming method of the above-described embodiment (e.g., resist solvent, developer, rinse solution, composition for forming antireflective film, composition for forming top coating, etc.) are preferably free from impurities such as metals, metal salts containing halogens, acids, alkalis, and components containing sulfur or phosphorus atoms. Examples of impurities containing metal atoms include Na, K, Ca, Fe, Cu, Mn, Mg, Al, Cr, Ni, Zn, Ag, Sn, Pb, Li, or salts thereof. The content of these impurities is preferably 200 ppb or less, more preferably 1 ppb or less, even better 100 ppt (parts per trillion), particularly preferably 10 ppt or less, and ideally substantially free (below the detection limit of the measuring device). [Example]

[0526] Hereinafter, the present invention will be described in more detail by way of examples, but the present invention is not limited to these examples.

[0527] <Preparation of the Compound> (Preparation Example B1) Preparation Example B1-1: Magnesium (4.2g) and tetrahydrofuran (19g) were stirred at 50°C, and a tetrahydrofuran (THF) solution of compound (1) (38g) (75g) was added dropwise at the same temperature. After the dropwise addition was complete, the mixture was stirred for 2 hours, cooled to room temperature, and tetrahydrofuran (75g) was added to obtain a THF solution of compound (1') (solution 1). In another container, dibenzothiophene 5-oxide (10g) and THF (75g) were placed and stirred at room temperature. Trimethylsilyl trifluoromethanesulfonate (TMSOTf) (63g) and solution 1 were added dropwise. After the dropwise addition was complete, the reaction was continued at room temperature for 1 hour to complete the reaction. Then, dichloromethane (100g) and water (100g) were added, and the mixture was stirred for 30 minutes. The aqueous layer was then removed. The organic layer was washed three times with ultrapure water (100g) and then concentrated under reduced pressure. The residue was concentrated by crystallization using dichloromethane / tert-butyl methyl ether to obtain the precursor (pre-1) (6.2g) as a white solid. In the following formula, "OTf-" represents trifluoromethanesulfonate.

[0528]

[0529] Manufacturing Example B1-2: Dichloromethane (50g) and water (50g) were added to the precursor (pre-1) (6.2g) and compound (B-an1) (5.8g), and the mixture was stirred thoroughly before separation. The organic layer was washed with 1% hydrochloric acid (50g) and then washed three times with pure water (50g). Diethyl ether (150g) was added to the organic layer, and the precipitated crystals were recovered by vacuum filtration. The crystals obtained by vacuum drying yielded compound (B0-1) (17.1g).

[0530]

[0531] (Manufacturing Examples B2~B12) Except for replacing compound (1) with compounds (2)~(12), the other operations are the same as in Manufacturing Example B1-1, and precursors (pre-2)~(pre-12) are obtained respectively. Except for replacing precursor (pre-1) with precursors (pre-2)~(pre-12), the other operations are the same as in Manufacturing Example B1-2, and compounds (B0-2)~(B0-12) are obtained respectively.

[0532]

[0533]

[0534]

[0535]

[0536]

[0537] (Manufacturing Examples B13~B16) Except for changing compound (B-an1) to compounds (B-an13)~(B-an16), the operation is the same as in Manufacturing Example B1, and compounds (B0-13)~(B0-16) are obtained respectively.

[0538]

[0539]

[0540] (Manufacturing Example D1) Dichloromethane (50g) and water (50g) were added to the precursor (pre-1) (36.2g) and compound (D-an1) (5.2g), and the mixture was stirred thoroughly and then separated. The organic layer was washed with 1% hydrochloric acid (50g) and then washed three times with pure water (50g). The precipitated crystals were recovered by adding diethyl ether (150g) to the organic layer and filtering under reduced pressure. The crystals obtained by drying under reduced pressure yielded compound (D0-1) (5.9g).

[0541]

[0542] (Manufacturing Examples D2~D12) Except for changing the precursor (pre-1) to the precursor (pre-2)~(pre-12), the operation is the same as in Manufacturing Example D1, and compounds (D0-2)~(D0-12) are obtained respectively.

[0543]

[0544]

[0545]

[0546] (Manufacturing Examples D13~D14) Except for changing compound (D-an1) to compound (D-an13)~(D-an14), the other operations are the same as in Manufacturing Example D1, and compounds (D0-13)~(D0-14) are obtained respectively.

[0547]

[0548]

[0549] The NMR measurement results of compounds (B0-1) to (B0-16) and compounds (D0-1) to (D0-14) manufactured in the above manufacturing examples are shown in Tables 1 to 7.

[0550]

[0551]

[0552]

[0553]

[0554]

[0555]

[0556]

[0557] <Manufacturing of Polymer Compounds> The polymer compounds (A1-01) to (A1-02) used in this embodiment were obtained by free radical polymerization of monomers that derive the constituent units of each polymer compound at specified molar ratios. For each obtained polymer compound, the weight average molecular weight (Mw) and molecular weight dispersion (Mw / Mn) were determined by GPC measurement (conversion to standard polystyrene). Furthermore, for each obtained polymer compound, the copolymerization composition ratio (the proportion of each constituent unit in the structural formula (molar ratio)) was determined by carbon-13 nuclear magnetic resonance spectroscopy (600MHz_13C-NMR).

[0558]

[0559] Polymer compound (A1-01): Weight average molecular weight (Mw) 9500, molecular weight dispersion (Mw / Mn) 1.72, l / m / n = 55 / 30 / 15. Polymer compound (A1-02): Weight average molecular weight (Mw) 9500, molecular weight dispersion (Mw / Mn) 1.75, l / m / n = 55 / 30 / 15.

[0560] <Preparation of inhibitor composition> (Examples 1-60, Comparative Examples 1-24) The inhibitor compositions of each example were prepared by mixing and dissolving the components shown in Tables 8-19.

[0561]

[0562]

[0563]

[0564]

[0565]

[0566]

[0567]

[0568]

[0569]

[0570]

[0571]

[0572]

[0573] In Tables 8-19, each abbreviation has the following meaning. The value in [ ] is the amount of blending (parts by mass). (A1)-01~(A1)-02: The above-mentioned polymer compounds (A1-01)~(A1-02). (A1)-1~(A1)-5: The following polymer compounds (A1-1)~(A1-5). Polymer compound (A1-1): Weight average molecular weight (Mw) 5500, molecular weight dispersion (Mw / Mn) 1.76, l / m=40 / 60. Polymer compound (A1-2): Weight average molecular weight (Mw) 5500, molecular weight dispersion (Mw / Mn) 1.66, l / m=40 / 60. Polymer compound (A1-3): Weight average molecular weight (Mw) 5500, molecular weight dispersion (Mw / Mn) 1.72, l / m / n = 30 / 60 / 10. Polymer compound (A1-4): Weight average molecular weight (Mw) 9500, molecular weight dispersion (Mw / Mn) 1.72, l / m / n = 55 / 30 / 15. Polymer compound (A1-5): Weight average molecular weight (Mw) 9500, molecular weight dispersion (Mw / Mn) 1.75, l / m / n = 55 / 30 / 15.

[0574]

[0575]

[0576] (B0)-1~(B0)-16: Acid generating agents composed of the above compounds (B0-1)~(B0-16).

[0577] (B1)-1~(B1)-14: Acid generating agents composed of the following compounds (B1-1)~(B1-14).

[0578]

[0579]

[0580]

[0581]

[0582] (D0)-1~(D0)-14: Photodegradable bases composed of the above compounds (D0-1)~(D0-14).

[0583] (D1)-1~(D1)-13: Acid diffusion control agents composed of compounds represented by the following chemical formulas (D1-1)~(D1-13).

[0584]

[0585]

[0586]

[0587]

[0588] (S)-1: A mixed solvent of propylene glycol monomethyl ether acetate and propylene glycol monomethyl ether = 60 / 40 (mass ratio).

[0589] <Formation of Resistant Pattern> Each resist composition was coated onto an 8-inch silicon substrate treated with hexamethyldisilazane (HMDS) using a spin coater. A pre-baking (PAB) process was then performed on a heated plate at 110°C for 60 seconds, followed by drying, to form a resist film with a thickness of 50 nm. Next, using an electronic line drawing apparatus JEOL-JBX-9300FS (manufactured by Japan Electronics Corporation), a 1:1 linewidth and spacing pattern (hereinafter referred to as "LS pattern") with a target size of 50 nm was drawn (exposed) at an accelerating voltage of 100 kV. Subsequently, a post-exposure heating (PEB) process was performed at 100°C for 60 seconds. Next, alkaline development was performed for 60 seconds at 23°C using a 2.38% by mass tetramethylammonium hydroxide (TMAH) aqueous solution "NMD-3" (trade name, manufactured by Tokyo Ohka Kogyo Co., Ltd.). Following this, a 15-second water rinse was performed using pure water. The result was a 1:1 LS pattern with a linewidth of 50 nm.

[0590] [Evaluation of Optimal Exposure (Eop)] Determine the optimal exposure Eop (mJ / cm2) for the target size LS pattern formed by the above <Formation of Resistant Pattern>. This is presented as "Eop (mJ / cm2)" in Tables 13-24.

[0591] [Evaluation of Defects] Each resist composition was coated onto an 8-inch silicon substrate treated with hexamethyldisilazane (HMDS) using a spin coater. The substrate was then pre-baked (PAB) at 110°C for 60 seconds on a hot plate and dried to form a resist coating film with a thickness of 50 nm. The number of foreign matter / defects in the coating film was measured using a Surfscan SP2 (product name) manufactured by KLA Tencor. Regarding the number of foreign matter / defects below 80 nm on the surface of the coating film, the relative number of each example was calculated when the number in Comparative Example 1 was set to 1.0, and the results were evaluated according to the following evaluation criteria. The results are presented as "defects" in Tables 20-31. (Evaluation Criteria) A: Below 0.2 B: 0.2~0.5 C: 0.5~1.0 D: Above 1.0

[0592]

[0593]

[0594]

[0595]

[0596]

[0597]

[0598]

[0599]

[0600]

[0601]

[0602]

[0603]

[0604] As shown in Tables 20-31, it was confirmed that the sensitivity and defects of the inhibitor composition of the Examples were good compared with those of the Comparative Examples.

[0605] The preferred embodiments of the present invention have been described above, but the present invention is not limited to these embodiments. Additions, omissions, substitutions, and other modifications to the structure can be implemented without departing from the spirit of the present invention. The present invention is not limited to the foregoing description, but only to the scope of the appended claims.

Claims

1. A resist composition that generates acid upon exposure and alters the solubility of a developer due to the action of the acid, comprising: a compound containing a cation (CO) of the following general formula (CO); wherein X01 and X02 are, respectively, independently alkyl, methanesulfonyl, fluorine, alkyl halide, alkoxy halide, alkylamino halide, alkylthio halide, cyano, nitro, dialkylphosphono, alkylsulfonyl, sulfonoxy, acylthio, sulfamoyl, thiocyanate, or thiocarbonyl, and are distinct from each other; R01 is an electron-donating group; R02 and R03 are each independently a substituent; nx1 and nx2 are each independently an integer from 1 to 4, n 1 is an integer from 0 to 3, and nx1 + nx2 + n1 ≦ 5; n2 and n3 are each independent integers from 0 to 4; when nx1 is 2 or more, the complex numbers X01 can be the same or different; when nx2 is 2 or more, the complex numbers X02 can be the same or different; when n1 is 2 or more, the complex numbers R01 can be the same or different; when n2 is 2 or more, the complex numbers R02 can be the same or different; when n3 is 2 or more, the complex numbers R03 can be the same or different.

2. The resist composition of claim 1, comprising: a resin component (A1) that changes the solubility of the developer due to the action of acid, and an acid generating agent component (B) that generates acid due to exposure, wherein the aforementioned acid generating agent component (B) comprises a compound represented by the following general formula (b0); wherein Mb+ is the aforementioned cation (CO), and Xb- is the relative anion.

3. The resist composition of claim 1, comprising: a resin component (A1) that changes the solubility of the developer due to the action of acid, and an acid diffusion control agent component (D) that controls the diffusion of acid generated by exposure, wherein the aforementioned acid diffusion control agent component (D) comprises a compound represented by the following general formula (d0); wherein Md+ is the aforementioned cation (CO), and Xd- is the relative anion.

4. The inhibitor composition of claim 1, comprising: a resin component (A0) having a constituent unit (a0) as shown in the following general formula (a0-1); wherein R is a hydrogen atom, an alkyl group having 1 to 5 carbon atoms, or a haloalkyl group having 1 to 5 carbon atoms, Ma+ is the aforementioned cation (C0), and Rx0- is a group containing an anion.

5. The inhibitor composition of claim 4, comprising: a resin component (A1) that changes the solubility of the developer due to the action of acid, and the resin component (A1) having the aforementioned constituent unit (a0).

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

7. A compound represented by the following general formula (M0); wherein X01 and X02 are, independently, acetylated, methanesulfonyl, fluorine, alkyl halide, alkoxy halide, alkylamino halide, alkylthio halide, cyano, nitro, dialkylphosphinyl, alkylsulfonyl, sulfonoxy, acethio, aminesulfonyl, thiocyanate, or thiocarbonyl, and are distinct from each other; R01 is an electron-donating group; R02 and R03 are each independently substituents; nx1 and nx2 are each independently integers from 1 to 4, n1 is an integer from 0 to 3, and nx1 + nx2 + n1 ≦ 5; n2 Each of the n3 series is an independent integer from 0 to 4; when nx1 is 2 or more, the complex X01 series can be the same or different; when nx2 is 2 or more, the complex X02 series can be the same or different; when n1 is 2 or more, the complex R01 series can be the same or different; when n2 is 2 or more, the complex R02 series can be the same or different; when n3 is 2 or more, the complex R03 series can be the same or different; X- is the relative anion.

8. An acid generating agent comprising a compound represented by the following general formula (B0); wherein X01 and X02 are, respectively, independently alkyl, methanesulfonyl, fluorine, alkyl halide, alkoxy halide, alkylamino halide, alkylthio halide, cyano, nitro, dialkylphosphinyl, alkylsulfonyl, sulfonoxy, thiothio, aminesulfonyl, thiocyanate, or thiocarbonyl, and are distinct from each other; R01 is an electron-donating group; R02 and R03 are each independently substituents; nx1 and nx2 are each independently integers from 1 to 4, n1 is an integer from 0 to 3, nx1 + nx2 + n1 ≤ 5; n2 Each of the n3 series is an independent integer from 0 to 4; when nx1 is 2 or more, the complex X01 series can be the same or different; when nx2 is 2 or more, the complex X02 series can be the same or different; when n1 is 2 or more, the complex R01 series can be the same or different; when n2 is 2 or more, the complex R02 series can be the same or different; when n3 is 2 or more, the complex R03 series can be the same or different; Xb- is a relative anion.

9. An acid diffusion control agent comprising a compound represented by the following general formula (D0); wherein X01 and X02 are, respectively, independently alkyl, methanesulfonyl, fluorine, alkyl halide, alkoxy halide, alkylamino halide, alkylthio halide, cyano, nitro, dialkylphosphinyl, alkylsulfonyl, sulfonoxy, sulfonyl, aminesulfonyl, thiocyanate, or thiocarbonyl, and are distinct from each other; R01 is an electron-donating group; R02 and R03 are each independently substituents; nx1 and nx2 are each independently integers from 1 to 4, n1 is an integer from 0 to 3, nx1 + nx2 + n1 ≦ 5; n2 Each of the n3 series is an independent integer from 0 to 4; when nx1 is 2 or more, the complex X01 series can be the same or different; when nx2 is 2 or more, the complex X02 series can be the same or different; when n1 is 2 or more, the complex R01 series can be the same or different; when n2 is 2 or more, the complex R02 series can be the same or different; when n3 is 2 or more, the complex R03 series can be the same or different; Xd- is a relative anion.

10. A polymer compound having a constituent unit (a0) as shown in the following general formula (A0-1); wherein, R is a hydrogen atom, an alkyl group having 1 to 5 carbon atoms, or a haloalkyl group having 1 to 5 carbon atoms; Rx0 is a group containing an anion; X01 and X02 are, respectively, independently acetylated, methanesulfonyl, fluorine, haloalkyl, haloalkoxy, haloalkylamino, haloalkylthio, cyano, nitro, dialkylphosphinyl, alkylsulfonyl, sulfonoxy, acethio, aminesulfonyl, thiocyanate, or thiocarbonyl, and are distinct from each other; R01 is an electron-donating group; R02 and R03 are each independently substituents; nx1 and nx2 are each independently integers from 1 to 4. n1 is an integer from 0 to 3, and nx1 + nx2 + n1 ≦ 5; n2 and n3 are each independent integers from 0 to 4; when nx1 is 2 or more, the complex numbers X01 can be the same or different; when nx2 is 2 or more, the complex numbers X02 can be the same or different; when n1 is 2 or more, the complex numbers R01 can be the same or different; when n2 is 2 or more, the complex numbers R02 can be the same or different; when n3 is 2 or more, the complex numbers R03 can be the same or different.