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

Abstract

An inhibitor composition comprising a base component (A) and a compound (B0) represented by general formula (b0). Wherein, Rb 0 is a condensed cyclic group obtained by the condensation of an aromatic ring and an alicyclic ring. The alicyclic group in the aforementioned condensed cyclic group has substituents, and at least one of the substituents comprises a hydrocarbon group having a bromine atom or an iodine atom. Yb 0 represents a binary linked base or a single bond. However, Yb 0 is bonded to the alicyclic bonds in the aforementioned condensed cyclic group. Vb 0 represents a single bond, an alkyl group, or a fluorinated alkyl group. R 0 represents a fluorinated alkyl group or fluorine atom with 1 to 5 carbon atoms. M m+ represents an organic cation with a valence of m. m is an integer greater than or equal to 1.

Description

Technical Field

[0001] This invention relates to inhibitor compositions, inhibitor pattern formation methods, compounds, and acid generating agents. This case is based on a priority claim made in Japan under Japanese Patent Application No. 2021-155752 filed on September 24, 2021, the contents of which are incorporated herein by reference. Prior Technology

[0002] In recent years, advancements in lithography technology have led to rapid miniaturization of patterns in the manufacturing of semiconductor devices and liquid crystal display devices. A common method for miniaturization is to shorten the wavelength (increase the energy) of the exposure light source.

[0003] For resist materials, the requirements are lithographic properties such as sensitivity to such exposure light sources and resolution that can reproduce patterns of minute dimensions. Conventional resist materials that meet such requirements have used chemically amplified resist compositions containing 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] During the formation of resist patterns, the behavior of acids generated by acid-generating agents through exposure is considered to be one of the factors that have a significant impact on photolithography properties. A variety of acid generating agents have been proposed for use in chemically amplifying inhibitor compositions. For example, known acid generating agents include onium salts such as monazite or strontium salts, oxime sulfonate acid generating agents, diazomethane acid generating agents, nitrobenzyl sulfonate acid generating agents, imino sulfonate acid generating agents, and disulfonate acid generating agents. As a onium salt acid generator, it is mainly used in onium ions such as triphenylstrontium in the cation portion. In the anionic portion of the onium salt acid generator, generally speaking, alkyl sulfonate ions or fluorinated alkyl sulfonate ions in which some or all of the hydrogen atoms of the alkyl group are replaced by fluorine atoms are used. Furthermore, in order to improve the lithography properties during the formation of the resist pattern, an onium salt acid generator with an anion having a specific structure has also been proposed as the anionic part of the onium salt acid generator (for example, see Patent Document 1). [Previous Technical Documents] [Patent Literature]

[0005] [Patent Document 1] Japanese Patent Application Publication No. 2018-92159 Summary of the Invention

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

[0007] With the advancement of lithography technology and the increasing miniaturization of resist patterns, such as in EUV (Extreme Ultraviolet) or EB (Electron Beam) lithography, the goal is to form patterns as fine as tens of nanometers. Therefore, the smaller the resist pattern size, the higher the sensitivity to the exposure light source required, while simultaneously demanding resist compositions that can form resist patterns with good in-plane uniformity (CDU) of pattern size. Furthermore, in terms of exposure light sources, especially EUV or EB, compared to ArF excimer lasers or KrF excimer lasers, there are fewer photons related to photosensitivity, thus requiring higher sensitivity of the resist composition.

[0008] However, in the inhibitor composition containing the onium salt acid generating agent described in Patent Document 1 above, since the anionic portion is a polycyclic structure containing a bicyclooctane skeleton, the uniformity of the inhibitor film of the onium salt acid generating agent can be improved by increasing hydrophobicity, but there is still room for further improvement in terms of sensitivity.

[0009] The present invention is made in view of the above-mentioned facts, and its object is to provide a resist composition that can form a resist pattern that achieves high sensitivity and good CDU, a method for forming a resist pattern using the resist composition, a novel compound for use as an acid generating agent of the resist composition, and an acid generating agent using the compound. [Methods used to solve problems]

[0010] To address the aforementioned issues, the present invention employs the following configuration. That is, the first embodiment of the present invention is a resist composition that generates acid by exposure and whose solubility in the developer changes due to the action of the acid. It contains a substrate component (A) whose solubility in the developer changes due to the action of the acid, and an acid generating agent component (B) that generates acid by exposure. The aforementioned acid generating agent component (B) includes a compound (B0) represented by the following general formula (b0).

[0011] [In the formula, Rb0 is a condensed cyclic group obtained by the condensation of an aromatic ring and an alicyclic ring. The alicyclic ring in the aforementioned condensed cyclic group has substituents, and at least one of the substituents contains a hydrocarbon group having a bromine atom or a hydrocarbon group having an iodine atom. Yb0 is a divalent linkage or a single bond. However, Yb0 is bonded to the alicyclic ring in the aforementioned condensed cyclic group. Vb0 is a single bond, an alkyl group, or a fluorinated alkyl group. R0 is a fluorinated alkyl group or a fluorine atom with 1 to 5 carbon atoms. Mm+ represents an m-valent organic cation. m is an integer greater than or equal to 1].

[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 on a support using the resist composition of the first state, 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 (b0).

[0014] [In the formula, Rb0 is a condensed cyclic group obtained by the condensation of an aromatic ring and an alicyclic ring. The alicyclic ring in the aforementioned condensed cyclic group has substituents, and at least one of the substituents contains a hydrocarbon group having an iodine atom. Yb0 is a divalent linked group or a single bond. However, Yb0 is bonded to the alicyclic ring in the aforementioned condensed cyclic group. Vb0 is a single bond, an alkyl group, or a fluorinated alkyl group. R0 is a fluorinated alkyl group or a fluorine atom with 1 to 5 carbon atoms. Mm+ represents an m-valent organic cation. m is an integer greater than or equal to 1].

[0015] The fourth state of the present invention is an acid generating agent containing the compound of the aforementioned third state. [Effects of the Invention]

[0016] According to the present invention, a resist composition capable of forming a resist pattern that achieves high sensitivity and good CDU can be provided, a method for forming a resist pattern using the resist composition, a novel compound for use as an acid generating agent of the resist composition, and an acid generating agent using the compound can be provided. Implementation

[0017] In this specification and the scope of this patent application, "aliphatic" is a relative concept compared to aromatic, and is defined as referring to bases, compounds, etc. that do not possess aromatic properties. Unless otherwise specified, "alkyl" refers to monovalent saturated hydrocarbon groups, including straight-chain, branched-chain, and cyclic groups. The same applies to alkyl groups in alkoxy groups. Unless otherwise specified, "alkyl" refers to divalent saturated hydrocarbon groups that are linear, branched, or cyclic. "Halogen atoms" can include fluorine atoms, chlorine atoms, bromine atoms, and iodine atoms. "Constituent unit" refers to the monomer unit (monomer unit) that makes up a polymer compound (resin, polymer, copolymer). When it is recorded as "may have substituents", it includes both the case of replacing the hydrogen atom (-H) with a monovalent group and the case of replacing the methylene group (-CH 2-) with a divalent group. "Exposure" is a concept that includes all exposure to radiation.

[0018] "Acid-decomposable group" is an acid-decomposable group that, through the action of an acid, can cause at least a portion of the bonds in its structure to break. Acids can increase the polarity of decomposing groups through the action of acids. Examples of such groups can be listed as those that decompose and generate polar groups through the action of acids. Examples of polar groups include carboxyl, hydroxyl, amino, and sulfonyl (-SO 3H). More specifically, acid-dissociative groups can be categorized as groups that protect the aforementioned polar groups with acid-dissociative groups (e.g., groups that protect the hydrogen atoms of a polar group containing OH with acid-dissociative groups).

[0019] "Acid-dissociable group" refers to either (i) or (ii) both of the following: (i) an acid-dissociable group that, by the action of an acid, can break the bond between the acid-dissociable group and the atom adjacent to the acid-dissociable group, or (ii) a group that, by the action of an acid, partially breaks the bond, and then, through a further decarbonation reaction, can break the bond between the acid-dissociable group and the atom adjacent to the acid-dissociable group. The acid-dissociating group that constitutes the acid-dissociating group must be a group with a lower polarity than the polar group generated by the dissociation of the acid-dissociating group. Therefore, when the acid dissociates the acid-dissociating group, a more polar group with higher polarity than the original acid-dissociating group is produced, thus increasing the overall polarity of the (A1) component. This increased polarity correspondingly alters the solubility in the developer; solubility increases when the developer is alkaline and decreases when the developer is organic.

[0020] "Substrate component" refers to organic compounds with film-forming capabilities. Organic compounds that can be used as substrate components are broadly classified into non-polymers and polymers. Non-polymers typically have a molecular weight of 500 or higher but less than 4000. The term "low molecular weight compound" refers to non-polymers with a molecular weight of 500 or higher but less than 4000. Polymers typically have a molecular weight of 1000 or higher. The terms "resin," "high molecular weight compound," or "polymer" refer to polymers with a molecular weight of 1000 or higher. The molecular weight of polymers is calculated using the weight-average molecular weight of polystyrene obtained through GPC (gel permeation chromatography).

[0021] "Derived constituent units" refers to the constituent units formed by the breaking of multiple bonds between carbon atoms, such as vinyl double bonds. "Acrylates" can also have their hydrogen atom at the α-position of the carbon atom replaced by a substituent. The substituent (Rαx) replacing the hydrogen atom at the α-position of the carbon atom can be an atom or a group other than the hydrogen atom. Furthermore, this also includes econic acid diesters where the substituent (Rαx) is replaced by a substituent containing an ester bond, or α-hydroxy acrylates where the substituent (Rαx) is replaced by a hydroxyalkyl group or a group that has modified its hydroxyl group. Moreover, unless otherwise specified, the carbon atom at the α-position of an acrylate is the carbon atom bonded to the carbonyl group of acrylic acid. Hereinafter, acrylates in which the hydrogen atom of the carbon atom bonded to the α-position is replaced by a substituent are called α-substituted acrylates.

[0022] "Derivative" is a concept encompassing compounds in which the hydrogen atom at the α-position is replaced by an alkyl group, a haloalkyl group, or other substituent, and such derivatives. Examples of such derivatives include those in compounds where the hydrogen atom at the α-position can be substituted by a substituent, where the hydrogen atom of the hydroxyl group is substituted by an organogroup; and those in compounds where a substituent other than a hydroxyl group is bonded to the hydrogen atom at the α-position. Furthermore, unless otherwise specified, the α-position refers to the first carbon atom adjacent to the functional group. Substituents at the α-position of the hydrogen atom in hydroxystyrene can be listed as being identical to Rαx.

[0023] In this specification and the scope of this patent application, depending on the structure represented by the chemical formula, there may be asymmetric carbon, resulting in either enantiomers or diastereomers. In this case, a single chemical formula is used to represent each isomer. These isomers can be used alone or as mixtures.

[0024] (Inhibitor composition) The resist composition of this embodiment is an acid that is generated by exposure, and its solubility in the developer changes due to the action of the acid. The resist composition contains a substrate component (A) whose solubility in the developer changes due to the action of acid (hereinafter also referred to as "(A) component"), and an acid-generating agent component (B) that generates acid through exposure (hereinafter also referred to as "(B) component").

[0025] 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 (B) in the exposed areas 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 areas of the resist film. Therefore, a difference in solubility in the developer arises between the exposed and unexposed areas. Thus, when the resist film is developed, if the resist composition is positive, the exposed areas of the resist film are dissolved and removed to form a positive resist pattern; if the resist composition is negative, the unexposed areas of the resist film are dissolved and removed to form a negative resist pattern.

[0026] 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 during the development process to form the resist pattern, or in a solvent development process where a developer containing an organic solvent (organic developer) is used in the same development process.

[0027] <(A)Component> In the resist composition of this embodiment, component (A) preferably includes a resin component (A1) whose solubility in the developer changes due to the action of acid (hereinafter also referred to as "(A1) component"). By using component (A1), the polarity of the substrate composition changes before and after exposure, thus achieving good development contrast not only in alkaline development processes but also in solvent development processes. As component (A), component (A1) may also be used in combination with other high molecular weight compounds and / or low molecular weight compounds.

[0028] In the inhibitor composition of this embodiment, component (A) can be used alone or in combination with two or more components.

[0029] In the resist composition of this embodiment, component (A) may also be a "substrate component that generates acid upon exposure and whose solubility in the developer changes due to the action of the acid". When component (A) is a substrate component that generates acid upon exposure and whose solubility in the developer changes due to the action of the acid, component (A1) described later is preferably a resin that generates acid upon exposure and whose solubility in the developer changes due to the action of the acid. As such a resin, a polymeric compound having constituent units that generate acid upon exposure can be used. The constituent units that generate acid upon exposure can be those that are known.

[0030] Regarding ingredient (A1) (A1) component refers to resin components whose solubility in developer changes due to the action of acid. As a component (A1), it is preferred to have a constituent unit (a1) containing an acid-decomposing group whose polarity increases by the action of an acid. In addition to the constituent unit (a1), component (A1) may also have other constituent units as needed.

[0031] ≪Constituted Unit (a1)≫ The constituent unit (a1) is a constituent unit containing an acid-decomposing group whose polarity increases through the action of an acid.

[0032] As acid-dissociative groups, examples of acid-dissociative groups proposed to date for use as components of chemically amplifying inhibitors in base resins can be cited. Specifically, the acid-dissociating groups proposed for the base resin used as components of chemically amplifying inhibitors include the following: "acetal-type acid-dissociating group", "tertiary alkyl ester-type acid-dissociating group", "secondary alkyl ester-type acid-dissociating group", and "tertiary alkoxycarbonyl acid-dissociating group".

[0033] Acetal type acid dissociation group: Among the aforementioned polar groups, acid-dissociating groups that protect carboxyl or hydroxyl groups can be exemplified by acid-dissociating groups represented by the following general formula (a1-r-1) (hereinafter referred to as "acetal-type acid-dissociating groups").

[0034] [In the formula, Ra'1 and Ra'2 are hydrogen atoms or alkyl groups. Ra'3 is a hydrocarbon group, and Ra'3 can also bond with either Ra'1 or Ra'2 to form a ring].

[0035] In formula (a1-r-1), at least one of Ra' 1 and Ra' 2 is preferably a hydrogen atom, and more preferably both are hydrogen atoms. When Ra'1 or Ra'2 is an alkyl group, the alkyl group may be the same as those listed in the description of α-substituted acrylates above as substituents that can be bonded to the carbon atom at the α-position, preferably an alkyl group with 1 to 5 carbon atoms. Specifically, linear or branched alkyl groups are preferred. More specifically, methyl, ethyl, propyl, isopropyl, n-butyl, isobutyl, tert-butyl, pentyl, isopentyl, neopentyl, etc., are preferred, especially methyl or ethyl, and particularly preferably methyl.

[0036] In formula (a1-r-1), the hydrocarbon group of Ra'3 can be listed as a straight-chain or branched-chain alkyl group, or a cyclic hydrocarbon group. The straight-chain alkyl group preferably has 1 to 5 carbon atoms, more preferably 1 to 4 carbon atoms, and even more preferably 1 or 2 carbon atoms. Specifically, examples include methyl, ethyl, n-propyl, n-butyl, n-pentyl, etc. Among these, methyl, ethyl, or n-butyl are particularly preferred; methyl or ethyl is even more preferred.

[0037] The branched chain alkyl group preferably has 3 to 10 carbon atoms, more preferably 3 to 5 carbon atoms. Specifically, examples include isopropyl, isobutyl, tert-butyl, isopentyl, neopentyl, 1,1-diethylpropyl, 2,2-dimethylbutyl, etc., with isopropyl being the most preferred.

[0038] 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. The monocyclic aliphatic hydrocarbon group is preferably a group obtained by removing one hydrogen atom from a monocyclic alkane. The monocyclic alkane is preferably one with 3 to 6 carbon atoms, and examples include cyclopentane and cyclohexane. The aliphatic hydrocarbon group of the polycyclic group is preferably a group obtained by removing one hydrogen atom from a polycyclic alkane. The polycyclic alkane is preferably one with 7 to 12 carbon atoms. Examples include adamantane, norcamphene, isocamphene, tricyclodecane, tetracyclododecane, etc.

[0039] When the cyclic hydrocarbon group of Ra'3 is an aromatic hydrocarbon group, the aromatic hydrocarbon group is a hydrocarbon group having at least one aromatic ring. The aromatic ring is not particularly limited as long as it has 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 most preferably 6 to 12. Specifically, aromatic rings can be exemplified by aromatic hydrocarbon rings such as benzene, naphthalene, anthracene, and phenanthrene; and aromatic heterocycles in which a portion of the carbon atom constituting the aforementioned aromatic hydrocarbon ring is replaced by a heteroatom. Heteratomes in aromatic heterocycles can be exemplified by oxygen atoms, sulfur atoms, and nitrogen atoms. Specifically, aromatic heterocycles can be exemplified by pyridine rings and thiophene rings. The aromatic hydrocarbon group in Ra' 3, specifically, can be categorized as a group (aryl or heteroaryl) obtained by removing one hydrogen atom from the aforementioned aromatic hydrocarbon ring or aromatic heterocycle; a group obtained by removing one hydrogen atom from an aromatic compound containing two or more aromatic rings (e.g., biphenyl, benzoyl, etc.); or a group obtained by substituting one hydrogen atom of the aforementioned aromatic hydrocarbon ring or aromatic heterocycle with 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.

[0040] The cyclic hydrocarbon group in Ra'3 can also have substituents. Examples of such substituents include -RP1, -RP2-ORP1, -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 "Ra x5"). 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 substituted with fluorine atoms. The aforementioned aliphatic cyclic hydrocarbon group may have one or more of the above-mentioned substituents, or each may have one or more of the above-mentioned substituents in multiples. Chain-like saturated hydrocarbon groups with 1 to 10 carbon atoms and a single valence, such as methyl, ethyl, propyl, butyl, pentyl, hexyl, heptyl, octyl, decyl, etc. Aliphatic cyclic saturated hydrocarbon groups with 3 to 20 carbon atoms and a monovalent valence, such as monocyclic aliphatic saturated hydrocarbon groups like cyclopropyl, cyclobutyl, cyclopentyl, cyclohexyl, cycloheptyl, cyclooctyl, cyclodecyl, and cyclododecyl; and polycyclic aliphatic saturated hydrocarbon groups like 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. Aromatic hydrocarbon groups with 6 to 30 carbon atoms and a 1-valent valence, such as those obtained by removing one hydrogen atom from the aromatic hydrocarbon rings of benzene, biphenyl, fumonisin, naphthalene, anthracene, phenanthrene, etc.

[0041] When Ra'3 is bonded to either Ra'1 or Ra'2 to form a ring, the cyclic group is preferably a 4-7 member ring, more preferably a 4-6 member ring. Specific examples of this cyclic group include tetrahydropyranyl and tetrahydrofuranyl.

[0042] 3rd grade alkyl ester type acid dissociative group: Among the aforementioned polar groups, acid-dissociative groups that protect the carboxyl group can be exemplified by acid-dissociative groups represented by the following general formula (a1-r-2). Furthermore, among the acid dissociative groups represented by the following formula (a1-r-2), those composed of alkyl groups are referred to for convenience as "tertiary alkyl ester type acid dissociative groups".

[0043] [In the formula, Ra'4~Ra'6 are hydrocarbon groups, and Ra'5 and Ra'6 can also bond with each other to form a ring].

[0044] The hydrocarbon group of Ra'4 can be listed as a straight-chain or branched-chain alkyl group, a chain or cyclic alkenyl group, or a cyclic hydrocarbon group. The linear or branched alkyl groups and cyclic hydrocarbon groups (monocyclic aliphatic hydrocarbon groups, polycyclic aliphatic hydrocarbon groups, and aromatic hydrocarbon groups) in Ra' 4 can be the same as those in Ra' 3 mentioned above. The chain or cyclic alkenyl group in Ra'4 is preferably an alkenyl group with 2 to 10 carbon atoms. The hydrocarbon groups of Ra' 5 and Ra' 6 can be listed as being the same as those of Ra' 3 mentioned above.

[0045] When Ra' 5 and Ra' 6 are bonded together to form a ring, it is appropriate to list the bases represented by the following general formula (a1-r2-1), the bases represented by the following general formula (a1-r2-2), and the bases represented by the following general formula (a1-r2-3). On the other hand, when Ra'4~Ra'6 are not bonded to each other and are independent hydrocarbon groups, it is appropriate to list the groups represented by the following general formula (a1-r2-4).

[0046] In formula (a1-r2-1), Ra' 10 represents a linear or branched alkyl group with 1 to 12 carbon atoms, which can be partially substituted by a halogen atom or a heteroatom-containing group. Ra' 11 represents a group that forms an aliphatic cyclic group together with the carbon atom bonded to Ra' 10. In formula (a1-r2-2), Ya is a carbon atom. Xa is a group that forms a cyclic hydrocarbon group together with Ya. Some or all of the hydrogen atoms in this cyclic hydrocarbon group can also be substituted. Ra 101 to Ra 103 are, independently, a linear saturated hydrocarbon group with 1 to 10 carbon atoms and a 1-valent chain, or an aliphatic cyclic saturated hydrocarbon group with 3 to 20 carbon atoms and a 1-valent chain. Some or all of the hydrogen atoms in this linear saturated hydrocarbon group and the aliphatic cyclic saturated hydrocarbon group can also be substituted. Two or more of Ra 101 to Ra 103 can also be bonded to each other to form a cyclic structure. In formula (a1-r2-3), Yaa is a carbon atom. Xaa is a group that forms an aliphatic cyclic group with Yaa. Ra 104 is an aromatic hydrocarbon group that may have substituents. In formula (a1-r2-4), Ra' 12 and Ra' 13 are each independently monovalent chain saturated hydrocarbon groups with 1 to 10 carbon atoms. Some or all of the hydrogen atoms in these chain saturated hydrocarbon groups may also be substituted. Ra' 14 is a hydrocarbon group that may have substituents. * indicates a bonding site.

[0047] 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 substituted by halogen atoms or heteroatom-containing groups.

[0048] The straight-chain alkyl group in Ra' 10 has 1 to 12 carbon atoms, preferably 1 to 10 carbon atoms, and most preferably 1 to 5 carbon atoms. The branched chain alkyl groups in Ra' 10 can be listed as being the same as those in Ra' 3 mentioned above.

[0049] In Ra' 10, some of the alkyl groups may also be substituted with halogen atoms or heteroatom-containing groups. For example, some of the hydrogen atoms constituting the alkyl group may also be substituted with halogen atoms or heteroatom-containing groups. Furthermore, some of the carbon atoms constituting the alkyl group (such as methylene groups) may also be substituted with heteroatom-containing groups. The heteroatoms referred to here can include oxygen, sulfur, and nitrogen atoms. Radicals containing heteroatoms can include (-O-), -C(=O)-O-, -OC(=O)-, -C(=O)-, -OC(=O)-O-, -C(=O)-NH-, -NH-, -S-, etc. -S(=O) 2-, -S(=O) 2-O-, etc.

[0050] In formula (a1-r2-1), Ra' 11 (an aliphatic cyclic group formed together with the carbon atoms bonded to Ra' 10) is preferably an aliphatic hydrocarbon group (alicyclic hydrocarbon group) listed as a monocyclic or polycyclic group of Ra' 3 in formula (a1-r-1). A monocyclic alicyclic hydrocarbon group is particularly preferred, and more specifically, cyclopentyl or cyclohexyl is even more preferred.

[0051] In formula (a1-r2-2), the cyclic hydrocarbon group formed by Xa and Ya together can be exemplified by removing one or more hydrogen atoms from the cyclic monovalent hydrocarbon group (aliphatic hydrocarbon group) in Ra' 3 in the aforementioned formula (a1-r-1). The cyclic hydrocarbon group formed by Xa and Ya together may also have substituents. Examples of such substituents are the same as those that the cyclic hydrocarbon group in Ra' 3 described above may have. In formula (a1-r2-2), the chain saturated hydrocarbon groups with 1 to 10 carbon atoms in Ra 101 to Ra 103 are monovalent, such as methyl, ethyl, propyl, butyl, pentyl, hexyl, heptyl, octyl, decyl, etc. Aliphatic cyclic saturated hydrocarbon groups with 3 to 20 carbon atoms in Ra 101 to Ra 103, such as monocyclic aliphatic saturated hydrocarbon groups like cyclopropyl, cyclobutyl, cyclopentyl, cyclohexyl, cycloheptyl, cyclooctyl, cyclodecyl, and cyclododecyl; and polycyclic aliphatic saturated hydrocarbon groups like 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, Ra 101~Ra 103 are preferably composed of hydrogen atoms and monovalent chain saturated hydrocarbon groups with 1 to 10 carbon atoms; even more preferably, hydrogen atoms, methyl, and ethyl groups; and especially preferably, hydrogen atoms.

[0052] The substituents of the chain saturated hydrocarbon groups represented by Ra 101 to Ra 103 above, or the aliphatic cyclic saturated hydrocarbon groups, can be, for example, groups that are the same as those in Ra x5 above.

[0053] Two or more of Ra 101 to Ra 103 are bonded together to form a cyclic structure, resulting in a carbon-carbon double bond group. Examples include cyclopentenyl, cyclohexenyl, methylcyclopentenyl, methylcyclohexenyl, cyclopentylenevinyl, and cyclohexylenevinyl. Among these, cyclopentenyl, cyclohexenyl, and cyclopentylenevinyl are particularly preferred from the viewpoint of ease of synthesis.

[0054] In formula (a1-r2-3), the aliphatic cyclic group formed by Xaa and Yaa together is preferably one of the aliphatic hydrocarbon groups listed as a monocyclic or polycyclic group of Ra' 3 in formula (a1-r-1). In formula (a1-r2-3), the aromatic hydrocarbon group in Ra 104 can be exemplified by a group obtained by removing one or more hydrogen atoms from an aromatic hydrocarbon ring having 5 to 30 carbon atoms. Ra 104 is particularly preferably a group obtained by removing one or more hydrogen atoms from an aromatic hydrocarbon ring having 6 to 15 carbon atoms; more preferably a group obtained by removing one or more hydrogen atoms from benzene, naphthalene, anthracene, or phenanthrene; even more preferably a group obtained by removing one or more hydrogen atoms from benzene, naphthalene, or anthracene; especially preferably a group obtained by removing one or more hydrogen atoms from benzene or naphthalene; and most preferably a group obtained by removing one or more hydrogen atoms from benzene.

[0055] The substituents that Ra 104 in formula (a1-r2-3) may have include, for example, methyl, ethyl, propyl, hydroxyl, carboxyl, halogen atom, alkoxy (methoxy, ethoxy, propoxy, butoxy, etc.), alkoxy carbonyl, etc.

[0056] 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. Examples of monovalent chain saturated hydrocarbon groups with 1 to 10 carbon atoms in Ra' 12 and Ra' 13 are identical to those in Ra 101 to Ra 103 mentioned above. Some or all of the hydrogen atoms in these chain saturated hydrocarbon groups may also be substituted. Ra' 12 and Ra' 13, wherein the alkyl group having 1 to 5 carbon atoms is particularly preferred; more preferably, it is an alkyl group having 1 to 5 carbon atoms; even more preferably, it is methyl or ethyl; and most preferably, it is methyl. When the chain saturated hydrocarbon groups represented by Ra' 12 and Ra' 13 above are substituted, the substituents may be, for example, the same groups as Ra x5 above.

[0057] In formula (a1-r2-4), Ra' 14 is a hydrocarbon group that may have substituents. The hydrocarbon group in Ra' 14 may be a straight-chain or branched-chain alkyl group, or a cyclic hydrocarbon group.

[0058] The linear alkyl group in Ra' 14 preferably has 1 to 5 carbon atoms, more preferably 1 to 4, and even more preferably 1 or 2. Specifically, examples include methyl, ethyl, n-propyl, n-butyl, n-pentyl, etc. Among these, methyl, ethyl, or n-butyl are particularly preferred; methyl or ethyl is even more preferred.

[0059] The branched chain alkyl group in Ra' 14 preferably has 3 to 10 carbon atoms, more preferably 3 to 5. Specifically, isopropyl, isobutyl, tert-butyl, isopentyl, neopentyl, 1,1-diethylpropyl, 2,2-dimethylbutyl, etc., are examples, with isopropyl being the most preferred.

[0060] 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. The monocyclic aliphatic hydrocarbon group is preferably a group obtained by removing one hydrogen atom from a monocyclic alkane. The monocyclic alkane is preferably one with 3 to 6 carbon atoms, and examples include cyclopentane and cyclohexane. The aliphatic hydrocarbon group of the polycyclic group is preferably a group obtained by removing one hydrogen atom from a polycyclic alkane. The polycyclic alkane is preferably one with 7 to 12 carbon atoms. Examples include adamantane, norcamphene, isocamphene, tricyclodecane, tetracyclododecane, etc.

[0061] The aromatic hydrocarbon groups in Ra' 14 can be the same as those in Ra 104. Among them, Ra' 14 is preferably a group obtained by removing one or more hydrogen atoms from an aromatic hydrocarbon ring having 6 to 15 carbon atoms; more preferably a group obtained by removing one or more hydrogen atoms from benzene, naphthalene, anthracene or phenanthrene; even more preferably a group obtained by removing one or more hydrogen atoms from benzene, naphthalene or anthracene; particularly preferably a group obtained by removing one or more hydrogen atoms from naphthalene or anthracene; and most preferably a group obtained by removing one or more hydrogen atoms from naphthalene. The substituents that Ra' 14 may have are listed as being the same as those that Ra 104 may have.

[0062] When Ra' 14 in formula (a1-r2-4) is a naphthyl group, the position of the bond between it and the tertiary carbon atom in the aforementioned formula (a1-r2-4) can be any position of the 1st or 2nd position of the naphthyl group. When Ra' 14 in formula (a1-r2-4) is an anthracene group, the position of the bond with the tertiary carbon atom in the aforementioned formula (a1-r2-4) can be any of the 1st, 2nd, or 9th positions of the anthracene group.

[0063] Specific examples of the basis represented by the aforementioned formula (a1-r2-1) are listed below.

[0064]

[0065]

[0066]

[0067] Specific examples of the basis represented by the aforementioned formula (a1-r2-2) are listed below.

[0068]

[0069]

[0070]

[0071] Specific examples of the basis represented by the aforementioned formula (a1-r2-3) are listed below.

[0072]

[0073] Specific examples of the basis represented by the aforementioned formula (a1-r2-4) are listed below.

[0074]

[0075] Secondary alkyl ester type acid dissociative group: Among the aforementioned polar groups, acid-dissociative groups that protect the carboxyl group can be exemplified by acid-dissociative groups represented by the following general formula (a1-r-4).

[0076] [In the formula, Ra' 10 is a hydrocarbon group. Ra' 11a and Ra' 11b are each independently a hydrogen atom, a halogen atom, or an alkyl group. Ra' 12 is a hydrogen atom or a hydrocarbon group. Ra' 10 and Ra' 11a or Ra' 11b can also bond to each other to form a ring. Ra' 11a or Ra' 11b and Ra' 12 can also bond to each other to form a ring.]

[0077] In the formula, the hydrocarbon groups in Ra' 10 and Ra' 12 can be the same as those in Ra' 3 mentioned above. In the formula, the alkyl groups in Ra' 11a and Ra' 11b can be the same as those in Ra' 1 mentioned above. In the formula, the hydrocarbon groups in Ra' 10 and Ra' 12, and the alkyl groups in Ra' 11a and Ra' 11b, may also have substituents. Examples of such substituents include Ra x5 mentioned above.

[0078] Ra' 10 can also bond with Ra' 11a or Ra' 11b to form a ring. This ring can be polycyclic or monocyclic, and can be alicyclic or aromatic. The alicyclic and aromatic rings may also contain heteroatoms.

[0079] The ring formed by the bonding of Ra' 10 with Ra' 11a or Ra' 11b is preferably a monocyclic alkene, a ring in which a portion of the carbon atom of the monocyclic alkene is replaced by a heteroatom (oxygen atom, sulfur atom, etc.), or a monocyclic diene; more preferably a cycloalkene with 3 to 6 carbon atoms, and even more preferably cyclopentene or cyclohexene.

[0080] The ring formed by the bonding of Ra' 10 with Ra' 11a or Ra' 11b can also be a condensation ring. Specifically, examples of such condensation rings include indane.

[0081] The ring formed by the bonding of Ra' 10 with Ra' 11a or Ra' 11b may also have substituents. Examples of such substituents include Ra x5 mentioned above.

[0082] Ra' 11a or Ra' 11b and Ra' 12 can also bond together to form a ring, which can be listed as the same as the ring formed by bonding Ra' 10 and Ra' 11a or Ra' 11b together.

[0083] Specific examples of the basis represented by the aforementioned formula (a1-r-4) are listed below.

[0084]

[0085] 3rd-order alkoxycarbonyl acid dissociation group: Among the aforementioned polar groups, the acid-dissociating groups that protect the hydroxyl group can be exemplified by the following general formula (a1-r-3) (hereinafter referred to as "tertiary alkoxycarbonyl acid dissociating groups" for convenience).

[0086] [In the formula, Ra' 7~Ra' 9 are alkyl groups respectively].

[0087] In formula (a1-r-3), Ra' 7 to Ra' 9 are preferably alkyl groups having 1 to 5 carbon atoms, and more preferably alkyl groups having 1 to 3 carbon atoms. Furthermore, the total number of carbon atoms of each alkyl group is preferably 3 to 7, more preferably 3 to 5, and most preferably 3 to 4.

[0088] Constituent units (a1) may include acrylates derived from carbon atoms bonded to the α-position whose hydrogen atoms can be substituted by substituents; acrylamide derived from hydroxylamine; a unit derived from hydroxystyrene or hydroxystyrene derivatives in which at least a portion of the hydrogen atoms in the hydroxyl group is protected by a substituent containing the aforementioned acid-degrading group; and a unit derived from vinyl benzoic acid or vinyl benzoic acid derivatives in which at least a portion of the hydrogen atoms in the -C(=O)-OH group is protected by a substituent containing the aforementioned acid-degrading group, etc.

[0089] The constituent unit (a1), among the above, is preferably a constituent unit derived from an acrylate in which the hydrogen atom of the carbon atom bonded to the α-position can be substituted by a substituent. A preferred specific example of this constituent unit (a1) can be listed as a constituent unit represented by the following general formula (a1-1) or (a1-2).

[0090] [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. Va 1 is a divalent hydrocarbon group that may have an ether bond. na1 is an integer from 0 to 2. Ra 1 is an acid-dissociable group represented by the above general formula (a1-r-1) or (a1-r-2). Wa 1 is a hydrocarbon group with a na2+1 valence, na2 is an integer from 1 to 3, and Ra 2 is an acid-dissociable group represented by the above general formula (a1-r-1) or (a1-r-3).]

[0091] In the aforementioned formula (a1-1), the alkyl group of R having 1 to 5 carbon atoms is preferably a straight-chain or branched-chain alkyl group having 1 to 5 carbon atoms, specifically including methyl, ethyl, propyl, isopropyl, n-butyl, isobutyl, tert-butyl, pentyl, isopentyl, neopentyl, etc. The alkyl halide having 1 to 5 carbon atoms is a group in which one or all of the hydrogen atoms of the aforementioned alkyl group having 1 to 5 carbon atoms are substituted with a halogen atom. This halogen atom is particularly preferably a fluorine atom. R is preferably a hydrogen atom, an alkyl group having 1 to 5 carbon atoms, or a fluorinated alkyl group having 1 to 5 carbon atoms. In terms of ease of industrial acquisition, it is best to be a hydrogen atom or a methyl group.

[0092] In the aforementioned formula (a1-1), the divalent hydrocarbon group in Va 1 can be either an aliphatic hydrocarbon group or an aromatic hydrocarbon group.

[0093] As a divalent hydrocarbon group in Va 1, the aliphatic hydrocarbon group can be saturated or unsaturated, but saturation is usually preferred. More specifically, the aliphatic hydrocarbon group can be listed as a straight-chain or branched-chain aliphatic hydrocarbon group, or an aliphatic hydrocarbon group containing a ring in its structure.

[0094] The aforementioned straight-chain aliphatic hydrocarbon group is preferably composed of 1 to 10 carbon atoms, more preferably 1 to 6 carbon atoms, even more preferably 1 to 4 carbon atoms, and most preferably 1 to 3 carbon atoms. The linear aliphatic hydrocarbon group is preferred to be a linear alkyl group. Specifically, examples include methylene [-CH 2-], ethyl [-(CH 2) 2-], trimethylene [-(CH 2) 3-], tetramethylene [-(CH 2) 4-], pentamethylene [-(CH 2) 5-], etc. The aforementioned branched chain aliphatic hydrocarbon group is preferably composed of 2 to 10 carbon atoms, more preferably 3 to 6 carbon atoms, even more preferably 3 or 4 carbon atoms, and most preferably 3 carbon atoms. Branched aliphatic hydrocarbon groups, preferably branched alkyl groups, specifically including alkylmethylene groups such as -CH(CH3)-, -CH(CH2CH3)-, -C(CH3)2-, -C(CH3)(CH2CH3)-, -C(CH3)(CH2CH2CH3)-, and -C(CH2CH3)2-; and alkylmethylene groups such as -CH(CH3)CH2-, -CH(CH3)CH(CH3)-. Alkyl ethyl groups such as -C(CH 3) 2CH 2-, -CH(CH 2CH 3)CH 2-, and -C(CH 2CH 3) 2-CH 2-; alkyl trimethylene groups such as -CH(CH 3)CH 2CH 2- and -CH 2CH(CH 3)CH 2-; and alkyl tetramethylene groups such as -CH(CH 3)CH 2CH 2CH 2- and -CH 2CH(CH 3)CH 2CH 2-. The alkyl group in the alkyl alkyl group is preferably a straight-chain alkyl group having 1 to 5 carbon atoms.

[0095] The aforementioned structures containing a ring-containing aliphatic hydrocarbon groups can include, for example, alicyclic hydrocarbon groups (derived by removing two hydrogen atoms from an aliphatic hydrocarbon ring), groups obtained by alicyclic hydrocarbon groups bonded to the end of a straight-chain or branched-chain aliphatic hydrocarbon group, and groups in which alicyclic hydrocarbon groups exist along the path of a straight-chain or branched-chain aliphatic hydrocarbon group. The aforementioned straight-chain or branched-chain aliphatic hydrocarbon groups can include those identical to the aforementioned straight-chain or branched-chain aliphatic 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 either polycyclic or monocyclic. For monocyclic alicyclic hydrocarbon groups, it is preferable to obtain a group obtained by removing two hydrogen atoms from a monocyclic alkane. The monocyclic alkane preferably has 3 to 6 carbon atoms, specifically cyclopentane, cyclohexane, etc. For polycyclic alicyclic hydrocarbon groups, it is preferable to obtain a group obtained by removing two hydrogen atoms from a polycyclic alkane, preferably having 7 to 12 carbon atoms, specifically adamantane, norcamphene, isocamphene, tricyclodecane, tetracyclododecane, etc.

[0096] As a divalent hydrocarbon group in Va 1, an aromatic hydrocarbon group is a hydrocarbon group with an aromatic ring. The aromatic hydrocarbon group preferably has 3 to 30 carbon atoms, more preferably 5 to 30, even more preferably 5 to 20, particularly preferably 6 to 15, and most preferably 6 to 12. However, the number of carbon atoms does not include the number of carbon atoms in the substituents. Aromatic rings, specifically those of benzene, biphenyl, fentanyl, naphthalene, anthracene, and phenanthrene, are examples of aromatic hydrocarbon rings. Aromatic heterocycles are also examples of aromatic hydrocarbon rings in which a portion of the carbon atom is substituted with a heteroatom. Heteroatoms in aromatic heterocycles can include oxygen, sulfur, and nitrogen atoms. Specifically, the aromatic hydrocarbon group may include groups (aryl groups) obtained by removing two hydrogen atoms from the aforementioned aromatic hydrocarbon ring; and groups (e.g., groups obtained by substituting one hydrogen atom of an aryl group (aryl group) obtained by removing one hydrogen atom from the aforementioned aromatic hydrocarbon ring through an alkyl substituent (e.g., groups obtained by further removing one hydrogen atom 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 substituent (alkyl chain in an aryl alkyl group) is preferably 1 to 4, more preferably 1 to 2, and particularly preferably 1.

[0097] In the aforementioned formula (a1-1), Ra 1 is the acid dissociative group represented by the above formula (a1-r-1) or (a1-r-2).

[0098] In the aforementioned formula (a1-2), the na2+1 valence hydrocarbon group in Wa1 can be either an aliphatic hydrocarbon group or an aromatic hydrocarbon group. This aliphatic hydrocarbon group refers to a hydrocarbon group that is not aromatic; it can be saturated or unsaturated, but is generally preferred to be saturated. The aforementioned aliphatic hydrocarbon groups can include straight-chain or branched-chain aliphatic hydrocarbon groups, aliphatic hydrocarbon groups containing rings in their structure, or groups obtained by combining straight-chain or branched-chain aliphatic hydrocarbon groups with aliphatic hydrocarbon groups containing rings in their structure. The aforementioned na2+1 valence is preferably 2~4 valence, and more preferably 2 or 3 valence.

[0099] In the aforementioned formula (a1-2), Ra 2 is the acid dissociative group represented by the above general formula (a1-r-1) or (a1-r-3).

[0100] The following shows specific examples of the constituent units represented by the aforementioned formula (a1-1). In the following formulas, Rα represents a hydrogen atom, a methyl group, or a trifluoromethyl group.

[0101]

[0102]

[0103]

[0104]

[0105]

[0106]

[0107]

[0108]

[0109] The constituent unit (a1) of component (A1) can be one or more. The constituent unit (a1) is preferably the constituent unit represented by the aforementioned formula (a1-1) because it can more easily improve the characteristics (sensitivity, shape, etc.) in lithography made by electron beam or EUV. Among them, the constituent unit (a1) is a constituent unit that includes the following general formula (a1-1-1).

[0110] [In the formula, Ra 1” is an acid dissociative group represented by the general formula (a1-r2-1), (a1-r2-3) or (a1-r2-4). * indicates the bonding site].

[0111] In the aforementioned equation (a1-1-1), R, Va 1, and na1 are the same as R, Va 1, and na1 in the aforementioned equation (a1-1). The description of the acid-dissociating group represented by the general formula (a1-r2-1), (a1-r2-3), or (a1-r2-4) is as described above. Among them, it is particularly preferable to choose a cyclic acid-dissociating group because it can improve reactivity when used in EB or EUV applications.

[0112] In the aforementioned formula (a1-1-1), Ra 1” is preferably an acid dissociative group represented by the general formula (a1-r2-1).

[0113] The proportion of the constituent unit (a1) in component (A1) is preferably 5 to 95 mol%, more preferably 10 to 90 mol%, and even more preferably 30 to 70 mol%, with respect to the total (100 mol%) of all constituent units constituting component (A1). It is particularly preferably 40 to 60 mol. By making the proportion of the constituent unit (a1) above the lower limit of the aforementioned preferred range, lithography properties such as sensitivity, CDU, resolution, and roughness improvement are enhanced. On the other hand, if it is below the upper limit of the aforementioned preferred range, a balance can be achieved with other constituent units, resulting in good lithography properties.

[0114] Other constituent units In addition to the aforementioned constituent unit (a1), component (A1) may also have other constituent units as needed. Other constituent units include, for example, those represented by the general formula (a10-1) described below (a10); those containing a cyclic group containing a lactone (a2); those derived from compounds represented by the general formula (a8-1) described below (a8); and those derived from compounds represented by the general formula (a0-1) described below (a01), etc.

[0115] Regarding the constituent unit (a10): The constituent unit (a10) is the constituent unit represented by the following general formula (a10-1).

[0116] [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 greater than or equal to 1].

[0117] 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 preferably a hydrogen atom, an alkyl group having 1 to 5 carbon atoms, or a fluorinated alkyl group having 1 to 5 carbon atoms. For industrial availability, it is more preferably a hydrogen atom, a methyl group, or a trifluoromethyl group; even more preferably a hydrogen atom or a methyl group; and most preferably a hydrogen atom.

[0118] In the aforementioned formula (a10-1), Ya x1 is a single bond or a divalent linker. In the aforementioned chemical formula, the divalent linking group in Ya x1 is not particularly limited, and can include divalent hydrocarbon groups that can have substituents, divalent linking groups containing heteroatoms, etc. as suitable examples.

[0119] Ya x1 is preferably a single bond, an ester bond [-C(=O)-O-, -OC(=O)-], an ether bond (-O-), a straight-chain or branched alkyl group, or a combination thereof; more preferably a single bond or an ester bond [-C(=O)-O-, -OC(=O)-].

[0120] In the aforementioned formula (a10-1), Wa x1 is an aromatic hydrocarbon group that may have substituents. The aromatic hydrocarbon group in Wa x1 can be exemplified by a group obtained by removing (n ax1+1) hydrogen atoms from an aromatic ring that may have substituents. The aromatic ring here is not particularly limited as long as it has a cyclic conjugated system with 4n+2 π electrons. The number of carbon atoms in the aromatic ring is preferably 5-30, more preferably 5-20, even more preferably 6-15, and particularly preferably 6-12. Specifically, the aromatic ring can be exemplified by aromatic hydrocarbon rings such as benzene, naphthalene, anthracene, and phenanthrene; or by aromatic heterocycles in which a portion of the carbon atoms constituting the aforementioned aromatic hydrocarbon ring is replaced by heteroatoms. The heteroatoms in the aromatic heterocycle can be exemplified by oxygen atoms, sulfur atoms, and nitrogen atoms. Specifically, aromatic heterocycles can be exemplified by pyridine rings and thiophene rings. Furthermore, the aromatic hydrocarbon group in Wa x1 can also be listed as a group obtained by removing (n ax1+1) hydrogen atoms from an aromatic compound (such as biphenyl, fumonisin, etc.) containing two or more aromatic rings that can have substituents. Of the above, Wa x1 is preferably a group obtained by removing (n ax1+1) hydrogen atoms from benzene, naphthalene, anthracene or biphenyl; more preferably a group obtained by removing (n ax1+1) hydrogen atoms from benzene or naphthalene; and even more preferably a group obtained by removing (n ax1+1) hydrogen atoms from benzene.

[0121] The aromatic hydrocarbon group in Wa x1 may or may not have substituents. Examples of substituents include alkyl, alkoxy, halogen atoms, and alkyl halides. The alkyl, alkoxy, halogen atoms, and alkyl halides listed are the same as those listed as substituents for the cyclic aliphatic hydrocarbon group in Ya x1. Preferably, the substituent is a straight-chain or branched-chain alkyl group having 1 to 5 carbon atoms, more preferably a straight-chain or branched-chain alkyl group having 1 to 3 carbon atoms, and even more preferably ethyl or methyl, especially methyl. The aromatic hydrocarbon group in Wa x1 preferably does not have substituents.

[0122] In the aforementioned formula (a10-1), n ​​ax1 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 most preferably 1 or 2.

[0123] The following shows a specific example of the constituent unit (a10) represented by the aforementioned formula (a10-1). In the following formulas, Rα represents a hydrogen atom, a methyl group, or a trifluoromethyl group.

[0124]

[0125]

[0126]

[0127] (A1) The constituent units (a10) of the component can be one or more. When component (A1) has a constituent unit (a10), the proportion of the constituent unit (a10) in component (A1) relative to the total of all constituent units constituting component (100 mol%) is preferably 5 to 95 mol%, more preferably 10 to 90 mol%, even more preferably 30 to 70 mol%, and particularly preferably 40 to 60 mol. Sensitivity is more easily improved by setting the proportion of the constituent unit (a10) above the lower limit. On the other hand, it is easier to achieve balance with other constituent units by setting it below the upper limit.

[0128] Regarding the constituent units (a2): In addition to the constituent unit (a1), component (A1) may further have a constituent unit (a2) containing a cyclic group containing a lactone (except for those equivalent to constituent unit (a1)). The lactone-containing cyclic group of the constituent unit (a2) effectively improves the adhesion of the resist film to the substrate when component (A1) is used to form the resist film. Furthermore, by having the constituent unit (a2), for example, by appropriately adjusting the acid diffusion length, improving the adhesion of the resist film to the substrate, and appropriately adjusting the solubility during development, the lithography properties are improved.

[0129] "Cyclic groups containing lactones" refers to cyclic groups whose ring skeleton contains a ring with -OC (=O)- (lactone ring). The lactone ring is considered the first ring; when only the lactone ring is present, it is called a monocyclic group. When other ring structures are present, regardless of their structure, it is called a polycyclic group. Cyclic groups containing lactones can be either monocyclic or polycyclic. The lactone-containing cyclic group in the constituent unit (a2) is not particularly limited and any type can be used. Specifically, the groups represented by the following general formulas (a2-r-1) to (a2-r-7) can be listed.

[0130] [In the formula, Ra' 21 are independently hydrogen atoms, alkyl groups, alkoxy groups, halogen atoms, alkyl halides, hydroxyl groups, -COOR", -OC(=O)R", hydroxyalkyl groups or cyano groups; R" is a hydrogen atom, alkyl group, or a cyclic group containing lactones; A" is an alkyl group, oxygen atom or sulfur atom with 1 to 5 carbon atoms that may contain oxygen atoms (-O-) or sulfur atoms (-S-); n' is an integer from 0 to 2; m' is 0 or 1. * indicates the bonding site].

[0131] In the aforementioned general formulas (a2-r-1) to (a2-r-7), the alkyl group in Ra' 21 is preferably an alkyl group having 1 to 6 carbon atoms. This alkyl group is preferably straight-chain or branched-chain. Specifically, examples include methyl, ethyl, propyl, isopropyl, n-butyl, isobutyl, tert-butyl, pentyl, isopentyl, neopentyl, and hexyl. Among these, methyl or ethyl is particularly preferred, and methyl is especially preferred. The alkoxy group in Ra' 21 is preferably an alkoxy group having 1 to 6 carbon atoms. The alkoxy group is preferably straight-chain or branched-chain. Specifically, groups formed by linking an alkyl group (as listed above in Ra' 21) with an oxygen atom (-O-) can be included. The halogen atom in Ra' 21 is preferably a fluorine atom. The alkyl halide in Ra' 21 may be a group in which some or all of the hydrogen atoms of the alkyl group in Ra' 21 are substituted with the aforementioned halogen atoms. The alkyl halide is preferably a fluorinated alkyl group, and more preferably a perfluoroalkyl group.

[0132] In Ra' 21, -COOR” and -OC(=O)R”, R” are both hydrogen atoms, alkyl groups, and cyclic groups containing lactones. The alkyl group in "R" can be straight-chain, branched-chain, or cyclic, and the number of carbon atoms is preferably 1 to 15. When R” is a straight-chain or branched-chain alkyl group, it is preferably 1 to 10 carbon atoms, more preferably 1 to 5 carbon atoms, and especially preferably methyl or ethyl. When "R" is a cyclic alkyl group, it is preferable to have 3 to 15 carbon atoms, more preferably 4 to 12 carbon atoms, and most preferably 5 to 10 carbon atoms. Specifically, examples include groups obtained by removing one or more hydrogen atoms from monocyclic alkanes that may or may not be substituted with fluorine atoms or fluorinated alkyl groups; and groups obtained by removing one or more hydrogen atoms from polycyclic alkanes such as bicyclic alkanes, tricyclic alkanes, and tetracyclic alkanes. More specifically, examples include groups obtained by removing one or more hydrogen atoms from monocyclic alkanes such as cyclopentane and cyclohexane; and groups obtained by removing one or more hydrogen atoms from polycyclic alkanes such as adamantane, norcamphene, isocamphene, tricyclic decane, and tetracyclic dodecane. The lactone-containing cyclic group in "R" can be listed as the same as the group represented by the aforementioned general formulas (a2-r-1) to (a2-r-7). The hydroxyalkyl group in Ra' 21 is preferably one with 1 to 6 carbon atoms. Specifically, it can be a group in Ra' 21 in which at least one hydrogen atom is substituted with a hydroxyl group.

[0133] Ra' 21 is preferably either a hydrogen atom or a cyano group, which are independently represented by the above-mentioned elements.

[0134] In the aforementioned general formulas (a2-r-2), (a2-r-3), and (a2-r-5), the alkyl group with 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, specific examples include the presence of -O- or -S- groups at the end of the aforementioned alkyl group or between carbon atoms, such as -O-CH 2-, -CH 2-O-CH 2-, -S-CH 2-, and -CH 2-S-CH 2-. A” is preferably an alkyl group with 1 to 5 carbon atoms or -O-, more preferably an alkyl group with 1 to 5 carbon atoms, and most preferably methylene.

[0135] The specific examples of the bases represented by the general formulas (a2-r-1) to (a2-r-7) are listed below.

[0136]

[0137]

[0138] As a constituent unit (a2), it is preferably a constituent unit derived from an acrylate in which the hydrogen atom of the carbon atom bonded to the α-position can be replaced by a substituent. The constituent unit (a2) is preferably represented by the following general formula (a2-1).

[0139] [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. Ya 21 is a single bond or a divalent linked group. La 21 is -O-, -COO-, -CON(R')-, -OCO-, -CONHCO-, or -CONHCS-, where R' represents a hydrogen atom or a methyl group. However, when La 21 is -O-, Ya 21 is not -CO-. Ra 21 is a cyclic group containing a lactone.

[0140] In the aforementioned formula (a2-1), R is the same as described above. R is preferably a hydrogen atom, an alkyl group having 1 to 5 carbon atoms, or a fluorinated alkyl group having 1 to 5 carbon atoms. For industrial availability, it is particularly preferred to be a hydrogen atom or a methyl group.

[0141] In the aforementioned formula (a2-1), the divalent linking group in Ya 21 is not particularly limited, and can be suitable examples such as divalent hydrocarbon groups that can have substituents, divalent linking groups containing heteroatoms, etc.

[0142] Ya 21 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.

[0143] In the aforementioned formula (a2-1), Ra 21 is a cyclic group containing lactone. The lactone-containing cyclic groups in Ra 21 can be represented by the groups represented by the aforementioned general formulas (a2-r-1) to (a2-r-7). Preferably, the bases are those represented by the aforementioned general formulas (a2-r-1), (a2-r-2), or (a2-r-6); more preferably, the bases are those represented by the aforementioned general formula (a2-r-2). Specifically, it is more preferably any one of the aforementioned chemical formulas (r-lc-1-1) to (r-lc-1-7), (r-lc-2-1) to (r-lc-2-18), or (r-lc-6-1); more preferably, any one of the aforementioned chemical formulas (r-lc-2-1) to (r-lc-2-18); and even more preferably, any one of the aforementioned chemical formulas (r-lc-2-1) or (r-lc-2-12).

[0144] (A1) The constituent units (a2) of the component can be one or more. When component (A1) has a constituent unit (a2), the proportion of constituent unit (a2) relative to the total of all constituent units constituting component (A1) (100 mol%) is preferably 5 to 60 mol%, more preferably 10 to 60 mol%, even more preferably 20 to 60 mol%, and particularly preferably 30 to 60 mol. If the proportion of the constituent unit (a2) is above the lower limit, the effects caused by the constituent unit (a2) can be fully obtained through the aforementioned effects. If it is below the upper limit, a balance with other constituent units can be achieved, and various lithography properties become good.

[0145] Regarding the constituent units (a8): The constituent unit (a8) is a constituent unit derived from compounds represented by the following general formula (a8-1).

[0146] [In the formula, W2 is a polymerizable group. Yax2 is a single bond or a (nax2+1) valence group. Yax2 and W2 can also form a condensation ring. R1 is a fluorinated alkyl group with 1 to 12 carbon atoms. R2 is an organogroup with 1 to 12 carbon atoms or a hydrogen atom that may have a fluorine atom. R2 and Yax2 can also bond to each other to form a ring structure. nax2 is an integer from 1 to 3].

[0147] The "polymerizable group" in W 2 refers to a group that can polymerize compounds containing polymerizable groups through free radical polymerization, such as a group containing multiple bonds between carbon atoms, such as ethylene double bonds.

[0148] A base containing a polymerizable group can be a base consisting solely of a polymerizable group, or a base consisting of a polymerizable group and other groups besides that polymerizable group. Examples of other groups besides that polymerizable group include divalent hydrocarbon groups that may have substituents and divalent linking groups containing heteroatoms. A group containing a polymerizable group, for example, can be represented by the chemical formula: C(R X11)(R X12)=C(R X13)-Ya x0-. In this chemical formula, RX11, RX12 and RX13 are hydrogen atoms, alkyl groups with 1 to 5 carbon atoms or alkyl halides with 1 to 5 carbon atoms, respectively, and Yax0 is a single bond or a divalent linkage.

[0149] The condensation ring formed by Yax2 and W2 can be categorized into condensation rings formed by polymerizable groups at the W2 site and Yax2, as well as condensation rings formed by groups other than polymerizable groups at the W2 site and Yax2. The condensation ring formed by Ya x2 and W 2 can also have substituents.

[0150] The following shows specific examples of the constituent unit (a8). In the following formula, Rα represents a hydrogen atom, a methyl group, or a trifluoromethyl group.

[0151]

[0152] In the above examples, the constituent unit (a8) is preferably selected from at least one group of constituent units represented by chemical formulas (a8-1-01) to (a8-1-04), (a8-1-06), (a8-1-08), (a8-1-09), and (a8-1-10); more preferably, it is selected from at least one group of constituent units represented by chemical formulas (a8-1-01) to (a8-1-04) and (a8-1-09).

[0153] (A1) The constituent units (a8) of the component can be one or more. When component (A1) has a constituent unit (a8), the proportion of the constituent unit (a8) relative to the total of all constituent units constituting component (100 mol%) is preferably 1 to 50 mol%, more preferably 5 to 45 mol%, and even more preferably 5 to 40 mol. By setting the proportion of the constituent unit (a8) above the optimal lower limit, the compatibility with the developer and rinse solution can be improved. On the other hand, if it is below the optimal upper limit, a balance with other constituent units can be achieved, resulting in good lithography properties.

[0154] Regarding the constituent unit (a01): The constituent unit (a01) is the constituent unit derived from the compound represented by the following general formula (a0-1).

[0155] [In the formula, W01 is a polymerizable group. Ya01 is a single bond or a divalent bond. Ra01 is an acid-dissociable group. q is an integer from 0 to 3. n is an integer greater than or equal to 1. However, n ≦ q × 2 + 4].

[0156] In formula (a0-1), W01 is a base containing a polymerizable group. The term "polymerizable group" in W 01 refers to a group that can polymerize compounds containing polymerizable groups through free radical polymerization, such as a group containing multiple bonds between carbon atoms, including ethylene double bonds. In the constituent unit (a01), the multiple bonds in the polymeric group break to form the main chain.

[0157] Polymerizable groups in W 01 include, for example, vinyl, allyl, acrylonitrile, methacrylonitrile, fluorovinyl, difluorovinyl, trifluorovinyl, difluorotrifluoromethylvinyl, trifluoroallyl, perfluoroallyl, trifluoromethylacrylonitrile, nonylfluorobutylacrylonitrile, vinyl ether, fluorinated vinyl ether, allyl ether, fluorinated allyl ether, styryl, vinylnaphthyl, fluorinated styryl, fluorinated vinylnaphthyl, norcamphene, fluorinated norcamphene, silyl, etc.

[0158] The term "base containing a polymerizable group" in W 01 can refer to a base consisting solely of a polymerizable group, or it can refer to a base consisting of a polymerizable group and other groups besides that polymerizable group. Examples of other groups besides that polymerizable group include divalent hydrocarbon groups that may have substituents, divalent linkage groups containing heteroatoms, etc.

[0159] • Divalent hydrocarbon groups that may have substituents: When the other group besides the polymerizable group is a divalent hydrocarbon group that can have substituents, the hydrocarbon group can be an aliphatic hydrocarbon group or an aromatic hydrocarbon group.

[0160] Aliphatic hydrocarbon groups other than the polymerizable group The aliphatic hydrocarbon group refers to a hydrocarbon group that is not aromatic. This aliphatic hydrocarbon group can be saturated or unsaturated, but saturation is generally preferred. The aforementioned aliphatic hydrocarbon groups can include straight-chain or branched-chain aliphatic hydrocarbon groups, or aliphatic hydrocarbon groups containing rings in their structure.

[0161] Straight-chain or branched-chain aliphatic hydrocarbon groups The linear aliphatic hydrocarbon group is preferably composed of 1 to 10 carbon atoms, more preferably 1 to 6 carbon atoms, even more preferably 1 to 4 carbon atoms, and most preferably 1 to 3 carbon atoms. The linear aliphatic hydrocarbon group is preferred to be a linear alkyl group. Specifically, examples include methylene [-CH 2-], ethyl [-(CH 2) 2-], trimethylene [-(CH 2) 3-], tetramethylene [-(CH 2) 4-], pentamethylene [-(CH 2) 5-], etc. The aliphatic hydrocarbon group of the branched chain is preferably composed of 2 to 10 carbon atoms, more preferably 3 to 6 carbon atoms, even more preferably 3 or 4 carbon atoms, and most preferably 3 carbon atoms. Branched aliphatic hydrocarbon groups, preferably branched alkyl groups, specifically -CH(CH3)-, -CH(CH2CH3)-, etc. -C(CH 3) 2-, -C(CH 3)(CH 2CH 3)-, -C(CH 3)(CH 2CH 2CH 3)-, -C(CH2CH3)2- and other alkylmethylene groups; -CH(CH3)CH2-, -CH(CH 3)CH(CH 3)-, -C(CH 3) 2CH 2-, -CH(CH 2CH 3)CH 2-, -C(CH 2CH 3) 2-CH 2- and other alkyl ethyl groups; -CH(CH 3)CH 2CH 2-, -CH2CH(CH3)CH2- and other alkyltrimethylene groups; Alkyl tetramethylene, alkyl alkyl groups, etc., such as -CH(CH 3)CH 2CH 2CH 2- and -CH 2CH(CH 3)CH 2CH 2-. The alkyl group in the alkyl alkyl group is preferably a straight-chain alkyl group with 1 to 5 carbon atoms.

[0162] The aforementioned straight-chain or branched-chain aliphatic hydrocarbon groups may or may not have substituents. Examples of substituents include fluorine atoms, fluorinated alkyl groups with 1 to 5 carbon atoms substituted with fluorine atoms, and carbonyl groups.

[0163] The structure contains cyclic aliphatic hydrocarbon groups. This structure contains a ring-shaped aliphatic hydrocarbon group. Examples of ring-shaped aliphatic hydrocarbon groups that contain heteroatom substituents (groups obtained by removing two hydrogen atoms from an aliphatic hydrocarbon ring), groups obtained by the aforementioned ring-shaped aliphatic hydrocarbon group bonded to the end of a straight-chain or branched-chain aliphatic hydrocarbon group, and groups where the aforementioned ring-shaped aliphatic hydrocarbon group exists in the middle of a straight-chain or branched-chain aliphatic hydrocarbon group, etc. Examples of the aforementioned straight-chain or branched-chain aliphatic hydrocarbon groups are the same as those described above. The cyclic aliphatic hydrocarbon group is preferably composed of 3 to 20 carbon atoms, and more preferably 3 to 12 carbon atoms. The cyclic aliphatic hydrocarbon group can be either polycyclic or monocyclic. For monocyclic alicyclic hydrocarbon groups, it is preferable to obtain a group by removing two hydrogen atoms from a monocyclic alkane. The monocyclic alkane preferably has 3 to 6 carbon atoms, specifically cyclopentane, cyclohexane, etc. For polycyclic alicyclic hydrocarbon groups, it is preferable to obtain a group by removing two hydrogen atoms from a polycyclic alkane, preferably having 7 to 12 carbon atoms, specifically adamantane, norcamphene, isocamphene, tricyclodecane, tetracyclododecane, etc.

[0164] Cyclic aliphatic hydrocarbon groups may or may not have substituents. Examples of substituents include alkyl, alkoxy, halogen atoms, alkyl halides, hydroxyl groups, and carbonyl groups. The alkyl group used as the aforementioned substituent is preferably an alkyl group having 1 to 5 carbon atoms; most preferably methyl, ethyl, propyl, n-butyl, or tert-butyl. The alkoxy group used as the aforementioned substituent is preferably an alkoxy group having 1 to 5 carbon atoms; more preferably methoxy, ethoxy, n-propoxy, iso-propoxy, n-butoxy, or tert-butoxy; and most preferably methoxy or ethoxy. Halogen atoms that can be used as substituents include fluorine atoms, chlorine atoms, bromine atoms, iodine atoms, etc., with fluorine atoms being the most preferred. As the aforementioned substituent, the alkyl halide can be any group in which some or all of the hydrogen atoms of the aforementioned alkyl group are substituted with the aforementioned halogen atoms. The carbon atom of the cyclic aliphatic hydrocarbon group constituting its ring structure can also be substituted by a substituent containing a heteroatom. The substituent containing a heteroatom is preferably -O-, -C(=O)-O-, -S-, -S(=O)2-, or -S(=O)2-O-.

[0165] Aromatic hydrocarbon groups in groups other than the polymerizable group. The aromatic hydrocarbon group is a hydrocarbon group having at least one aromatic ring. The aromatic ring is not particularly limited as long as it possesses 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 5-30, more preferably 5-20, even more preferably 6-15, and most preferably 6-12. However, this number of carbon atoms does not include the number of carbon atoms in the substituents. Specifically, aromatic rings can be exemplified by aromatic hydrocarbon rings such as benzene, naphthalene, anthracene, and phenanthrene; and aromatic heterocycles in which a portion of the carbon atoms constituting the aforementioned aromatic hydrocarbon rings are substituted with heteroatoms. Heteratoms in aromatic heterocycles can be exemplified by oxygen atoms, sulfur atoms, and nitrogen atoms. Specifically, aromatic heterocycles can be exemplified by pyridine rings and thiophene rings. Specifically, aromatic hydrocarbon groups may include groups (aryl or heteroaryl) obtained by removing two hydrogen atoms from the aforementioned aromatic hydrocarbon ring or aromatic heterocycle; groups obtained by removing two hydrogen atoms from an aromatic compound containing two or more aromatic rings (e.g., biphenyl, benzo[a], etc.); and groups obtained by substituting one hydrogen atom of an aryl or heteroaryl group (aryl or heteroaryl) with an alkyl group (e.g., groups obtained by further removing one hydrogen atom from an aryl group of 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.

[0166] The aforementioned aromatic hydrocarbon group may also have its hydrogen atoms replaced by substituents. For example, the hydrogen atoms of the aromatic ring bonded to the aromatic hydrocarbon group may also be replaced by substituents. Examples of substituents include alkyl groups, alkoxy groups, halogen atoms, alkyl halides, and hydroxyl groups. The alkyl group used as the aforementioned substituent is preferably an alkyl group having 1 to 5 carbon atoms; most preferably methyl, ethyl, propyl, n-butyl, or tert-butyl. As the aforementioned substituents, alkoxy groups, halogen atoms, and alkyl halides can be exemplified by substituents that replace the hydrogen atoms of the aforementioned cyclic aliphatic hydrocarbon groups.

[0167] • Divalent linkages containing heteroatoms: When the other group besides the polymerizable group is a divalent linker containing heteroatoms, preferred examples of such linkers include -O-, -C(=O)-O-, etc. -C(=O)-, -OC(=O)-O-, -C(=O)-NH-, -NH-, -NH-C(=NH)- (H can be substituted by alkyl, acetylated, etc. substituents), -S-, -S(=O)2-, -S(=O) 2-O-, general formula -Y 21-OY 22-, -Y 21-O-, -Y 21-C(=O)-O-, -C(=O)-OY 21-, -[Y 21-C(=O)-O] m”-Y 22-, -Y 21-OC(=O)-Y 22- or -Y 21-S(=O) 2-OY 22- represent the base [where Y 21 and Y 22 are independently divalent hydrocarbon groups that can have substituents, O is an oxygen atom, and m” is an integer from 0 to 3], etc. When the aforementioned divalent linker containing heteroatoms is -C(=O)-NH-, -C(=O)-NH-C(=O)-, -NH-, or -NH-C(=NH)-, its H atoms may be substituted by substituents such as alkyl or acetyl groups. These substituents (alkyl, acetyl, etc.) preferably have 1 to 10 carbon atoms, more preferably 1 to 8, and particularly preferably 1 to 5. General formula -Y 21-OY 22-, -Y 21-O-, -Y 21-C(=O)-O-, -C(=O)-OY 21-, -[Y 21-C(=O)-O] m”-Y 22-, -Y 21-OC(=O)-Y 22-or In -Y 21-S(=O) 2-OY 22-, Y 21 and Y 22 are each independently a divalent hydrocarbon group that can have substituents. Such divalent hydrocarbon groups can be the same as those listed in the description of divalent linking groups (divalent hydrocarbon groups that can have substituents). Y 21 is preferably a straight-chain aliphatic hydrocarbon group, more preferably a straight-chain alkyl group, even more preferably a straight-chain alkyl group with 1 to 5 carbon atoms, and especially preferably methylene or ethyl group. Y22 is preferably a straight-chain or branched-chain aliphatic hydrocarbon group; more preferably methylene, ethyl, or alkylmethylene. The alkyl group in the alkylmethylene group is preferably a straight-chain alkyl group with 1 to 5 carbon atoms, more preferably a straight-chain alkyl group with 1 to 3 carbon atoms, and most preferably methyl. In the base represented by the formula -[Y 21-C(=O)-O] m”-Y 22-, m” is an integer from 0 to 3, preferably an integer from 0 to 2, more preferably 0 or 1, and most preferably 1. In other words, the base represented by the formula -[Y 21-C(=O)-O] m”-Y 22- is preferably the base represented by the formula -Y 21-C(=O)-OY 22-. Among them, the base represented by the formula -(CH 2) a'-C(=O)-O-(CH 2) b'- is even more preferred. In this formula, a' is an integer from 1 to 10, preferably an integer from 1 to 8, more preferably an integer from 1 to 5, even more preferably 1 or 2, and most preferably 1. b' is an integer from 1 to 10, preferably an integer from 1 to 8, more preferably an integer from 1 to 5, even more preferably 1 or 2, and most preferably 1.

[0168] W 01, for example, can be used to list chemical formulas: C(R X11)(R X12)=C(R X13)-Ya x0- represents the base. In this chemical formula, RX11, RX12 and RX13 are hydrogen atoms, alkyl groups with 1 to 5 carbon atoms or alkyl halides with 1 to 5 carbon atoms, respectively, and Yax0 is a single bond or a divalent linkage.

[0169] The alkyl groups having 1 to 5 carbon atoms in RX11, RX12, and RX13 are preferably straight-chain or branched-chain alkyl groups having 1 to 5 carbon atoms. Specifically, examples include methyl, ethyl, propyl, isopropyl, n-butyl, isobutyl, tert-butyl, pentyl, isopentyl, and neopentyl. The alkyl halide having 1 to 5 carbon atoms is a group in which some or all of the hydrogen atoms of the aforementioned alkyl groups having 1 to 5 carbon atoms are substituted with halogen atoms. The halogen atom is particularly preferably a fluorine atom. Of these, RX11 and RX12 are preferably hydrogen atoms, alkyl groups having 1 to 5 carbon atoms, or fluorinated alkyl groups having 1 to 5 carbon atoms, respectively. In terms of ease of industrial acquisition, hydrogen atoms and methyl groups are more preferred; hydrogen atoms are especially preferred. Furthermore, RX13 is preferably a hydrogen atom, an alkyl group having 1 to 5 carbon atoms, or a fluorinated alkyl group having 1 to 5 carbon atoms. In terms of ease of industrial acquisition, it is more preferably a hydrogen atom or a methyl group; and especially preferably a hydrogen atom.

[0170] The divalent linker in Ya x0 is not particularly limited. Examples of suitable examples include divalent hydrocarbon groups that may have substituents and divalent linkers containing heteroatoms, which are the same as those mentioned above.

[0171] Of the above, Ya x0 is preferably an ester bond [-C(=O)-O-, -OC(=O)-], ether bond (-O-), straight-chain or branched alkyl group, aromatic hydrocarbon group or combination thereof, or single bond. Among these, Ya x0 is more preferably a combination of ester bond [-C(=O)-O-, -OC(=O)-] and straight-chain alkyl group, or single bond; even more preferably a single bond.

[0172] In formula (a0-1), Ya 01 is a single bond or a divalent linker. The divalent linker in Ya 01 is not particularly limited, and suitable examples include divalent hydrocarbon groups that may have substituents, divalent linkers containing heteroatoms, etc., which are the same as those mentioned above.

[0173] In formula (a0-1), Ya 01 is preferably an ester bond [-C(=O)-O-, -OC(=O)-], an ether bond (-O-), a straight-chain or branched alkyl group, an aromatic hydrocarbon group, or a combination thereof, or a single bond. Among these, Ya 01 is more preferably a combination of an ester bond [-C(=O)-O-, -OC(=O)-] and a straight-chain alkyl group, or a single bond; and even more preferably a single bond.

[0174] In formula (a0-1), Ra 01 is an acid dissociative group. Specifically, acid dissociative groups can be categorized as "acetal-type acid dissociative groups", "tertiary alkyl ester-type acid dissociative groups", and "secondary alkyl ester-type acid dissociative groups" as mentioned above.

[0175] The following shows specific examples of the constituent unit (a01). In the following formulas, Rα represents a hydrogen atom, a methyl group, or a trifluoromethyl group.

[0176]

[0177]

[0178]

[0179]

[0180] The constituent unit (a01) of component (A1) may be one or more. The proportion of the constituent unit (a01) in component (A1) is preferably 5 to 95 mol%, more preferably 10 to 90 mol%, and even more preferably 30 to 70 mol%, and particularly preferably 40 to 60 mol%, relative to the total of all constituent units constituting component (A1) (100 mol%). By making the proportion of the constituent unit (a01) above the lower limit of the aforementioned preferred range, lithography properties such as sensitivity, CDU, resolution, and roughness are improved. On the other hand, if 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.

[0181] The (A1) component contained in the inhibitor composition can be used alone or in combination with two or more components. In the inhibitor composition of this embodiment, the (A1) component may include polymeric compounds having repeating structures of constituent units (a1), and more preferably polymeric compounds having repeating structures of constituent units (a1) and constituent units (a10); polymeric compounds having repeating structures of constituent units (a01) and constituent units (a10). As a component (A1), polymeric compounds composed of repeating structures of constituent units (a1) and (a10) are particularly suitable examples from the above; polymeric compounds composed of repeating structures of constituent units (a01) and (a10).

[0182] In a polymer compound having repeating structures of constituent units (a1) and constituent units (a10), the proportion of constituent units (a1) relative to the total (100 mol%) of all constituent units constituting the polymer compound is preferably 10 to 90 mol%, more preferably 20 to 80 mol%, even more preferably 30 to 70 mol%, and particularly preferably 40 to 60 mol. Furthermore, the proportion of the constituent units (a10) in the polymer compound, relative to the total of all constituent units constituting the polymer compound (100 mol%), is preferably 10 to 90 mol%, more preferably 20 to 80 mol%, even more preferably 30 to 70 mol%, and particularly preferably 40 to 60 mol.

[0183] The molar ratio (unit (a1):unit (a10)) of the polymer compound is preferably 2:8 to 8:2, more preferably 3:7 to 7:3, and even more preferably 4:6 to 6:4.

[0184] In a polymer compound having repeating structures of constituent units (a01) and constituent units (a10), the proportion of constituent unit (a01) relative to the total of all constituent units constituting the polymer compound (100 mol%) is preferably 10 to 90 mol%, more preferably 20 to 80 mol%, even more preferably 30 to 70 mol%, and particularly preferably 40 to 60 mol. Furthermore, the proportion of the constituent units (a10) in the polymer compound, relative to the total of all constituent units constituting the polymer compound (100 mol%), is preferably 10 to 90 mol%, more preferably 20 to 80 mol%, even more preferably 30 to 70 mol%, and particularly preferably 40 to 60 mol.

[0185] The molar ratio (unit (a01):unit (a10)) of the polymer compound is preferably 2:8 to 8:2, more preferably 3:7 to 7:3, and even more preferably 4:6 to 6:4.

[0186] The (A1) component can be manufactured by dissolving the monomers of each constituent unit in a polymerization solvent and then polymerizing them by adding free radical polymerization initiators such as azobisisobutyronitrile (AIBN) and dimethyl azobisisobutyrate (e.g., V-601). Alternatively, the (A1) component can be manufactured by dissolving the monomer of the derived constituent unit (a1) and the monomer of other constituent units (e.g., constituent unit (a10)) as needed in a polymerization solvent, adding the free radical polymerization initiator as described above to perform polymerization, and then carrying out a deprotection reaction. Furthermore, during polymerization, chain transfer agents such as HS-CH2-CH2-CH2-C(CF3)2-OH can be used to introduce -C(CF3)2-OH groups at the ends. In this way, copolymers with hydroxyalkyl groups in which a portion of the hydrogen atoms of the alkyl group is substituted with fluorine atoms are effective in reducing development defects or reducing LER (line edge roughness: unevenness of the line sidewalls).

[0187] The weight average molecular weight (Mw) of component (A1) (based on polystyrene conversion by gel permeation chromatography (GPC)) is not particularly limited, but is preferably 1,000 to 50,000, more preferably 2,000 to 30,000, and even more preferably 3,000 to 20,000. (A1) If the Mw of component is below the preferred upper limit of the range, it has sufficient solubility in the resist solvent for use as a resist agent; if it is above the preferred lower limit of the range, it has good resistance to dry etching or good resist pattern cross-sectional shape. (A1) The dispersion (Mw / Mn) of the component is not particularly limited, but is preferably 1.0 to 4.0, more preferably 1.0 to 3.0, and especially preferably 1.0 to 2.0. Furthermore, Mn represents the number average molecular weight.

[0188] Regarding ingredient (A2) The resist composition of this embodiment may also be combined with a substrate component (hereinafter referred to as "(A2) component") that is not equivalent to the aforementioned (A1) component and whose solubility in the developer changes due to the action of acid, as component (A). (A2) The ingredients are not particularly limited, and can be selected from the majority of previously known base material ingredients used as chemically amplifying inhibitor components. (A2) Components can be used alone or in combination of two or more high molecular weight compounds.

[0189] The proportion of component (A1) in component (A) relative to the total mass of component (A) is preferably 25% by mass or more, more preferably 50% by mass or more, and even more preferably 75% by mass or more, and can also be 100% by mass. If the proportion is 25% by mass or more, it is easy to form a resist pattern with excellent lithography properties such as high sensitivity, resolution, and roughness improvement.

[0190] In the resist composition of this embodiment, the content of component (A) can be adjusted according to the desired resist film thickness.

[0191] <Acid-generating component (B)> The (B) component in the inhibitor composition of this embodiment includes a compound (B0) represented by the following general formula (b0) (hereinafter also referred to as the "(B0) component").

[0192] ≪Compound(B0)≫ (B0) is a compound represented by the following general formula (b0).

[0193] [In the formula, Rb0 is a condensed cyclic group obtained by the condensation of an aromatic ring and an alicyclic ring. The alicyclic ring in the aforementioned condensed cyclic group has substituents, and at least one of the substituents contains a hydrocarbon group having a bromine atom or a hydrocarbon group having an iodine atom. Yb0 is a divalent linkage or a single bond. However, Yb0 is bonded to the alicyclic ring in the aforementioned condensed cyclic group. Vb0 is a single bond, an alkyl group, or a fluorinated alkyl group. R0 is a fluorinated alkyl group or a fluorine atom with 1 to 5 carbon atoms. Mm+ represents an m-valent organic cation. m is an integer greater than or equal to 1].

[0194] {(B0) component's anionic portion} In the above general formula (b0), Rb0 is a condensed cyclic group obtained by the condensation of an aromatic ring and an alicyclic ring.

[0195] The aromatic ring is not particularly limited as long as it has 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 most preferably 6 to 14. Specifically, aromatic rings can be exemplified by aromatic hydrocarbon rings such as benzene, naphthalene, anthracene, and phenanthrene; and aromatic heterocycles in which a portion of the carbon atom constituting the aforementioned aromatic hydrocarbon ring is replaced by a heteroatom. Heteratomes in aromatic heterocycles can be exemplified by oxygen atoms, sulfur atoms, and nitrogen atoms. Specifically, aromatic heterocycles can be exemplified by pyridine rings and thiophene rings.

[0196] The alicyclic ring can be monocyclic or polycyclic. The number of carbon atoms in the alicyclic ring is preferably 4 to 30, more preferably 4 to 20, even more preferably 4 to 15, and most preferably 4 to 10. Alicyclic rings specifically include monocyclic aliphatic rings such as cyclobutane, cyclopentane, cyclohexane, and cyclooctane; polycyclic aliphatic rings such as adamantane, norcamphene, isocamphene, tricyclodecane, and tetracyclododecane; and aliphatic heterocycles in which a portion of the carbon atom constituting the monocyclic or polycyclic aliphatic ring is replaced by a heteroatom. Heteroatoms in aliphatic heterocycles can include oxygen, sulfur, and nitrogen atoms. Specifically, aliphatic heterocycles can include tetrahydropyran rings, thiane rings, and piperidine rings.

[0197] The condensation ring group in Rb 0 can have one aromatic ring condensed on one alicyclic ring, two or more aromatic rings condensed on one alicyclic ring, two or more alicyclic rings condensed on one aromatic ring, or alicyclic and aromatic rings can be repeatedly condensed. Furthermore, when multiple alicyclic rings and multiple aromatic rings are condensed, they can be the same or different.

[0198] The condensed cyclic group in Rb 0 is preferably a condensed cyclic group having one aromatic ring condensed on one alicyclic ring, or a condensed cyclic group having two or more aromatic rings condensed on one alicyclic ring; more preferably a condensed cyclic group having one aromatic hydrocarbon ring condensed on one monocyclic aliphatic ring, or a condensed cyclic group having two or more aromatic hydrocarbon rings condensed on one monocyclic aliphatic ring; and even more preferably a condensed cyclic group having two aromatic hydrocarbon rings condensed on one monocyclic aliphatic ring.

[0199] Specifically, condensed cyclic groups in Rb 0 can be exemplified by fu; and polycyclic alkanes with one or more aromatic rings condensed on a polycyclic skeleton having a cross-linked ring system. Specific examples of the aforementioned cross-linked cyclic polycyclic alkanes include bicyclic alkanes such as bicyclic [2.2.1]heptane (norbornene) and bicyclic [2.2.2]octane. The condensed cyclic group in Rb 0, more specifically, is preferably a condensed cyclic group having two or three aromatic rings condensed on a bicycloalkane, and more preferably a condensed cyclic group having two or three aromatic rings condensed on a bicyclo[2.2.2]octane. Specific examples of condensed ring bases in Rb 0 can be listed below, represented by the bases in equations (r-br-1) to (r-br-2). In the equations, * indicates the bonding site of Yb 0 in equation (b0).

[0200]

[0201] In the above general formula (b0), the condensed cyclic group in Rb0 is preferably a condensed cyclic group having two or three aromatic rings condensed on a bicycloalkane, more preferably a condensed cyclic group having two or three aromatic rings condensed on a bicyclo[2.2.2]octane, and even more preferably a group represented by the above formulas (r-br-1)~(r-br-2).

[0202] In the above general formula (b0), the alicyclic group in the condensed cyclic group of Rb0 has substituents, and among the aforementioned substituents, at least one includes a hydrocarbon group having a bromine atom or a hydrocarbon group having an iodine atom. Hydrocarbon groups containing bromine atoms, or hydrocarbon groups containing iodine atoms, can be listed as linear or branched alkyl groups, or cyclic hydrocarbon groups.

[0203] The linear alkyl group preferably has 1 to 5 carbon atoms. Specifically, examples include methyl, ethyl, n-propyl, n-butyl, and n-pentyl. The branched chain alkyl group preferably has 3 to 10 carbon atoms, more preferably 3 to 5. Specifically, examples include isopropyl, isobutyl, tert-butyl, isopentyl, neopentyl, 1,1-diethylpropyl, 2,2-dimethylbutyl, etc.

[0204] The cyclic hydrocarbon group can be an aliphatic hydrocarbon group or an aromatic hydrocarbon group, and it can be a polycyclic group or a monocyclic group. The cyclic hydrocarbon group can be exemplified by the group obtained by removing one hydrogen atom from the aromatic or aliphatic ring of the aforementioned Rb 0 condensed cyclic group.

[0205] The hydrocarbon group having a bromine atom or a hydrocarbon group having an iodine atom, preferably a cyclic hydrocarbon group or more preferably an aromatic hydrocarbon group.

[0206] The hydrocarbon group may have one or more substituents other than bromine and iodine atoms. Examples of substituents include alkyl, fluorine, chlorine, alkoxy (methoxy, ethoxy, propoxy, butoxy, etc.), hydroxy, cyano, amino, and nitro groups. Furthermore, regarding the hydrocarbon group, a portion of the carbon atom (such as methylene) constituting the hydrocarbon group can also be substituted by a group containing heteroatoms. The heteroatoms referred to here can include oxygen atoms, sulfur atoms, and nitrogen atoms. Radicals containing heteroatoms can 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.

[0207] The hydrocarbon group can also be one that has both bromine and iodine atoms. That is, the alicyclic group in the condensation ring of Rb 0 can have a hydrocarbon group with both bromine and iodine atoms.

[0208] The total number of bromine and iodine atoms in the hydrocarbon group is preferably an integer from 1 to 3, more preferably 2 or 3, and even more preferably 3. The more bromine and iodine atoms a hydrocarbon group has in total, the greater the tendency to achieve high sensitivity during inhibitor pattern formation.

[0209] The substituents in the alicyclic group of Rb 0 are preferably represented by the following general formula (X-1).

[0210] [In the formula, X01 is a single bond or a divalent linkage group. Ri01 is a hydrocarbon group with a bromine atom or a hydrocarbon group with an iodine atom. In the formula, * indicates the alicyclic bonding site in the condensed cyclic group of Rb0 in formula (b0).]

[0211] In the above general formula (X-1), X 01 is a divalent linker. A suitable list of divalent linkers includes those containing an oxygen atom. Divalent linkages containing oxygen atoms include, for example, non-hydrocarbon linkages containing oxygen atoms such as oxygen atoms (ether bond: -O-), ester bond (-C(=O)-O-), oxycarbonyl group (-OC(=O)-), amide bond (-C(=O)-NH-), carbonyl group (-C(=O)-), carbonate bond (-OC(=O)-O-), etc.; combinations of these non-hydrocarbon linkages containing oxygen atoms with alkyl groups, etc. Sulfonyl groups (-SO 2-) can also be further linked to these combinations.

[0212] The alkyl group can be categorized into straight-chain alkyl groups and branched-chain alkyl groups. Straight-chain alkyl groups can be exemplified by methylene [-CH 2-], ethyl [-(CH 2) 2-], trimethylene [-(CH 2) 3-], tetramethylene [-(CH 2) 4-], pentamethylene [-(CH 2) 5-], etc. Branched chain alkyl groups, such as -CH(CH3)-, can be listed as... -CH(CH 2CH 3)-, -C(CH 3) 2-, -C(CH 3)(CH 2CH 3)-, Alkyl methylene groups such as -C(CH 3)(CH 2CH 2CH 3)- and -C(CH 2CH 3) 2-; -CH(CH 3)CH 2-, -CH(CH 3)CH(CH 3)-, -C(CH 3) 2CH 2-, Alkyl groups such as -CH(CH2CH3)CH2- and -C(CH2CH3)2-CH2- are ethyl groups. Alkyltrimethylenes such as -CH(CH 3)CH 2CH 2- and -CH 2CH(CH 3)CH 2-; alkyltetramethylenes such as -CH(CH 3)CH 2CH 2CH 2- and -CH 2CH(CH 3)CH 2CH 2-; and alkyl alkylenes such as -CH(CH 3)CH 2CH 2- and -CH 2CH(CH 3)CH 2CH 2-.

[0213] Furthermore, X 01 can also be -N(Ra)-C(=O)-, -N(Ra)-, -C(Ra)(Ra)-N(Ra)-, -C(Ra)(N(Ra)(Ra))-, -C(=O)-N(Ra)-, or any of these groups combined with an alkyl group. Furthermore, each Ra group is independently a hydrogen atom or an alkyl group.

[0214] In the above general formula (X-1), X01 is preferably -O-, -OCO-, -COO-, or any of these groups combined with an alkyl group; more preferably -OCO-, -COO-, or a combination of -OCO- or -COO- with an alkyl group; even more preferably -COO-. Furthermore, regarding the specific example of X 01, the descriptions of each linking group are consistent with the structure in the general formula (X-1). That is, for example, regarding -COO-, the carbon atom bonded to the carbon atom in -COO- is the alicyclic carbon atom in the condensed cyclic group of Rb 0. Also, the oxygen atom bonded to the carbon atom in -COO- is Ri 01 in the general formula (X-1).

[0215] In the above general formula (X-1), Ri 01 is a hydrocarbon group having a bromine atom or a hydrocarbon group having an iodine atom. The hydrocarbon group can be the same as the hydrocarbon group having a bromine atom or a hydrocarbon group having an iodine atom mentioned above.

[0216] In the above general formula (X-1), Ri 01 is preferably an aromatic hydrocarbon group having a bromine atom or an aromatic hydrocarbon group having an iodine atom; more preferably a phenyl or naphthyl group having a bromine atom or a phenyl or naphthyl group having an iodine atom; and even more preferably a phenyl group having a bromine atom or a phenyl group having an iodine atom.

[0217] In the above general formula (X-1), Ri 01 can also be a hydrocarbon group having both bromine and iodine atoms.

[0218] The total number of bromine and iodine atoms in the hydrocarbon group is preferably an integer from 1 to 3, more preferably 2 or 3, and even more preferably 3. The more bromine and iodine atoms a hydrocarbon group has in total, the greater the tendency to achieve high sensitivity during inhibitor pattern formation.

[0219] The aforementioned hydrocarbon group (aromatic hydrocarbon group) may also have substituents other than bromine and iodine atoms. When the aforementioned hydrocarbon group (aromatic hydrocarbon group) has substituents other than bromine and iodine atoms, the substituents are preferably alkyl groups having 1 to 5 carbon atoms, fluorine atoms, or hydroxyl groups.

[0220] In the above general formula (b0), Yb0 is a divalent linker or a single bond. However, Yb0 is bonded to the alicyclic bonds in the aforementioned condensed cyclic group. The divalent linkages in Yb0 can be used to list divalent linkages containing oxygen atoms. When Yb0 is a divalent bonding group containing an oxygen atom, it can contain atoms other than oxygen atoms. Examples of atoms other than oxygen atoms include carbon atoms, hydrogen atoms, sulfur atoms, and nitrogen atoms. A divalent group containing an oxygen atom, for example, can be listed as the same divalent group containing an oxygen atom as in X 01 above.

[0221] The divalent linker containing an oxygen atom can be exemplified by the linkers represented by the following general formulas (y-al-1) to (y-al-8). Furthermore, in the following general formulas (y-al-1) to (y-al-7), the alicyclic group bonded to the Rb 0 condensation cyclic group in the above general formula (b0) is V' 101 in the following general formulas (y-al-1) to (y-al-7).

[0222] [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].

[0223] 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.

[0224] The alkyl groups in V' 101 and V' 102 can be either straight-chain or branched-chain, with straight-chain alkyl groups being more preferred. The alkyl groups in V' 101 and V' 102, specifically, can be exemplified by methylene [-CH 2-]; -CH(CH 3)-, -CH(CH 2CH 3)-, -C(CH 3) 2-, Alkyl methylene groups such as -C(CH 3)(CH 2CH 3)-, -C(CH 3)(CH 2CH 2CH 3)-, and -C(CH 2CH 3) 2-; ethyl [-CH 2CH 2-]; -CH(CH 3)CH 2-, Alkyl ethyl groups such as -CH(CH 3)CH(CH 3)-, -C(CH 3) 2CH 2-, and -CH(CH 2CH 3)CH 2-; trimethylene (n-propyl)[-CH 2CH 2CH 2-]; Alkyltrimethylenes such as -CH(CH 3)CH 2CH 2- and -CH 2CH(CH 3)CH 2-; tetramethylenes [-CH 2CH 2CH 2CH 2-]; alkyltetramethylenes such as -CH(CH 3)CH 2CH 2CH 2- and -CH 2CH(CH 3)CH 2CH 2-; pentamethylenes [-CH 2CH 2CH 2CH 2CH 2-], etc. Furthermore, a portion of the methylene group in the aforementioned alkyl group of V' 101 or V' 102 may also be substituted with a divalent aliphatic cyclic group having 5 to 10 carbon atoms. The preferred aliphatic cyclic group is cyclohexyl, 1,5-adamantyl, or 2,6-adamantyl.

[0225] Yb 0 is preferably a divalent linker containing an ester bond or a divalent linker containing an ether bond; more preferably a linker represented by the formulas (y-al-1) to (y-al-6) above, and even more preferably a linker represented by the formulas (y-al-1) or (y-al-6) above.

[0226] In the above general formula (b0), V b0 represents an enyl group, a fluorinated enyl group, or a single bond. The alkylene group and the fluorinated alkylene group in V b0 are preferably composed of 1 to 4 carbon atoms and more preferably 1 to 3 carbon atoms, respectively. The fluorinated alkylene group in V b0 may be a group in which some or all of the hydrogen atoms of the alkylene group are substituted with fluorine atoms.

[0227] In the above general formula (b0), V b0 is preferably an enylalkyl group or a fluorinated enylalkyl group; more preferably an enylalkyl group having 1 to 4 carbon atoms, or a fluorinated enylalkyl group having 1 to 4 carbon atoms; and even more preferably a straight-chain enylalkyl group having 1 to 4 carbon atoms, or a branched-chain fluorinated enylalkyl group having 1 to 4 carbon atoms.

[0228] In the above general formula (b0), R0 is a fluorinated alkyl group having 1 to 5 carbon atoms or a fluorine atom. R0 is preferably a fluorine atom or a perfluoroalkyl group having 1 to 5 carbon atoms, and more preferably a fluorine atom.

[0229] In this embodiment, the anion portion of the (B0) component is preferably represented by the following general formula (b0-an0) from the viewpoint of improving sensitivity and CDU.

[0230] [In the formula, Rx1 to Rx4 each independently represent a hydrocarbon group or hydrogen atom that may have substituents, or two or more of them may bond together to form a ring structure. Ry1 to Ry2 each independently represent a hydrocarbon group or hydrogen atom that may have substituents, or they may bond together to form a ring structure.] It can be a double bond or a single bond. Rz 1 to Rz 4, when the valence allows, can independently represent a hydrocarbon group or hydrogen atom that may have substituents, or two or more can bond together to form a ring structure. However, at least one of two or more Rx 1 to Rx 4, Ry 1 to Ry 2, or at least two or more Rz 1 to Rz 4 can bond together to form an aromatic ring. Furthermore, at least one of Rx 1 to Rx 4, Ry 1 to Ry 2, and Rz 1 to Rz 4 has an anionic group represented by the following general formula (b0-r-an1), with the entire anionic portion becoming an n-valent anion. Furthermore, at least one of Rx 1 to Rx 4, Ry 1 to Ry 2, and Rz 1 to Rz 4 contains a hydrocarbon group with a bromine atom or a hydrocarbon group with an iodine atom. (n is an integer of 1 or more).

[0231] [In the formula, Yb0 is a divalent linker or a single bond. Vb0 is a single bond, an alkyl group, or a fluorinated alkyl group. * indicates the bonding site].

[0232] In formula (b0-an0), Rx1 to Rx4 represent hydrocarbon groups or hydrogen atoms that can have substituents, or two or more that can bond together to form a ring structure. The Ry1 to Ry2 series independently represent hydrocarbon groups or hydrogen atoms that can have substituents, or they can bond together to form a ring structure. Rz 1 to Rz 4, when the atomic valence allows, represent the hydrocarbon group or hydrogen atom that can have substituents, or two or more that can bond together to form a ring structure.

[0233] The hydrocarbon groups in Rx 1~Rx 4, Ry 1~Ry 2, and Rz 1~Rz 4 can be aliphatic or aromatic hydrocarbon groups, and can be cyclic or chain hydrocarbon groups. For example, among Rx 1~Rx 4, Ry 1~Ry 2, and Rz 1~Rz 4, the hydrocarbon groups that can have substituents can be listed as cyclic groups that can have substituents, chain alkyl groups that can have substituents, or chain alkenyl groups that can have substituents.

[0234] 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 is usually preferred to be saturated. Also, the cyclic hydrocarbon groups in Rx 1~Rx 4, Ry 1~Ry 2, and Rz 1~Rz 4 can also contain heteroatoms, similar to heterocycles.

[0235] The aromatic hydrocarbon groups in Rx 1~Rx 4, Ry 1~Ry 2, and Rz 1~Rz 4 are hydrocarbon groups having an aromatic ring. The number of carbon atoms in this aromatic hydrocarbon group is preferably 3~30, more preferably 5~30, even more preferably 5~20, particularly preferably 6~15, and most preferably 6~12. However, this number of carbon atoms does not include the number of carbon atoms in the substituents. The aromatic rings possessed by the aromatic hydrocarbon groups in Rx 1~Rx 4, Ry 1~Ry 2, and Rz 1~Rz 4 can specifically include benzene, naphthalene, naphthalene, anthracene, phenanthrene, biphenyl, or aromatic heterocycles in which a portion of the carbon atom constituting such aromatic rings is substituted with a heteroatom. The heteroatoms in the aromatic heterocycles can include oxygen atoms, sulfur atoms, nitrogen atoms, etc. From the viewpoint of compatibility with component (A), the aromatic rings possessed by the aromatic hydrocarbon groups in Rx 1~Rx 4, Ry 1~Ry 2, and Rz 1~Rz 4 preferably do not contain heteroatoms; more preferably, they are aromatic rings of benzene, naphthalene, anthracene, phenanthrene, biphenyl, etc. Aromatic hydrocarbon groups in Rx 1~Rx 4, Ry 1~Ry 2, and Rz 1~Rz 4, specifically, include groups obtained by removing one hydrogen atom from the aforementioned aromatic ring (aryl: for example, phenyl, naphthyl, etc.), and groups obtained by substituting one hydrogen atom of the aforementioned aromatic ring with 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 most preferably 1 carbon atom.

[0236] Cyclic aliphatic hydrocarbon groups in Rx 1~Rx 4, Ry 1~Ry 2, and Rz 1~Rz 4 can be listed as aliphatic hydrocarbon groups containing rings in their structure. The structure contains a ring of aliphatic hydrocarbon groups, such as alicyclic hydrocarbon groups (derived by removing one hydrogen atom from an aliphatic hydrocarbon ring), alicyclic hydrocarbon groups bonded to the end of a straight or branched aliphatic hydrocarbon group, and alicyclic hydrocarbon groups present in the middle of a straight or branched aliphatic hydrocarbon group. 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 either a polycyclic or monocyclic group. For monocyclic alicyclic hydrocarbon groups, it is preferable to obtain a group by removing one or more hydrogen atoms from a monocyclic alkane. The monocyclic alkane is preferably composed of 3 to 6 carbon atoms, specifically cyclopentane, cyclohexane, etc. For polycyclic alicyclic hydrocarbon groups, it is preferable to obtain a group by removing one or more hydrogen atoms from a polycyclic alkane, preferably composed of 7 to 30 carbon atoms.

[0237] A straight-chain aliphatic hydrocarbon group that can be bonded to an alicyclic hydrocarbon group is preferably composed of 1 to 10 carbon atoms, more preferably 1 to 6 carbon atoms, even more preferably 1 to 4 carbon atoms, and most preferably 1 to 3 carbon atoms. The straight-chain aliphatic hydrocarbon group is preferably a straight-chain alkyl group, specifically including methylene [-CH 2-], ethyl [-(CH 2) 2-], trimethylene [-(CH 2) 3-], tetramethylene [-(CH 2) 4-], pentamethylene [-(CH 2) 5-], etc. A branched aliphatic hydrocarbon group that can be bonded to an alicyclic hydrocarbon group, preferably having 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. The branched aliphatic hydrocarbon group is preferably a branched alkyl group; specifically, -CH(CH3)- can be listed. -CH(CH 2CH 3)-, -C(CH 3) 2-, -C(CH 3)(CH 2CH 3)-, Alkyl methylene groups such as -C(CH 3)(CH 2CH 2CH 3)- and -C(CH 2CH 3) 2-; -CH(CH 3)CH 2-, -CH(CH 3)CH(CH 3)-, -C(CH 3) 2CH 2-, Alkyl groups such as -CH(CH2CH3)CH2- and -C(CH2CH3)2-CH2- are ethyl groups. Alkyltrimethylammonium compounds such as -CH(CH3)CH2CH2- and -CH2CH(CH3)CH2-; alkyltetramethylene compounds such as -CH(CH3)CH2CH2CH2- and -CH2CH(CH3)CH2CH2-; and alkyl alkylene compounds such as alkyltetramethylene. Preferably, the alkyl group in the alkyl alkylene compounds is a straight-chain alkyl group having 1 to 5 carbon atoms.

[0238] Furthermore, for the cyclic groups Rx 1~Rx 4, Ry 1~Ry 2, and Rz 1~Rz 4, in relation to -COOR XYZ and -OC(=O)R XYZ, R XYZ can also be listed as cyclic groups containing lactones or cyclic groups containing -SO 2-.

[0239] "Cyclic groups containing -SO₂⁻" refers to cyclic groups whose ring skeleton contains a ring with -SO₂⁻. Specifically, it refers to cyclic groups in which the sulfur atom (S) in -SO₂⁻ forms part of the ring skeleton of the cyclic group. The ring containing -SO₂⁻ in its ring skeleton is counted as the first ring. When it has only this ring, it is called a monocyclic group. When it has other ring structures, it is called a polycyclic group regardless of its structure. Cyclic groups containing -SO₂⁻ can be monocyclic or polycyclic. The cyclic group containing -SO 2- is particularly preferred to have a cyclic group containing -O-SO 2- in its cyclic skeleton, that is, a cyclic group containing a sultone ring in which -OS- in -O-SO 2- forms part of the cyclic skeleton. The cyclic bases containing -SO 2-, more specifically, can be represented by the following general formulas (b5-r-1) to (b5-r-4).

[0240] [In the formula, Rb' 51 are independently hydrogen atoms, alkyl groups, alkoxy groups, halogen atoms, alkyl halides, hydroxyl groups, -COOR", -OC(=O)R", hydroxyalkyl groups or cyano groups; R" is a hydrogen atom, alkyl group, cyclic group containing lactone, or cyclic group containing -SO 2-; B" is an alkyl group, oxygen atom or sulfur atom with 1 to 5 carbon atoms that may contain oxygen atoms or sulfur atoms, and n' is an integer from 0 to 2. * indicates the bonding site].

[0241] In the aforementioned general formulas (b5-r-1) to (b5-r-2), B” is an alkyl group, oxygen atom, or sulfur atom with 1 to 5 carbon atoms that may contain oxygen atoms or sulfur atoms. B" is preferably an alkyl group having 1 to 5 carbon atoms or -O-, more preferably an alkyl group having 1 to 5 carbon atoms, and even more preferably a methylene group.

[0242] In the aforementioned general formulas (b5-r-1) to (b5-r-4), Rb' 51 is independently a hydrogen atom, alkyl group, alkoxy group, halogen atom, haloalkyl group, hydroxyl group, -COOR", -OC(=O)R", hydroxyalkyl group or cyano group, and preferably independently a hydrogen atom or cyano group.

[0243] The following lists specific examples of the bases represented by the general formulas (b5-r-1) to (b5-r-4). In the formulas, "Ac" represents acetyl.

[0244]

[0245]

[0246]

[0247] Substituents in the cyclic groups Rx 1~Rx 4, Ry 1~Ry 2, and Rz 1~Rz 4 can be listed as substituents that are the same as those that can be present in the polycyclic aromatic cyclic groups in Rb 0 mentioned above. Of the substituents in the cyclic groups of Rx 1~Rx 4, Ry 1~Ry 2, and Rz 1~Rz 4, from the viewpoint of compatibility with component (A), alkyl, halogen atom, and halogenated alkyl are particularly preferred.

[0248] Alkyl groups that may have substituents: The chain alkyl groups Rx 1~Rx 4, Ry 1~Ry 2, and Rz 1~Rz 4 can be either straight-chain or branched-chain. The alkyl group is linear, preferably with 1 to 20 carbon atoms, more preferably with 1 to 15 carbon atoms, and most preferably with 1 to 10 carbon atoms. Specifically, examples include methyl, ethyl, propyl, butyl, pentyl, hexyl, heptyl, octyl, nonyl, decyl, undecyl, dodecyl, tridecyl, isotriadecyl, tetradecyl, pentadecyl, hexadecyl, isohexadecanyl, heptadecanyl, octadecyl, nonadecanyl, eicosyl, dodecyl, dodecyl, etc. Branched alkyl groups are preferably composed of 3 to 20 carbon atoms, more preferably 3 to 15 carbon atoms, and most preferably 3 to 10 carbon atoms. Specifically, examples include 1-methylethyl, 1,1-dimethylethyl, 1-methylpropyl, 2-methylpropyl, 1-methylbutyl, 2-methylbutyl, 3-methylbutyl, 1-ethylbutyl, 2-ethylbutyl, 1-methylpentyl, 2-methylpentyl, 3-methylpentyl, 4-methylpentyl, etc.

[0249] Alkenyl groups that may have substituents in a chain: The chain-like alkenyl groups Rx 1~Rx 4, Ry 1~Ry 2, and Rz 1~Rz 4 can be either straight-chain or branched-chain, preferably with 2~10 carbon atoms, more preferably with 2~5 carbon atoms, even more preferably with 2~4 carbon atoms, and most preferably with 3 carbon atoms. Examples of straight-chain alkenyl groups include vinyl, allyl, and butenyl. Examples of branched-chain alkenyl groups include 1-propenyl, 2-propenyl, 1-methylpropenyl, and 2-methylpropenyl.

[0250] Substituents in the chain-like alkyl or alkenyl groups of Rx 1~Rx 4, Ry 1~Ry 2, Rz 1~Rz 4, such as alkoxy groups, halogen atoms, alkyl halides, hydroxyl groups, carbonyl groups, nitro groups, amino groups, and cyclic groups among the aforementioned Rx 1~Rx 4, Ry 1~Ry 2, Rz 1~Rz 4, are particularly preferred as substituents in the chain-like alkyl or alkenyl groups of Rx 1~Rx 4, Ry 1~Ry 2, Rz 1~Rz 4, from the viewpoint of compatibility with component (A), halogen atoms, alkyl halides, and cyclic groups among the aforementioned Rx 1~Rx 4, Ry 1~Ry 2, Rz 1~Rz 4.

[0251] In the aforementioned equation (b0-an0), Ry 1 to Ry 2 can also be bonded to each other to form a ring structure. The ring structure formed by Ry 1 to Ry 2 shares one side of the six-membered ring in formula (b0-an0) (the bond between the carbon atoms bonded by Ry 1 and Ry 2 respectively). This ring structure can be an alicyclic hydrocarbon or an aromatic hydrocarbon. Furthermore, this ring structure can also be a polycyclic structure formed by it and other ring structures.

[0252] The alicyclic hydrocarbons formed by Ry 1 to Ry 2 can be polycyclic or monocyclic. Monocyclic alicyclic hydrocarbons are preferably monocyclic alkanes. These monocyclic alkanes preferably have 3 to 6 carbon atoms, specifically cyclopentane and cyclohexane. Polycyclic alicyclic hydrocarbons are preferably polycyclic alkanes. These polycyclic alkanes preferably have 7 to 30 carbon atoms.

[0253] Aromatic hydrocarbon rings formed by Ry 1 to Ry 2 may 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. From the viewpoint of compatibility with component (A), the aromatic hydrocarbon rings formed by Ry 1 to Ry 2 are preferably free of heteroatoms; more preferably, they are aromatic rings of benzene, naphthalene, anthracene, phenanthrene, biphenyl, etc.

[0254] The ring structures formed by Ry 1 to Ry 2 (alicyclic hydrocarbons, aromatic hydrocarbons) may also have substituents. Examples of substituents here include those identical to those in the ring structures of Rx 1 to Rx 4, Ry 1 to Ry 2, and Rz 1 to Rz 4 (e.g., alkyl, alkoxy, halogen atom, alkyl halide, hydroxyl, nitro, carbonyl, etc.). Among these, from the viewpoint of compatibility with component (A), alkyl, halogen atom, and alkyl halide are particularly preferred as substituents in the ring structures formed by Ry 1 to Ry 2.

[0255] The ring structure formed by Ry 1 to Ry 2, in particular, is more preferably an aromatic hydrocarbon that can have substituents, from the perspective of the short diffusion of acid produced by exposure and the diffusion control of acid.

[0256] In the aforementioned formula (b0-an0), two or more Rz1 to Rz4 can bond with each other to form a ring structure. For example, Rz1 can form a ring structure with any of Rz2 to Rz4. Specifically, examples include the ring structure of one side of the six-membered ring in the common formula (b0-an0) (the bond between the carbon atoms bonded by Rz1 and Rz2 and the carbon atoms bonded by Rz3 and Rz4), the ring structure formed by the bond between Rz1 and Rz2, and the ring structure formed by the bond between Rz3 and Rz4. The ring structure formed by two or more of Rz 1 to Rz 4 can be an alicyclic hydrocarbon or an aromatic hydrocarbon, preferably an aromatic hydrocarbon. Furthermore, the ring structure can also be a polycyclic structure formed by it and other ring structures.

[0257] Alicyclic hydrocarbons formed from two or more of Rz 1 to Rz 4 can be either polycyclic or monocyclic. Monocyclic alicyclic hydrocarbons are preferably monocyclic alkanes. These monocyclic alkanes preferably have 3 to 6 carbon atoms, specifically cyclopentane, cyclohexane, etc. Polycyclic alicyclic hydrocarbons are preferably polycyclic alkanes. These polycyclic alkanes preferably have 7 to 30 carbon atoms, specifically more preferably polycyclic alkanes with a cross-linked ring system such as adamantane, norcamphene, isocamphene, tricyclodecane, tetracyclododecane, etc.; and polycyclic alkanes with a condensed ring system such as a steroidal skeleton. It can also be a heterocyclic structure in which part of the carbon atom is replaced by a heteroatom, preferably a nitrogen-containing heterocycle, specifically cyclic amides, etc.

[0258] Aromatic hydrocarbon rings formed from two or more of Rz 1 to Rz 4 may include benzene, naphthalene, anthracene, phenanthrene, biphenyl, or aromatic heterocycles in which a portion of the carbon atom constituting such aromatic rings is substituted with a heteroatom. From the viewpoint of compatibility with component (A), aromatic hydrocarbon rings formed from two or more of Rz 1 to Rz 4 are preferably free of heteroatoms; more preferably, they are aromatic rings of benzene, naphthalene, anthracene, phenanthrene, biphenyl, etc.

[0259] The ring structures (alicyclic hydrocarbons and aromatic hydrocarbons) formed by Rz 1 to Rz 4 may also have substituents. The substituents mentioned here can be those identical to the substituents in the ring structures of Rx 1 to Rx 4, Ry 1 to Ry 2, and Rz 1 to Rz 4 (e.g., alkyl, alkoxy, halogen atom, alkyl halide, hydroxyl, nitro, carbonyl, etc.). Among these, from the viewpoint of compatibility with component (A), alkyl, halogen atom, and alkyl halide are particularly preferred as substituents in the ring structures formed by Rz 1 to Rz 4.

[0260] The ring structure formed by two or more of Rz1 to Rz4, from the perspective of diffusion control of the acid generated by exposure, is preferably a ring structure with one side of the six-membered ring in the common formula (b0-an0) (the bond between the carbon atoms bonded by Rz1 and Rz2 and the carbon atoms bonded by Rz3 and Rz4), and more preferably an aromatic ring structure.

[0261] Furthermore, in the aforementioned formula (b0-an0), "when the atomic valence is permissible" refers to the following. That is, when the carbon atoms bonded by Rz1 and Rz2 form single bonds with the carbon atoms bonded by Rz3 and Rz4, all of Rz1, Rz2, Rz3, and Rz4 are present. When the carbon atoms bonded by Rz1 and Rz2 form double bonds with the carbon atoms bonded by Rz3 and Rz4, only one of Rz1 or Rz2 is present, and only one of Rz3 or Rz4 is present. Furthermore, for example, when Rz1 and Rz3 bond to form an aromatic ring structure, Rz2 and Rz4 are not present.

[0262] In the aforementioned equation (b0-an0), two or more Rx1 to Rx4 can be bonded together to form a ring structure. For example, Rx1 can form a ring structure with any of Rx2 to Rx4. The ring structure formed by two or more of Rx1 to Rx4 can be an alicyclic hydrocarbon or an aromatic hydrocarbon. Furthermore, this ring structure can also be a polycyclic structure formed by it and other ring structures.

[0263] Alicyclic hydrocarbons formed from two or more of Rx 1 to Rx 4 can be polycyclic or monocyclic. Monocyclic alicyclic hydrocarbons are preferably monocyclic alkanes. These monocyclic alkanes preferably have 3 to 6 carbon atoms, specifically cyclopentane, cyclohexane, etc. Polycyclic alicyclic hydrocarbons are preferably polycyclic alkanes. These polycyclic alkanes preferably have 7 to 30 carbon atoms, specifically more preferably polycyclic alkanes with a cross-linked ring system such as adamantane, norcamphene, isocamphene, tricyclodecane, tetracyclododecane, etc.; and polycyclic alkanes with a condensed ring system such as a steroidal skeleton.

[0264] The aromatic hydrocarbon rings formed by two of Rx 1 to Rx 4 may include benzene, naphthalene, anthracene, phenanthrene, biphenyl, or aromatic heterocycles in which a portion of the carbon atom constituting such aromatic rings is replaced by a heteroatom. From the viewpoint of compatibility with component (A), the aromatic hydrocarbon rings formed by two of Rx 1 to Rx 4 are preferably free of heteroatoms; more preferably, they are aromatic rings of benzene, naphthalene, anthracene, phenanthrene, biphenyl, etc.

[0265] The ring structures (alicyclic hydrocarbons and aromatic hydrocarbons) formed by Rx 1 to Rx 4 may also have substituents. The substituents mentioned here can be those identical to the substituents in the ring structures of Rx 1 to Rx 4, Ry 1 to Ry 2, and Rz 1 to Rz 4 (e.g., alkyl, alkoxy, halogen atom, alkyl halide, hydroxyl, nitro, carbonyl, etc.). Among these, from the viewpoint of compatibility with component (A), alkyl, halogen atom, and alkyl halide are particularly preferred as substituents in the ring structures formed by Rx 1 to Rx 4.

[0266] A ring structure formed by two or more of Rx1 to Rx4, of which alicyclic hydrocarbons are particularly preferred from the viewpoint of acid diffusion control. Furthermore, the ring structure formed by two or more of Rx 1 to Rx 4, from the viewpoint of acid diffusion control, is preferably a ring structure in which at least one of the aforementioned Rx 1 to Rx 2 is bonded to and cross-linked with at least one of the aforementioned Rx 3 to Rx 4, and more preferably the ring structure is an alicyclic hydrocarbon.

[0267] When at least one of the aforementioned Rx 1 to Rx 2 and at least one of the aforementioned Rx 3 to Rx 4 form a ring structure, the number of carbon atoms in the bicyclic structure (which also includes ring structures in which carbon atoms of Ry 1, Ry 2, Rz 1 and Rz 2, Rz 3 and Rz 4 are bonded to each other) is preferably 7 to 16.

[0268] In the aforementioned formula (b0-an0), two or more of Rx 1 to Rx 4, Ry 1 to Ry 2, or two or more of Rz 1 to Rz 4 are bonded together to form an aromatic ring. This aromatic ring is the same as the aromatic ring described in the above general formula (b0).

[0269] In the aforementioned formula (b0-an0), at least one of Rx 1~Rx 4, Ry 1~Ry 2, and Rz 1~Rz 4 has an anionic group represented by the aforementioned general formula (b0-r-an1), and all anionic portions become n-valent anions. n is an integer greater than or equal to 1. Rx 1~Rx 4, Ry 1~Ry 2, and Rz 1~Rz 4 can each be one of the aforementioned anionic groups. Furthermore, when two or more of Rx 1~Rx 4 are bonded to each other to form a ring structure, the carbon atom forming the ring structure or the hydrogen atom bonded to the carbon atom can also be substituted by the aforementioned anionic group. When two or more of Ry 1~Ry 2 are bonded to each other to form a ring structure, the carbon atom forming the ring structure or the hydrogen atom bonded to the carbon atom can also be substituted by the aforementioned anionic group. When two or more of Rz1 to Rz4 are bonded to each other to form a ring structure, the carbon atom forming the ring structure or the hydrogen atom bonded to the carbon atom can also be substituted by the aforementioned anionic group.

[0270] In the aforementioned formula (b0-r-an1), the divalent linkage in Yb0 is the same as the divalent linkage in Yb0 in the aforementioned general formula (b0). In the aforementioned formula (b0-r-an1), the alkylene group or fluorinated alkylene group in Vb0 is the same as the alkylene group or fluorinated alkylene group in Vb0 in the above general formula (b0).

[0271] Specific examples of the anionic group represented by the aforementioned formula (b0-r-an1) include, for example, when Yb0 is a single bond, fluorinated alkyl sulfonate anions such as trifluoromethanesulfonate anion or perfluorobutanesulfonate anion. When Yb0 is a divalent bonding group containing an oxygen atom, any of the following formulas (b0-r-an11) to (b0-r-an13) can be used to represent the anion.

[0272] [In the formula, Vb” 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. Rb 102 is a fluorine atom or a fluorinated alkyl group with 1 to 5 carbon atoms. vb” is an integer from 0 to 3, and qb” is an integer from 1 to 20, respectively. nb” is 0 or 1].

[0273] In the aforementioned formulas (b0-r-an11) to (b0-r-an13), Vb” 101 is a single bond, an alkyl group having 1 to 4 carbon atoms, or a fluorinated alkyl group having 1 to 4 carbon atoms. Vb” 101 is preferably a single bond, an alkyl group (methylene) having 1 carbon atom, or a fluorinated alkyl group having 1 to 3 carbon atoms.

[0274] In the aforementioned formulas (b0-r-an11) to (b0-r-an13), Rb 102 is a fluorine atom or a fluorinated alkyl group having 1 to 5 carbon atoms. Rb 102 is preferably a perfluoroalkyl group having 1 to 5 carbon atoms or a fluorine atom, and more preferably a fluorine atom.

[0275] In the aforementioned formulas (b0-r-an11)~(b0-r-an13), vb” is an integer from 0 to 3, preferably 0 or 1. "qb" is an integer from 1 to 20, preferably an integer from 1 to 10; even more preferably an integer from 1 to 5; even more preferably 1, 2 or 3; and most preferably 1 or 2. "nb" can be 0 or 1, with 0 being preferable.

[0276] The number of anionic groups in component (B0) can be one or more. (B0) Component, the entire anionic portion is composed of n-valent anions. n is an integer greater than or equal to 1, preferably 1 or 2, and more preferably 1.

[0277] In the aforementioned formula (b0-an0), at least one of Rx 1~Rx 4, Ry 1~Ry 2, and Rz 1~Rz 4 contains a hydrocarbon group having a bromine atom or a hydrocarbon group having an iodine atom. The preferred form of this hydrocarbon group having a bromine atom or a hydrocarbon group having an iodine atom is the same as that described in the above general formula (b0).

[0278] From the viewpoint of acid diffusion inhibition, the anionic portion of component (B0) is preferably represented by the following general formula (b0-an1).

[0279] [In the formula, Rx5~Rx6 represent hydrocarbon groups or hydrogen atoms that may have substituents. Rx7~Rx8 represent hydrocarbon groups or hydrogen atoms that may have substituents, or they may bond together to form a ring structure. p is 1 or 2. When p=2, the multiple Rx7~Rx8 can be different from each other. Ry1~Ry2 represent hydrocarbon groups or hydrogen atoms that may have substituents, or they may bond together to form a ring structure.] It can be a double bond or a single bond. Rz 1 to Rz 4, when the valence allows, can each independently represent a hydrocarbon group or hydrogen atom that may have substituents, or two or more can bond together to form a ring structure. However, two or more of Rx 5 to Rx 6, Rx 7 to Rx 8, Ry 1 to Ry 2, or Rz 1 to Rz 4 are bonded together to form an aromatic ring. Furthermore, at least one of Rx 5 to Rx 8, Ry 1 to Ry 2, and Rz 1 to Rz 4 has an anionic group represented by the following general formula (b0-r-an1), with the entire anionic portion becoming an n-valent anion. Furthermore, at least one of Rx 5 to Rx 8, Ry 1 to Ry 2, and Rz 1 to Rz 4 contains a hydrocarbon group with a bromine atom or a hydrocarbon group with an iodine atom. (n is an integer greater than or equal to 1).

[0280] [In the formula, Yb0 is a divalent linker or a single bond. Vb0 is a single bond, an alkyl group, or a fluorinated alkyl group. * indicates the bonding site].

[0281] In the aforementioned formula (b0-an1), Rx5 to Rx6 each independently represent a hydrocarbon group or hydrogen atom that may have substituents. The hydrocarbon groups that may have substituents in Rx5 to Rx6 are the same as those in Rx1 to Rx4 in the aforementioned formula (b0-an0) for the hydrocarbon groups that may have substituents.

[0282] In the aforementioned formula (b0-an1), Rx 7 to Rx 8 represent hydrocarbon groups or hydrogen atoms that may have substituents, or they may bond together to form a ring structure. The explanation of Rx 7 to Rx 8 is the same as that for Rx 1 to Rx 4 in the aforementioned formula (b0-an0).

[0283] In the aforementioned formula (b0-an1), p is 1 or 2. When p=2, the complex numbers Rx7 to Rx8 can be different from each other. Among the anions represented by the general formula (b0-an1), when p=1, they have a bicyclic heptane ring structure, and when p=2, they have a bicyclic octane ring structure.

[0284] In the aforementioned formula (b0-an1), Ry 1 to Ry 2 independently represent hydrocarbon groups or hydrogen atoms that may have substituents, or they may bond together to form a ring structure. These Ry 1 to Ry 2 are the same as those in the aforementioned formula (b0-an0). Rz 1 to Rz 4, when the atomic valence allows, independently represent hydrocarbon groups or hydrogen atoms that can have substituents, or two or more that can bond together to form a ring structure. These Rz 1 to Rz 4 are the same as Rz 1 to Rz 4 in the above formula (b0-an0).

[0285] In the aforementioned formula (b0-an1), two or more of Rx 5~Rx 6, Rx 7~Rx 8, Ry 1~Ry 2, or Rz 1~Rz 4 are bonded together to form an aromatic ring. This aromatic ring is the same as that described in the above general formula (b0).

[0286] In the aforementioned formula (b0-an1), at least one of Rx 5~Rx 8, Ry 1~Ry 2 and Rz 1~Rz 4 has an anionic group represented by the above formula (b0-r-an1), and all anionic groups become n-valent anions. n is an integer greater than or equal to 1, preferably 1 or 2, and more preferably 1.

[0287] In the aforementioned formula (b0-an1), at least one of Rx 5~Rx 8, Ry 1~Ry 2, and Rz 1~Rz 4 comprises a hydrocarbon group having a bromine atom or a hydrocarbon group having an iodine atom. The preferred form of this hydrocarbon group having a bromine atom or a hydrocarbon group having an iodine atom is the same as the hydrocarbon group having a bromine atom or a hydrocarbon group having an iodine atom described in the above general formula (b0).

[0288] Of the above, the anion portion of component (B0) is preferably the anion represented by p=2 in the aforementioned formula (b0-an1), which is also the anion represented by the following general formula (b0-an2), from the point of view of improving sensitivity and CDU.

[0289] [In the formula, Rx5 to Rx6 each independently represent a hydrocarbon group or hydrogen atom that may have a substituent. A plurality of Rx7 to Rx8 each independently represent a hydrocarbon group or hydrogen atom that may have a substituent, or two or more may bond together to form a ring structure. Ry1 to Ry2 each independently represent a hydrocarbon group or hydrogen atom that may have a substituent, or may bond together to form a ring structure.] It can be a double bond or a single bond. Rz 1 to Rz 4, when the valence allows, can independently represent a hydrocarbon group or hydrogen atom that may have substituents, or two or more can bond together to form a ring structure. However, two or more of Rx 5 to Rx 6, Rx 7 to Rx 8, Ry 1 to Ry 2, or two or more of Rz 1 to Rz 4 are bonded together to form an aromatic ring. Furthermore, at least one of Rx 5 to Rx 8, Ry 1 to Ry 2, and Rz 1 to Rz 4 has an anionic group represented by the following general formula (b0-r-an1), with the entire anionic portion becoming an n-valent anion. Furthermore, at least one of Rx 5 to Rx 8, Ry 1 to Ry 2, and Rz 1 to Rz 4 contains a hydrocarbon group with a bromine atom or a hydrocarbon group with an iodine atom. (n is an integer of 1 or more).

[0290] [In the formula, Yb0 is a divalent linker or a single bond. Vb0 is a single bond, an alkyl group, or a fluorinated alkyl group. * indicates the bonding site].

[0291] In the aforementioned equation (b0-an2), Rx 5~Rx 6, Rx 7~Rx 8, Ry 1~Ry 2, and Rz 1~Rz 4 are the same as Rx 5~Rx 6, Rx 7~Rx 8, Ry 1~Ry 2, and Rz 1~Rz 4 in the aforementioned equation (b0-an1).

[0292] In the aforementioned formula (b0-an2), two or more of Rx 5~Rx 6, two or more of Rx 7~Rx 8, two or more of Ry 1~Ry 2, or two or more of Rz 1~Rz 4 are bonded together to form an aromatic ring. This aromatic ring is the same as that described in the above general formula (b0).

[0293] In the aforementioned formula (b0-an2), at least one of Rx 5~Rx 8, Ry 1~Ry 2 and Rz 1~Rz 4 has an anionic group represented by the above formula (b0-r-an1), and all anionic portions are n-valent anions. n is an integer greater than or equal to 1, preferably 1 or 2, and more preferably 1.

[0294] In the aforementioned formula (b0-an2), at least one of Rx 5~Rx 8, Ry 1~Ry 2, and Rz 1~Rz 4 comprises a hydrocarbon group having a bromine atom or a hydrocarbon group having an iodine atom. The preferred form of this hydrocarbon group having a bromine atom or a hydrocarbon group having an iodine atom is the same as the hydrocarbon group having a bromine atom or a hydrocarbon group having an iodine atom described in the aforementioned general formula (b0).

[0295] In the aforementioned formulas (b0-an0), (b0-an1), and (b0-an2), Ry 1 to Ry 2, through the short diffusion of the acid generated by exposure and the diffusion control of the acid, are preferably bonded to each other to form a ring structure. The formed ring structure is more preferably an aromatic hydrocarbon (aromatic ring, aromatic heterocycle) that can have substituents.

[0296] In the aforementioned formulas (b0-an0), (b0-an1), and (b0-an2), Rz1 to Rz4 are preferably bonded to each other to form a ring structure from the perspective of diffusion control of the acid generated by exposure. The formed ring structure is preferably a ring structure that shares one side of the six-membered ring in the formula (the bond between the carbon atoms bonded to Rz1 and Rz2 and the bond between the carbon atoms bonded to Rz3 and Rz4); more preferably, it is an aromatic hydrocarbon (aromatic ring, aromatic heterocycle) that can have substituents.

[0297] In the aforementioned formulas (b0-an1) and (b0-an2), Rx 7 to Rx 8, through the short diffusion of the acid generated by exposure and the diffusion control of the acid, are preferably bonded to each other to form a ring structure. The formed ring structure is more preferably an aromatic hydrocarbon (aromatic ring, aromatic heterocycle) that can have substituents. In the aforementioned formula (b0-an2), the ring structure formed in Rx 7 to Rx 8 is preferably a ring structure on one side of the six-membered ring in the common formula (the bond between the same carbon atoms bonded by Rx 7 and Rx 8); more preferably, it is an aromatic hydrocarbon (aromatic ring, aromatic heterocycle) that may have substituents.

[0298] For all anions represented by the aforementioned formula (b0-an2), the number of ring structures formed by the bonds between each of Rx 7~Rx 8, Ry 1~Ry 2, and Rz 1~Rz 4 can be 1 or more, preferably 2 or 3.

[0299] In this embodiment, the anion portion of the (B0) component is preferably an anion represented by the following general formula (b0-an3) from the viewpoint of improving sensitivity and CDU.

[0300] [In the formula, Rx5~Rx6 series independently represent hydrocarbon groups or hydrogen atoms that can have substituents.] It can be a double bond or a single bond. Rz 1 to Rz 4, when the valence allows, independently represent a hydrocarbon group or hydrogen atom that can have substituents, or two or more can bond together to form a ring structure. However, at least one of Rx 5 to Rx 6 and Rz 1 to Rz 4 has an anionic group represented by the following general formula (b0-r-an1), with the entire anionic part becoming an n-valent anion. n is an integer of 1 or more. Also, at least one of Rx 5 to Rx 6 and Rz 1 to Rz 4 contains a hydrocarbon group with a bromine atom or a hydrocarbon group with an iodine atom. R 021 is an alkyl, alkoxy, halogen atom, alkyl halide, hydroxyl, carbonyl, or nitro group. n1 is an integer of 1 to 3. n11 is an integer of 0 to 8. R 022 is an alkyl, alkoxy, halogen atom, alkyl halide, hydroxyl, carbonyl, or nitro group. n2 is an integer of 1 to 3. n21 is an integer from 0 to 8. [In the formula, Yb0 is a divalent linker or a single bond. Vb0 is a single bond, an alkyl group, or a fluorinated alkyl group. * indicates the bonding site].

[0301] In the aforementioned equation (b0-an3), Rx 5~Rx 6 and Rz 1~Rz 4 are the same as Rx 5~Rx 6 and Rz 1~Rz 4 in the aforementioned equation (b0-an1).

[0302] In the aforementioned formula (b0-an3), R 021 is an alkyl, alkoxy, halogen atom, alkyl halide, hydroxyl, carbonyl or nitro group. The alkyl group in R 021 is preferably an alkyl group having 1 to 5 carbon atoms; more preferably methyl, ethyl, propyl, n-butyl, or tert-butyl. The alkoxy group in R 021 is preferably an alkoxy group with 1 to 5 carbon atoms; more preferably a methoxy group, an ethoxy group, an n-propoxy group, an iso-propoxy group, an n-butoxy group, or a tert-butoxy group; and even more preferably a methoxy group or an ethoxy group. The halogen atom in R 021 is preferably a fluorine atom. The alkyl halogen in R 021 can be an alkyl group with 1 to 5 carbon atoms, such as methyl, ethyl, propyl, n-butyl, tert-butyl, etc., in which some or all of the hydrogen atoms are replaced by the aforementioned halogen atoms. Among them, R 021 is preferably an alkyl group, a halogen atom, or a halogenated alkyl group, from the viewpoint of compatibility with component (A).

[0303] In the aforementioned formula (b0-an3), n1 is an integer from 1 to 3, preferably 1 or 2, and even more preferably 1. In the aforementioned formula (b0-an3), n11 is an integer from 0 to 8, preferably an integer from 0 to 4; more preferably 0, 1 or 2; and even more preferably 0 or 1.

[0304] In the aforementioned formula (b0-an3), R 022 is an alkyl group, an alkoxy group, a halogen atom, a halogenated alkyl group, a hydroxyl group, a carbonyl group, or a nitro group, and examples of the same type as R 021 can be listed. Among these, from the viewpoint of compatibility with component (A), alkyl groups, halogen atoms, and halogenated alkyl groups are particularly preferred as R 022. In the aforementioned formula (b0-an3), n2 is an integer from 1 to 3, preferably 1 or 2, and especially preferably 1. In the aforementioned formula (b0-an3), n21 is an integer from 0 to 8, preferably an integer from 0 to 4; more preferably 0, 1 or 2; and especially preferably 0 or 1.

[0305] However, in the aforementioned formula (b0-an3), at least one of Rx 5~Rx 6 and Rz 1~Rz 4 has an anionic group represented by the aforementioned formula (b0-r-an1), and all anionic portions become n-valent anions. n is an integer greater than or equal to 1, preferably 1 or 2, and more preferably 1.

[0306] In the aforementioned formula (b0-an3), at least one of Rx 5~Rx 6 and Rz 1~Rz 4 contains the aforementioned hydrocarbon group with a bromine atom or hydrocarbon group with an iodine atom. The preferred form of this hydrocarbon group with a bromine atom or hydrocarbon group with an iodine atom is the same as that of the hydrocarbon group with a bromine atom or hydrocarbon group with an iodine atom described in the aforementioned general formula (b0).

[0307] In the aforementioned formulas (b0-an0), (b0-an1), (b0-an2), and (b0-an3), from the viewpoint of superior effect of the present invention, at least one of the aforementioned Rz1 to Rz4 preferably has an anionic group. When two or more of the aforementioned Rz1 to Rz4 are bonded to each other to form a ring structure, the carbon atom forming the ring structure or the hydrogen atom bonded to the carbon atom can also be replaced by the aforementioned anionic group.

[0308] In the aforementioned formulas (b0-an0), (b0-an1), (b0-an2), and (b0-an3), from the viewpoint of superior effect of the present invention, at least one of the aforementioned Rz1 to Rz4 preferably includes the aforementioned hydrocarbon group having a bromine atom or a hydrocarbon group having an iodine atom. When two or more of the aforementioned Rz1 to Rz4 are bonded to each other to form a ring structure, the hydrogen atoms bonded to the carbon atoms forming the ring structure may also be substituted by the hydrocarbon group having a bromine atom or a hydrocarbon group having an iodine atom.

[0309] The following shows a specific example of the anionic portion of component (B0).

[0310]

[0311]

[0312]

[0313]

[0314] The anionic portion of component (B0) is preferably an anion represented by any one of the chemical formulas (b0-an-1) to (b0-an-18), (b0-an-26), and (b0-an-27) as described above; more preferably an anion represented by any one of the chemical formulas (b0-an-1) to (b0-an-10), (b0-an-26), and (b0-an-27); and even more preferably an anion represented by any one of the chemical formulas (b0-an-1) to (b0-an-9).

[0315] {(B0) component's cationic portion} In the above general formula (b0), M m+ represents an organic cation with a valence of m. Among them, strontium cation and monium cation are particularly preferred. m is an integer greater than or equal to 1.

[0316] A preferred cation portion ((M m+) 1 / m) can be represented by the following general formulas (ca-1) to (ca-3) for organic cations.

[0317] [In the formula, R 201~R 207 each independently represent an aryl, alkyl, or alkenyl group that may have substituents. R 201~R 203 and R 206~R 207 may also bond together with the sulfur atom in the formula to form a ring. R 208~R 209 each independently represent a hydrogen atom or an alkyl group having 1~5 carbon atoms. R 210 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 -SO 2- that may have substituents. L 201 represents -C(=O)- or -C(=O)-O-].

[0318] In the above general formulas (ca-1) to (ca-3), the aryl groups in R 201 to R 207 can be unsubstituted aryl groups with 6 to 20 carbon atoms, preferably phenyl or naphthyl. The alkyl groups in R 201 to R 207 are chain-like or cyclic alkyl groups, preferably having 1 to 30 carbon atoms. The alkenyl group in R 201~R 207 is preferably composed of 2~10 carbon atoms. R 201~R 207 and R 210 may have substituents, for example, alkyl, halogen atom, haloalkyl, carbonyl, cyano, amino, aryl, and groups represented by the following general formulas (ca-r-1)~(ca-r-7).

[0319] [In the formula, R' 201 are respectively 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].

[0320] 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 is usually preferred to be saturated.

[0321] 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 most preferably 6 to 10. However, this number of carbon atoms does not include the number of carbon atoms in the substituents. The aromatic rings possessed by the aromatic hydrocarbon groups in R' 201 can specifically include benzene, naphthalene, anthracene, phenanthrene, biphenyl, or aromatic heterocycles in which a portion of the carbon atoms constituting the aromatic rings are substituted with heteroatoms. Heteroatoms in aromatic heterocycles can include oxygen atoms, sulfur atoms, nitrogen atoms, etc. Specifically, the aromatic hydrocarbon group in R' 201 can be exemplified by groups obtained by removing one hydrogen atom from the aforementioned aromatic ring (aryl: for example, phenyl, naphthyl, etc.), and groups obtained by substituting one hydrogen atom of the aforementioned aromatic ring with an alkyl group (for example, arylalkyl groups such as benzyl, phenethyl, 1-naphthylmethyl, 2-naphthylmethyl, 1-naphthylethyl, 2-naphthylethyl, etc.). The aforementioned alkyl group (the alkyl chain in the arylalkyl group) preferably has 1 to 4 carbon atoms, more preferably 1 to 2 carbon atoms, and particularly preferably 1 carbon atom.

[0322] The cyclic aliphatic hydrocarbon groups in R' 201 can be listed as aliphatic hydrocarbon groups containing rings in their structure. The structure contains a ring of aliphatic hydrocarbon groups, such as alicyclic hydrocarbon groups (derived by removing one hydrogen atom from an aliphatic hydrocarbon ring), alicyclic hydrocarbon groups bonded to the end of a straight or branched aliphatic hydrocarbon group, and alicyclic hydrocarbon groups present in the middle of a straight or branched aliphatic hydrocarbon group. The aforementioned alicyclic hydrocarbon group preferably has 3 to 20 carbon atoms, more preferably 3 to 12. The aforementioned alicyclic hydrocarbon group can be either a polycyclic or monocyclic group. The monocyclic alicyclic hydrocarbon group is preferably a group obtained by removing one or more hydrogen atoms from a monocyclic alkane. The monocyclic alkane preferably has 3 to 6 carbon atoms, specifically cyclopentane, cyclohexane, etc. The polycyclic alicyclic hydrocarbon group is preferably a group obtained by removing one or more hydrogen atoms from a polycyclic alkane, preferably a polycyclic alkane with 7 to 30 carbon atoms. More preferably, the polycyclic alkane is a polycyclic alkane with a cross-linked ring system, such as adamantane, norcamphene, isocamphene, tricyclodecane, tetracyclododecane, etc.; or a polycyclic alkane with a condensed ring system, such as a cyclic group with a steroidal skeleton.

[0323] Among them, the cyclic aliphatic hydrocarbon group in R' 201 is preferably a group obtained by removing one or more hydrogen atoms from a monocyclic alkane or polycyclic alkane; more preferably a group obtained by removing one hydrogen atom from a polycyclic alkane; particularly preferably adamantyl or norbornel; and most preferably adamantyl.

[0324] The aliphatic hydrocarbon group, which can be bonded to a straight-chain or branched-chain alicyclic hydrocarbon group, preferably has 1 to 10 carbon atoms, more preferably 1 to 6 carbon atoms, even more preferably 1 to 4 carbon atoms, and most preferably 1 to 3 carbon atoms. The linear aliphatic hydrocarbon group is preferred to be a linear alkyl group. Specifically, examples include methylene [-CH 2-], ethyl [-(CH 2) 2-], trimethylene [-(CH 2) 3-], tetramethylene [-(CH 2) 4-], pentamethylene [-(CH 2) 5-], etc. Branched aliphatic hydrocarbon groups, preferably branched alkyl groups, specifically -CH(CH3)-, -CH(CH2CH3)-, etc. -C(CH 3) 2-, -C(CH 3)(CH 2CH 3)-, -C(CH 3)(CH 2CH 2CH 3)-, -C(CH2CH3)2- and other alkylmethylene groups; -CH(CH3)CH2-, -CH(CH 3)CH(CH 3)-, -C(CH 3) 2CH 2-, -CH(CH 2CH 3)CH 2-, -C(CH 2CH 3) 2-CH 2- and other alkyl ethyl groups; -CH(CH 3)CH 2CH 2-, -CH2CH(CH3)CH2- and other alkyltrimethylene groups; Alkyl tetramethylene, alkyl alkyl groups, etc., such as -CH(CH 3)CH 2CH 2CH 2- and -CH 2CH(CH 3)CH 2CH 2-. The alkyl group in the alkyl alkyl group is preferably a straight-chain alkyl group with 1 to 5 carbon atoms.

[0325] Furthermore, the cyclic hydrocarbon groups in R' 201 can also contain heteroatoms, just like heterocycles. Specifically, examples include the cyclic groups containing lactones represented by the aforementioned general formulas (a2-r-1) to (a2-r-7), the cyclic groups containing -SO 2- represented by the aforementioned general formulas (b5-r-1) to (b5-r-4), and the other heterocyclic groups represented by the aforementioned chemical formulas (r-hr-1) to (r-hr-16).

[0326] Substituents in the cyclic group of R'201 can include, for example, alkyl, alkoxy, halogen atom, haloalkyl, hydroxy, carbonyl, nitro, etc. The alkyl group used as a substituent is preferably an alkyl group having 1 to 5 carbon atoms; most preferably methyl, ethyl, propyl, n-butyl, or tert-butyl. The alkoxy group used as a substituent is preferably an alkoxy group with 1 to 5 carbon atoms; more preferably methoxy, ethoxy, n-propoxy, iso-propoxy, n-butoxy, or tert-butoxy; and most preferably methoxy or ethoxy. The halogen atom used as a substituent is preferably a fluorine atom. As a substituent, a halogenated alkyl group can be listed as an alkyl group with 1 to 5 carbon atoms, such as methyl, ethyl, propyl, n-butyl, tert-butyl, etc., in which some or all of the hydrogen atoms are replaced by the aforementioned halogen atoms. The carbonyl group, as a substituent, is a methylene (-CH 2-) group that replaces the hydrocarbon group that forms a ring.

[0327] Alkyl groups that may have substituents: R' 201 is a chain alkyl group, which may be either straight-chain or branched-chain. The alkyl group is linear, preferably having 1 to 20 carbon atoms, more preferably 1 to 15 carbon atoms, and most preferably 1 to 10 carbon atoms. Branched alkyl groups are preferably composed of 3 to 20 carbon atoms, more preferably 3 to 15 carbon atoms, and most preferably 3 to 10 carbon atoms. Specifically, examples include 1-methylethyl, 1-methylpropyl, 2-methylpropyl, 1-methylbutyl, 2-methylbutyl, 3-methylbutyl, 1-ethylbutyl, 2-ethylbutyl, 1-methylpentyl, 2-methylpentyl, 3-methylpentyl, 4-methylpentyl, etc.

[0328] Alkenyl groups that may have substituents in a chain: The chain-like alkenyl group of R' 201 can be either straight-chain or branched-chain, preferably with 2 to 10 carbon atoms, more preferably with 2 to 5 carbon atoms, even more preferably with 2 to 4 carbon atoms, and most preferably with 3 carbon atoms. Examples of straight-chain alkenyl groups include vinyl, allyl, and butenyl. Examples of branched-chain alkenyl groups include 1-methylvinyl, 2-methylvinyl, 1-methylpropenyl, and 2-methylpropenyl. The alkenyl group is chain-like, preferably linear; more preferably vinyl or propenyl; and especially preferably vinyl.

[0329] Substituents in the chain-like alkyl or alkenyl groups of R' 201 may include, for example, alkoxy groups, halogen atoms, alkyl halides, hydroxyl groups, carbonyl groups, nitro groups, amino groups, and cyclic groups in R' 201.

[0330] 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 that are the same as the acid-dissociable groups represented by the above formula (a1-r-2) may also be listed as cyclic groups with substituents or chain alkyl groups with substituents.

[0331] R' 201 is preferably a cyclic group that may have substituents, and more preferably a cyclic hydrocarbon group that may have substituents. More specifically, for example, it is preferably a phenyl, naphthyl, or a group obtained by removing one or more hydrogen atoms from a polycyclic alkane; a cyclic group containing a lactone represented by the aforementioned general formulas (a2-r-1) to (a2-r-7); or a cyclic group containing -SO 2- represented by the aforementioned general formulas (b5-r-1) to (b5-r-4), etc.

[0332] In the above general formulas (ca-1) to (ca-3), when R 201 to R 203 and R 206 to R 207 are bonded to each other to form a ring together with the sulfur atom in the formula, they can also be bonded through heteroatoms such as sulfur atoms, oxygen atoms, and nitrogen atoms, or functional groups such as carbonyl, -SO-, -SO 2-, -SO 3-, -COO-, -CONH-, or -N(RN)- (where RN is an alkyl group with 1 to 5 carbon atoms). As for the ring formed, its ring skeleton includes one ring containing the sulfur atom in the formula, and the sulfur-containing ring is preferably a 3 to 10-membered ring, and more preferably a 5 to 7-membered ring. Specific examples of the rings formed include thiophene rings, thiazole rings, benzothiophene rings, dibenzothiophene rings, 9H-thioxanthium rings, thioxanone rings, thioxanthium rings, phenoxanthium rings, tetrahydrothiophenonium rings, and tetrahydrothiopyranonium rings.

[0333] R 208~R 209 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 they are alkyl groups, they can also bond together to form a ring.

[0334] R 210 can be an aryl group, an alkyl group, an alkenyl group, or a cyclic group containing SO 2- that may have a substituent. The aryl group in R 210 can be any unsubstituted aryl group with 6 to 20 carbon atoms, preferably phenyl or naphthyl. The alkyl group in R 210 is a chain or cyclic alkyl group, preferably having 1 to 30 carbon atoms. The alkenyl group in R 210 is preferably composed of 2 to 10 carbon atoms. In R 210, a cyclic group containing SO 2- with substituents may be used, preferably a "polycyclic group containing -SO 2-", and more preferably a group represented by the above general formula (b5-r-1).

[0335] The suitable cations represented by the aforementioned formula (ca-1) can be specifically listed as those represented by the following chemical formulas (ca-1-1) to (ca-1-113).

[0336] [] []

[0337] [] []

[0338] [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].

[0339] [] []

[0340] [] []

[0341] [] [In the formula, R” 201 is a hydrogen atom or a substituent, which is the same as those listed as substituents that R 201~R 207 and R 210~R 212 may have.]

[0342]

[0343] [] []

[0344]

[0345] Suitable cations represented by the aforementioned formula (ca-2) include, specifically, diphenyl monazine cations, bis(4-tert-butylphenyl)monazine cations, etc.

[0346] The suitable cations represented by the aforementioned formula (ca-3) can be specifically listed as those represented by the following formulas (ca-3-1) to (ca-3-6).

[0347]

[0348] Of the above, the cation portion ((M m+) 1 / m) is preferably a cation represented by the general formula (ca-1). Furthermore, from the viewpoint of improving the decomposability of the cation, in the cation represented by the preferred general formula (ca-1), R 201 to R 203 are each independently aryl groups that can have substituents, and as such substituents, they have at least one electron-attracting group; or R 201 to R 203 are each independently aryl groups that can have substituents, and any two of R 201 to R 203 are bonded to each other to form a ring together with the sulfur atom in the formula; in the cation represented by the even more preferred general formula (ca-1), R 201 to R 203 are each independently aryl groups that can have substituents, and as such substituents, they have at least one electron-attracting group.

[0349] The electron-attracting group can be one type or two or more types. Furthermore, the electron-attracting group can be a monovalent electron-attracting group or a divalent electron-attracting group. Electron-attracting groups can specifically include acetyl, halogen atom, alkyl halide, alkoxy halide, aryloxy halide, alkylamino halide, alkylthio halide, cyano, nitro, dialkylphosphinyl, diarylphosphinyl, alkylsulfonyl, cycloalkylsulfonyl, arylsulfonyl, sulfonoxy, acethio, aminesulfonyl, thiocyanate, and thiocarbonyl groups. From the viewpoint of high sensitivity, the electron-attracting group is preferably a fluorine atom, a fluorinated alkyl group, or a cycloalkylsulfonyl group; more preferably a fluorine atom or a cycloalkylsulfonyl group; and even more preferably a fluorine atom.

[0350] The cation portion ((M m+) 1 / m) is preferably a cation represented by any one of the above chemical formulas (ca-1-65) to (ca-1-67), (ca-1-70), or (ca-1-94) to (ca-1-106); more preferably a cation represented by any one of the above chemical formulas (ca-1-67), (ca-1-70), or (ca-1-103); and even more preferably a cation represented by the above chemical formula (ca-1-103).

[0351] In the inhibitor composition of this embodiment, component (B0) is preferably a compound represented by the following general formula (b0-1).

[0352] [In the formula, Rx1 to Rx4 each independently represent a hydrocarbon group or hydrogen atom that may have substituents, or two or more of them may bond together to form a ring structure. Ry1 to Ry2 each independently represent a hydrocarbon group or hydrogen atom that may have substituents, or they may bond together to form a ring structure.] It can be a double bond or a single bond. Rz 1 to Rz 4, when the valence allows, can independently represent a hydrocarbon group or hydrogen atom that may have substituents, or two or more can bond together to form a ring structure. However, at least one of two or more Rx 1 to Rx 4, Ry 1 to Ry 2, or at least one of two or more Rz 1 to Rz 4 can bond together to form an aromatic ring. Furthermore, at least one of Rx 1 to Rx 4, Ry 1 to Ry 2, and Rz 1 to Rz 4 has an anionic group represented by the following general formula (b0-r-an1), with the entire anionic portion becoming an n-valent anion. Furthermore, at least one of Rx 1 to Rx 4, Ry 1 to Ry 2, and Rz 1 to Rz 4 contains a hydrocarbon group with a bromine atom or a hydrocarbon group with an iodine atom. n is an integer greater than or equal to 1. m is an integer greater than or equal to 1, and M m+ represents an organic cation with a valence of m.

[0353] [In the formula, Yb0 is a divalent linker or a single bond. Vb0 is a single bond, an alkyl group, or a fluorinated alkyl group. R0 is a fluorinated alkyl group or a fluorine atom with 1 to 5 carbon atoms. * indicates the bonding site].

[0354] The anionic portion of the compound represented by the above general formula (b0-1) is the same as the anion represented by the above general formula (b0-an0). The cationic portion of the compound represented by the above general formula (b0-1) is the same as the cationic portion of the compound represented by the above general formula (b0). Preferably, the cationic portion is represented by the general formula (ca-1). Furthermore, from the viewpoint of improving the decomposability of the cation, in the cation represented by the preferred general formula (ca-1), R 201 to R 203 are each independently aryl groups that can have substituents, and as such substituents, they have at least one electron-attracting group; or R 201 to R 203 are each independently aryl groups that can have substituents, and any two of R 201 to R 203 are bonded to each other to form a ring together with the sulfur atom in the formula; in the cation represented by the even more preferred general formula (ca-1), R 201 to R 203 are each independently aryl groups that can have substituents, and as such substituents, they have at least one electron-attracting group.

[0355] Specific examples of (B0) components are listed below, but are not limited to these.

[0356]

[0357]

[0358] In the inhibitor composition of this embodiment, component (B0) can be used alone or in combination with two or more components. In the inhibitor composition of this embodiment, the content of component (B0) relative to 100 parts by mass of component (A) is preferably 5 to 60 parts by mass, more preferably 10 to 55 parts by mass, even more preferably 15 to 50 parts by mass, and particularly preferably 20 to 45 parts by mass. If the content of component (B0) is above the lower limit of the aforementioned preferred range, the lithography properties such as sensitivity, resolution, CDU, LWR (linewidth roughness), and shape will be further improved during resist pattern formation. On the other hand, if it is below the upper limit of the preferred range, a homogeneous solution can be easily obtained when the components of the resist composition are dissolved in an organic solvent, and the storage stability of the resist composition is further improved.

[0359] 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. Alternatively, it can be 100% by mass.

[0360] The (B) component in the inhibitor composition of this embodiment may also contain an acid generating agent component (B1) other than the above-mentioned (B0) component (hereinafter also referred to as "(B1) component").

[0361] ≪(B1) component≫ (B1) The ingredients may include onium salt acid generators such as monazite or strontium salts; 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 others.

[0362] Onium salt acid generators, for example, include compounds represented by the following general formula (b-1) (hereinafter also referred to as "(b-1) component"), compounds represented by the general formula (b-2) (hereinafter also referred to as "(b-2) component") or compounds represented by the general formula (b-3) (hereinafter also referred to as "(b-3) component").

[0363] [In the formula, R101 and R104~R108 are independently cyclic groups that can have substituents, chain-like alkyl groups that can have substituents, or chain-like alkenyl groups that can have substituents, respectively. R104 and R105 can 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 independently single bonds, alkyl groups, or fluorinated alkyl groups, respectively. L101~L102 are independently single bonds or oxygen atoms, respectively. L103~L105 are independently single bonds, -CO-, or -SO2-, respectively. m is an integer greater than or equal to 1, and M'm+ is an onium cation with an m valence.]

[0364] {Anion Section} ･(b-1) Anions in the composition In formula (b-1), R 101 is a cyclic group that may have substituents, a chain alkyl group that may have substituents, or a chain alkenyl group that may have substituents.

[0365] 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 is usually preferred to be saturated.

[0366] The aromatic hydrocarbon group in R 101 is a hydrocarbon group having an aromatic ring. The number of carbon atoms in this aromatic hydrocarbon group is preferably 3 to 30, more preferably 5 to 30, even more preferably 5 to 20, particularly preferably 6 to 15, and most preferably 6 to 10. However, this number of carbon atoms does not include the number of carbon atoms in the substituents. The aromatic rings possessed by the aromatic hydrocarbon groups in R 101 can specifically include those of benzene, naphthalene, anthracene, phenanthrene, biphenyl, or aromatic heterocycles in which a portion of the carbon atom constituting the aromatic ring is substituted with a heteroatom. Heteroatoms in aromatic heterocycles can include oxygen atoms, sulfur atoms, nitrogen atoms, etc. Specifically, the aromatic hydrocarbon groups in R 101 can be categorized as groups obtained by removing one hydrogen atom from the aforementioned aromatic ring (aryl: for example, phenyl, naphthyl, etc.), and groups obtained by substituting one hydrogen atom of the aforementioned aromatic ring with an alkyl group (for example, arylalkyl groups such as benzyl, phenethyl, 1-naphthylmethyl, 2-naphthylmethyl, 1-naphthylethyl, 2-naphthylethyl, etc.). The number of carbon atoms in the aforementioned alkyl group (alkyl chain in arylalkyl group) is preferably 1 to 4, more preferably 1 to 2, and particularly preferably 1.

[0367] The cyclic aliphatic hydrocarbon groups in R 101 can be listed as aliphatic hydrocarbon groups whose structures contain rings. The structure contains a ring of aliphatic hydrocarbon groups, such as alicyclic hydrocarbon groups (derived by removing one hydrogen atom from an aliphatic hydrocarbon ring), alicyclic hydrocarbon groups bonded to the end of a straight or branched aliphatic hydrocarbon group, and alicyclic hydrocarbon groups present in the middle of a straight or branched aliphatic hydrocarbon group. The aforementioned alicyclic hydrocarbon group preferably has 3 to 20 carbon atoms, more preferably 3 to 12. The aforementioned alicyclic hydrocarbon group can be either a polycyclic or monocyclic group. The monocyclic alicyclic hydrocarbon group is preferably a group obtained by removing one or more hydrogen atoms from a monocyclic alkane. The monocyclic alkane preferably has 3 to 6 carbon atoms, specifically cyclopentane, cyclohexane, etc. The polycyclic alicyclic hydrocarbon group is preferably a group obtained by removing one or more hydrogen atoms from a polycyclic alkane, preferably a polycyclic alkane with 7 to 30 carbon atoms. More preferably, the polycyclic alkane is a polycyclic alkane with a cross-linked ring system, such as adamantane, norcamphene, isocamphene, tricyclodecane, tetracyclododecane, etc.; or a polycyclic alkane with a condensed ring system, such as a cyclic group with a steroidal skeleton.

[0368] Among them, the cyclic aliphatic hydrocarbon group in R 101 is preferably a group obtained by removing one or more hydrogen atoms from a monocyclic alkane or a polycyclic alkane, more preferably a group obtained by removing one hydrogen atom from a polycyclic alkane; even more preferably adamantyl or norbornel; and especially preferably adamantyl.

[0369] A straight-chain aliphatic hydrocarbon group that can be bonded to an alicyclic hydrocarbon group, preferably having 1 to 10 carbon atoms, more preferably 1 to 6, even more preferably 1 to 4, and most preferably 1 to 3. The straight-chain aliphatic hydrocarbon group is preferably a straight-chain alkyl group, specifically including methylene [-CH 2-], ethyl [-(CH 2) 2-], trimethylene [-(CH 2) 3-], tetramethylene [-(CH 2) 4-], pentamethylene [-(CH 2) 5-], etc. A branched aliphatic hydrocarbon group that can be bonded to an alicyclic hydrocarbon group, preferably having 2 to 10 carbon atoms, more preferably 3 to 6, even more preferably 3 or 4, and most preferably 3. The branched aliphatic hydrocarbon group is preferably a branched alkyl group, specifically, examples include -CH(CH 3)-, -CH(CH 2CH 3)-, and -C(CH 3) 2-. Alkyl methylene groups such as -C(CH 3)(CH 2CH 3)-, -C(CH 3)(CH 2CH 2CH 3)-, and -C(CH 2CH 3) 2-; -CH(CH 3)CH 2-, -CH(CH 3)CH(CH 3)-, Alkyl ethyl groups such as -C(CH 3) 2CH 2-, -CH(CH 2CH 3)CH 2-, and -C(CH 2CH 3) 2-CH 2-; alkyl trimethylene groups such as -CH(CH 3)CH 2CH 2- and -CH 2CH(CH 3)CH 2-; -CH(CH 3)CH 2CH 2CH 2-, Alkyl groups such as -CH2CH(CH3)CH2CH2-, alkyl tetramethylene, and alkyl alkylene groups. The alkyl group in the alkyl alkylene group is preferably a straight-chain alkyl group with 1 to 5 carbon atoms.

[0370] Furthermore, the cyclic hydrocarbon group in R 101 can also contain heteroatoms, similar to heterocycles. Specifically, examples include the lactone-containing cyclic groups represented by the aforementioned general formulas (a2-r-1) to (a2-r-7), the -SO 2- containing cyclic groups represented by the aforementioned general formulas (b5-r-1) to (b5-r-4), and the heterocyclic groups represented by the following chemical formulas (r-hr-1) to (r-hr-16). In the formulas, * indicates the bonding site of Y 101 in formula (b-1).

[0371]

[0372] Substituents in the cyclic group of R 101 can include, for example, alkyl, alkoxy, halogen atom, alkyl halide, hydroxyl, carbonyl, nitro, etc. The alkyl group used as a substituent is preferably an alkyl group having 1 to 5 carbon atoms; most preferably methyl, ethyl, propyl, n-butyl, or tert-butyl. The alkoxy group used as a substituent is preferably an alkoxy group with 1 to 5 carbon atoms; more preferably methoxy, ethoxy, n-propoxy, iso-propoxy, n-butoxy, or tert-butoxy; and most preferably methoxy or ethoxy. Halogen atoms that can be used as substituents include fluorine atoms, chlorine atoms, bromine atoms, iodine atoms, etc., with fluorine atoms being the most preferred. As a substituent, a halogenated alkyl group can be listed as an alkyl group with 1 to 5 carbon atoms, such as methyl, ethyl, propyl, n-butyl, tert-butyl, etc., in which some or all of the hydrogen atoms are replaced by the aforementioned halogen atoms. The carbonyl group, as a substituent, is a methylene (-CH 2-) group that replaces the hydrocarbon group that forms a ring.

[0373] The cyclic hydrocarbon group in R 101 can also be a condensed cyclic group comprising a condensed ring obtained by the condensation of an aliphatic hydrocarbon ring and an aromatic ring. Examples of the aforementioned condensed ring include polycyclic alkanes with a cross-linked ring system, wherein one or more aromatic rings are condensed. Specific examples of the aforementioned cross-linked polycyclic alkanes include bicyclic [2.2.1]heptane (norbornene) and bicyclic [2.2.2]octane. The aforementioned condensed cyclic group is preferably a condensed cyclic group comprising two or three aromatic rings condensed on a bicyclic alkanes, and more preferably a condensed cyclic group comprising two or three aromatic rings condensed on a bicyclic [2.2.2]octane. Specific examples of the condensed cyclic group in R 101 include those represented by the above formulas (r-br-1) to (r-br-2). In this case, * indicates the bonding location of Y 101 in equation (b-1).

[0374] The condensed cyclic group in R 101 may have substituents, such as alkyl, alkoxy, halogen atom, haloalkyl, hydroxyl, carbonyl, nitro, aromatic hydrocarbon group, alicyclic hydrocarbon group, etc. Alkyl, alkoxy, halogen atom, or haloalkyl that are substituents of the aforementioned condensed cyclic group may be the same as those listed as substituents of the cyclic group in R 101 above. Aromatic hydrocarbon groups that serve as substituents for the aforementioned condensed cyclic groups can be categorized as groups obtained by removing one hydrogen atom from the aromatic ring (aryl: for example, phenyl, naphthyl, etc.), groups obtained by substituting one hydrogen atom of the aforementioned aromatic ring with 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. Alicyclic hydrocarbon groups that serve as substituents for the aforementioned condensed cyclic groups can be categorized as: groups obtained by removing one hydrogen atom from monocyclic alkanes such as cyclopentane and cyclohexane; groups obtained by removing one hydrogen atom from polycyclic alkanes such as adamantane, norcamphene, isocamphene, tricyclodecane, and tetracyclododecane; cyclic groups containing lactones represented by the aforementioned general formulas (a2-r-1) to (a2-r-7); cyclic groups containing -SO 2- represented by the aforementioned general formulas (b5-r-1) to (b5-r-4); and heterocyclic groups represented by the aforementioned formulas (r-hr-7) to (r-hr-16), etc.

[0375] Alkyl groups that may have substituents: R 101 can be a chain alkyl group, either straight-chain or branched-chain. The alkyl group is linear, preferably with 1 to 20 carbon atoms, more preferably with 1 to 15 carbon atoms, and most preferably with 1 to 10 carbon atoms. Branched alkyl groups preferably have 3 to 20 carbon atoms, more preferably 3 to 15, and most preferably 3 to 10. Specifically, examples include 1-methylethyl, 1-methylpropyl, 2-methylpropyl, 1-methylbutyl, 2-methylbutyl, 3-methylbutyl, 1-ethylbutyl, 2-ethylbutyl, 1-methylpentyl, 2-methylpentyl, 3-methylpentyl, 4-methylpentyl, etc.

[0376] Alkenyl groups that may have substituents in a chain: The chain-like alkenyl group of R 101 can be either straight-chain or branched-chain, preferably with 2 to 10 carbon atoms, more preferably 2 to 5, even more preferably 2 to 4, and most preferably 3. Examples of straight-chain alkenyl groups include vinyl, allyl, and butenyl. Examples of branched-chain alkenyl groups include 1-methylvinyl, 2-methylvinyl, 1-methylpropenyl, and 2-methylpropenyl. The alkenyl group is chain-like, preferably linear; more preferably vinyl or propenyl; and especially preferably vinyl.

[0377] Substituents in the chain-like alkyl or alkenyl groups of R 101 may include, for example, alkoxy groups, halogen atoms, alkyl halides, hydroxyl groups, carbonyl groups, nitro groups, amino groups, and cyclic groups in R 101.

[0378] Of the above, R 101 is preferably a cyclic group that may have substituents, and more preferably a cyclic hydrocarbon group that may have substituents. More specifically, the cyclic hydrocarbon group is preferably phenyl, naphthyl, or a group obtained by removing one or more hydrogen atoms from a polycyclic alkane; a cyclic group containing lactone represented by the aforementioned general formulas (a2-r-1) to (a2-r-7); a cyclic group containing -SO 2- represented by the aforementioned general formulas (b5-r-1) to (b5-r-4); more preferably a group obtained by removing one or more hydrogen atoms from a polycyclic alkane or a cyclic group containing -SO 2- represented by the aforementioned general formulas (b5-r-1) to (b5-r-4); and even more preferably adamantyl or a cyclic group containing -SO 2- represented by the aforementioned general formula (b5-r-1).

[0379] In formula (b-1), Y 101 is a single bond or a divalent linkage containing an oxygen atom. When Y 101 is a divalent bonding group containing an oxygen atom, Y 101 may also contain atoms other than oxygen atoms. Examples of atoms other than oxygen atoms include carbon atoms, hydrogen atoms, sulfur atoms, nitrogen atoms, etc. Divalent linkages containing oxygen atoms include, for example, non-hydrocarbon oxygen-containing linkages such as oxygen atoms (ether bond: -O-), ester bond (-C(=O)-O-), oxycarbonyl group (-OC(=O)-), amide bond (-C(=O)-NH-), carbonyl group (-C(=O)-), carbonate bond (-OC(=O)-O-), etc.; combinations of these non-hydrocarbon oxygen-containing linkages with alkyl groups, etc. A sulfonyl group (-SO 2-) may also be further linked to this combination. Examples of divalent oxygen-containing linkages include those represented by the general formulas (y-al-1) to (y-al-7). Furthermore, at this time, in the above general formulas (y-al-1) to (y-al-7), the one bonded to R 101 in the above formula (b-1) is V' 101 in the above general formulas (y-al-1) to (y-al-7).

[0380] Y 101 is preferably a divalent linker containing an ester bond or a divalent linker containing an ether bond; more preferably, it is a linker represented by the formulas (y-al-1) to (y-al-5) above.

[0381] In formula (b-1), V 101 is a single bond, an enyl group, or a fluorinated enyl group. Preferably, the enyl group or fluorinated enyl group in V 101 has 1 to 4 carbon atoms. The fluorinated enyl group in V 101 may be a group in which some or all of the hydrogen atoms of the enyl group in V 101 are substituted with fluorine atoms. V 101 is particularly preferably a single bond or a fluorinated enyl group having 1 to 4 carbon atoms.

[0382] In formula (b-1), R 102 is a fluorine atom or a fluorinated alkyl group having 1 to 5 carbon atoms. R 102 is preferably a fluorine atom or a perfluoroalkyl group having 1 to 5 carbon atoms, and more preferably a fluorine atom.

[0383] Specific examples of the anionic part represented by the aforementioned formula (b-1) include, for example, when Y 101 is a single bond, fluorinated alkyl sulfonate anions such as trifluoromethanesulfonate anion or perfluorobutanesulfonate anion.

[0384] ･(b-2) Anions in the composition In formula (b-2), R104 and R105 are respectively cyclic groups that can have substituents, chain alkyl groups that can have substituents, or chain alkenyl groups that can have substituents, and can be listed as the same as R101 in formula (b-1). However, R104 and R105 can also be bonded to each other to form a ring. R 104 and R 105 are preferably chain alkyl groups that may have substituents, more preferably straight-chain or branched-chain alkyl groups, or straight-chain or branched-chain fluorinated alkyl groups. The chain alkyl group preferably has 1 to 10 carbon atoms, more preferably 1 to 7 carbon atoms, and even more preferably 1 to 3 carbon atoms. For the chain alkyl groups of R104 and R105, the smaller the number of carbon atoms within the above-mentioned range, the better, for reasons such as good solubility in solvents used as inhibitors. Furthermore, the more hydrogen atoms replaced by fluorine atoms in the chain alkyl groups of R104 and R105, the stronger the acid, and the better the transparency to high-energy light or electron beams below 250 nm. The proportion of fluorine atoms in the aforementioned chain alkyl group, i.e., the fluorination rate, is preferably 70 to 100%, more preferably 90 to 100%, and most preferably a perfluoroalkyl group in which all hydrogen atoms are replaced by fluorine atoms. In formula (b-2), V 102 and V 103 are independent single bonds, alkyl groups, or fluorinated alkyl groups, respectively, and can be listed as being the same as V 101 in formula (b-1). In equation (b-2), L101 and L102 are either single bonds or oxygen atoms, respectively.

[0385] ･(b-3) Anions in the composition In formula (b-3), R106 to R108 are independently cyclic groups that may have substituents, chain alkyl groups that may have substituents, or chain alkenyl groups that may have substituents, and can be listed as the same as R101 in formula (b-1). In equation (b-3), the L 103 to L 105 series are independently single bonds, -CO-, or -SO 2-.

[0386] Of the above, the anionic portion of component (B) is preferred, and the anionic portion of component (b-1) is even more preferred.

[0387] {Cation Section} In the aforementioned formulas (b-1), (b-2), and (b-3), M'm+ represents an onium cation with a valence of m. Among these, strontium cations and monium cations are particularly preferred. m is an integer greater than or equal to 1.

[0388] A preferred cation portion ((M' m+) 1 / m) can be represented by the organic cations represented by the aforementioned general formulas (ca-1) to (ca-3).

[0389] 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) in the inhibitor composition 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 relative to 100 parts by mass of component (A). By ensuring that the content of component (B1) falls within the aforementioned preferred range, pattern formation is fully achieved. Furthermore, when the components of the inhibitor composition are dissolved in an organic solvent, a homogeneous solution is easily obtained, resulting in good storage stability as an inhibitor composition, which is therefore preferable.

[0390] <Other Ingredients> In addition to components (A) and (B) mentioned above, the inhibitor composition of this embodiment may further contain other components. Examples of other components include components (D), (E), (F), and (S) shown below.

[0391] ≪Alkali component (D)≫ In addition to components (A) and (B), the resist composition of this embodiment preferably further contains an alkaline component (hereinafter also referred to as "component (D)") that captures the acid generated by exposure (i.e. controls the diffusion of acid). Component (D) acts as a quencher (acid diffusion control agent) in the resist composition to capture the acid generated by exposure. (D) Components include, for example, photodisintegrating bases (D1) that lose their acid diffusion control upon exposure and decompose, and nitrogen-containing organic compounds (D2) that are not equivalent to (D1) component (hereinafter referred to as "(D2) component"). Among these, photodisintegrating bases ((D1) component) are particularly preferred because they can easily improve roughness reduction. Furthermore, by containing (D1) component, the characteristics of high sensitivity and suppression of coating defects are easily improved.

[0392] Regarding (D1) ingredients By becoming a resist composition containing (D1), the contrast between the exposed and unexposed areas of the resist film can be further improved when forming a resist pattern. As a component (D1), it is not particularly limited as long as it decomposes by exposure and loses its acid diffusion control. It is more preferably one or more compounds selected from the group consisting of compounds represented by the following general formula (d1-1) (hereinafter referred to as "(d1-1) component"), compounds represented by the following general formula (d1-2) (hereinafter referred to as "(d1-2) component") and compounds represented by the following general formula (d1-3) (hereinafter referred to as "(d1-3) component"). The components (d1-1) to (d1-3) lose their acid diffusion control (alkalinity) due to decomposition in the exposed portion of the resist film, and therefore do not act as quenchers. However, they act as quenchers in the unexposed portion of the resist film.

[0393] [In the formula, Rd1~Rd4 are cyclic groups that may have substituents, chain alkyl groups that may have substituents, or chain alkenyl groups that may have substituents. However, in Rd2 of formula (d1-2), there is no fluorine atom bonded to the carbon atom adjacent to the S atom. Yd1 is a single bond or a divalent linked group. m is an integer greater than or equal to 1, and Mm+ are organic cations with an independent valence of m].

[0394] {(d1-1)Component} ...Anion section In formula (d1-1), Rd1 can be a cyclic group that may have substituents, a chain alkyl group that may have substituents, or a chain alkenyl group that may have substituents, and examples can be the same as R'201 mentioned above. Of these, Rd 1 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. Substituents that may be present in these groups include hydroxyl, side oxygen, alkyl, aryl, fluorine atom, fluorinated alkyl, lactone-containing cyclic groups represented by the above general formulas (a2-r-1) to (a2-r-7), ether bonds, ester bonds, or combinations thereof. When an ether bond or ester bond is included as a substituent, it may also be separated by an alkyl group; in this case, the substituent is preferably a linking group represented by the above formulas (y-al-1) to (y-al-5). Furthermore, when the aromatic hydrocarbon group, aliphatic cyclic group, or chain alkyl group in Rd 1 has the linking group represented by the above general formulas (y-al-1) to (y-al-7) as a substituent, the carbon atom of the aromatic hydrocarbon group, aliphatic cyclic group, or chain alkyl group in Rd 1 in the above general formulas (y-al-1) to (y-al-7) that is bonded to the carbon atom of the aromatic hydrocarbon group, aliphatic cyclic group, or chain alkyl group in the above general formulas (d3-1) to (y-al-7) is V' 101. The aforementioned aromatic hydrocarbon groups can be categorized as phenyl, naphthyl, and polycyclic structures containing a bicyclooctane skeleton (polycyclic structures composed of a bicyclooctane skeleton and other ring structures). The aforementioned aliphatic cyclic group is more preferably a group obtained by removing one or more hydrogen atoms from polycyclic alkanes such as adamantane, norcamphene, isocamphene, tricyclodecane, and tetracyclododecane. The aforementioned chain-like alkyl group preferably has 1 to 10 carbon atoms. Specifically, 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.

[0395] When the aforementioned chain-like alkyl group is a fluorinated alkyl group having fluorine atoms or fluorinated alkyl groups as substituents, 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.

[0396] The following shows a preferred example of the anionic portion of component (d1-1).

[0397]

[0398] ･･Cation section In formula (d1-1), M m+ is an organic cation with a valence of m. The organic cation of M m+ can be the same as the cations represented by the aforementioned general formulas (ca-1) to (ca-3), more preferably the cations represented by the aforementioned general formula (ca-1), and even more preferably the cations represented by the aforementioned formulas (ca-1-1) to (ca-1-113). (d1-1) ingredient, can be used alone or in combination of two or more.

[0399] {(d1-2)Component} ...Anion section In formula (d1-2), Rd2 is a cyclic group that may have substituents, a chain alkyl group that may have substituents, or a chain alkenyl group that may have substituents, and examples can be the same as R'201 mentioned above. However, in Rd2, the carbon atom adjacent to the S atom is not bonded with a fluorine atom (it is not fluorine-substituted). As a result, the anion of the (d1-2) component becomes a moderately weak acid anion, which enhances the quenching ability of the (D) component. Rd2 is preferably a chain alkyl group that may have substituents, or an aliphatic cyclic group that may have substituents, more preferably an aliphatic cyclic group that may have substituents.

[0400] The chain-like alkyl group is preferably composed of 1 to 10 carbon atoms, more preferably 3 to 10. The aliphatic cyclic group is preferably a group obtained by removing one or more hydrogen atoms from adamantane, norcamphene, isocamphene, tricyclodecane, tetracyclododecane, etc. (which may have substituents); or a group obtained by removing one or more hydrogen atoms from camphor.

[0401] The hydrocarbon group of Rd 2 may also have substituents, which may be the same as those that may be present in the hydrocarbon group (aromatic hydrocarbon group, aliphatic cyclic group, chain alkyl group) of Rd 1 in the aforementioned formula (d1-1).

[0402] Of the components (d1-2), the anionic portion is preferably camphor sulfonic acid anion.

[0403] The following shows a preferred specific example of the anionic portion of component (d1-2).

[0404]

[0405] ･･Cation section In formula (d1-2), M m+ is an organic cation with an m valence, which is the same as M m+ in the aforementioned formula (d1-1). (d1-2) Components can be used alone or in combination of two or more.

[0406] {(d1-3)Component} ...Anion section In formulas (d1-3), Rd3 can be a cyclic group with substituents, a chain alkyl group with substituents, or a chain alkenyl group with substituents. Examples include those identical to R'201 mentioned above. Preferably, it is a cyclic group containing fluorine atoms, a chain alkyl group, or a chain alkenyl group. It is particularly preferred to be a fluorinated alkyl group, and even more preferably, it is the same as the fluorinated alkyl group of Rd1 mentioned above.

[0407] In formula (d1-3), Rd4 is a cyclic group that may have substituents, a chain alkyl group that may have substituents, or a chain alkenyl group that may have substituents, and examples can be the same as R'201 mentioned above. Preferably, the alkyl, alkoxy, alkenyl, or cyclic groups may have substituents. The alkyl group in Rd 4 is preferably a straight-chain or branched alkyl group having 1 to 5 carbon atoms. Specifically, examples include methyl, ethyl, propyl, isopropyl, n-butyl, isobutyl, tert-butyl, pentyl, isopentyl, neopentyl, etc. A portion of the hydrogen atom in the alkyl group of Rd 4 may also be substituted with hydroxyl, cyano, etc. The alkoxy group in Rd 4 is preferably an alkoxy group with 1 to 5 carbon atoms. Specifically, examples of alkoxy groups with 1 to 5 carbon atoms include methoxy, ethoxy, n-propoxy, iso-propoxy, n-butoxy, and tert-butoxy. Among these, methoxy and ethoxy are particularly preferred.

[0408] The alkenyl group in Rd 4 can be the same as that in R' 201 mentioned above, preferably vinyl, propenyl (allyl), 1-methylpropenyl, or 2-methylpropenyl. These groups may further have an alkyl group with 1 to 5 carbon atoms or a haloalkyl group with 1 to 5 carbon atoms as a substituent.

[0409] The cyclic group in Rd 4 can be the same as that in R' 201 mentioned above, preferably an alicyclic group obtained by removing one or more hydrogen atoms from cycloalkanes such as cyclopentane, cyclohexane, adamantane, norcamphene, isocamphene, tricyclodecane, and tetracyclododecane, or an aromatic group such as phenyl or naphthyl. When Rd 4 is an alicyclic group, the resist composition dissolves well in organic solvents, thereby improving its lithography properties. Furthermore, when Rd 4 is an aromatic group, the resist composition exhibits excellent light absorption efficiency in lithography using EUV or other light sources, resulting in good sensitivity and lithography properties.

[0410] In equation (d1-3), Yd1 is a single bond or a divalent linker. The divalent linking group in Yd 1 is not particularly limited and can include divalent hydrocarbon groups (aliphatic hydrocarbon groups, aromatic hydrocarbon groups) that can have substituents, divalent linking groups containing heteroatoms, etc. These can be the same as the divalent hydrocarbon groups that can have substituents and divalent linking groups containing heteroatoms listed in the description of the divalent linking group in Ya 21 of the above formula (a2-1). Yd1 is preferably a carbonyl group, an ester bond, an amide bond, an enyl group, or a combination thereof. The enyl group is more preferably a straight-chain or branched enyl group, and even more preferably a methylene or enyl ethyl group.

[0411] The following shows a preferred specific example of the anionic portion of the (d1-3) components.

[0412]

[0413]

[0414] ･･Cation section In formula (d1-3), M m+ is an organic cation with an m valence, which is the same as M m+ in the aforementioned formula (d1-1). (d1-3) Components can be used alone or in combination of two or more.

[0415] (D1) Component can be any one of the above-mentioned components (d1-1) to (d1-3) or a combination of two or more. When the inhibitor composition contains component (D1), the content of component (D1) in the inhibitor composition is preferably 0.5 to 20 parts by mass, more preferably 1 to 15 parts by mass, and even more preferably 3 to 10 parts by mass relative to 100 parts by mass of component (A1). If the content of component (D1) is above the lower limit of the optimal value, it is easy to obtain particularly good lithography properties and resist pattern shape. On the other hand, if it is below the upper limit value, sensitivity can be well maintained and flux is also excellent.

[0416] In the inhibitor composition of this embodiment, component (D1) preferably contains the above-mentioned component (d1-1). In the inhibitor composition of this embodiment, the content of component (d1-1) is preferably 50% by mass or more, more preferably 70% by mass or more, and even more preferably 90% by mass or more. Component (D) may also be composed solely of compound (d1-1).

[0417] (D1) Manufacturing method of component: The manufacturing methods of the aforementioned components (d1-1) and (d1-2) are not particularly limited and can be manufactured by known methods. Furthermore, the manufacturing method of components (d1-3) is not particularly limited, for example, it is manufactured in the same way as the method described in US 2012-0149916.

[0418] Regarding (D2) ingredients As component (D), it may also contain nitrogen-containing organic compounds that are not equivalent to component (D1) above (hereinafter referred to as "component (D2)"). As for component (D2), it is not particularly limited as long as it acts as an acid diffusion control agent and is not equivalent to component (D1), and can be used freely from those known to the public. Aliphatic amines are particularly preferred, especially secondary or tertiary aliphatic amines. Aliphatic amines refer to amines having one or more aliphatic groups, preferably having 1 to 12 carbon atoms. Aliphatic amines can be categorized as amines (alkylamines or alkylolamines) or cyclic amines obtained by substituting at least one hydrogen atom of ammonia NH 3 with an alkyl or hydroxyalkyl group having 12 or fewer carbon atoms. Specific examples of alkylamines and alkylolamines include monoalkylamines such as n-hexylamine, n-heptylamine, n-octylamine, n-nonylamine, and n-decylamine; dialkylamines such as diethylamine, di-n-propylamine, di-n-heptylamine, di-n-octylamine, and dicyclohexylamine; trialkylamines such as trimethylamine, triethylamine, tri-n-propylamine, tri-n-butylamine, tri-n-pentylamine, tri-n-hexylamine, tri-n-heptylamine, tri-n-octylamine, tri-n-nonylamine, tri-n-decylamine, and tri-n-dodecylamine; and alkylolamines such as diethanolamine, triethanolamine, diisopropanolamine, triisopropanolamine, di-n-octanolamine, and tri-n-octanolamine. Of these, trialkylamines with 5 to 10 carbon atoms are particularly preferred, especially tri-n-pentylamine or tri-n-octylamine.

[0419] Cyclic amines, for example, include heterocyclic compounds containing a nitrogen atom as a heteroatom. These heterocyclic compounds can be monocyclic (aliphatic monocyclic amines) or polycyclic (aliphatic polycyclic amines). Aliphatic monocyclic amines, specifically, include piperidine, piperazine, etc. Aliphatic polycyclic amines, preferably those with 6 to 10 carbon atoms, include, for example, 1,5-diazabicyclo[4.3.0]-5-nonene, 1,8-diazabicyclo[5.4.0]-7-undecene, hexamethylenetetramine, and 1,4-diazabicyclo[2.2.2]octane.

[0420] Other aliphatic amines include triethanolamine (2-methoxymethoxyethyl)amine, triethanolamine {2-(2-methoxyethoxy)ethyl}amine, triethanolamine {2-(2-methoxyethoxymethoxy)ethyl}amine, triethanolamine {2-(1-methoxyethoxy)ethyl}amine, triethanolamine {2-(1-ethoxyethoxy)ethyl}amine, triethanolamine {2-(1-ethoxypropoxy)ethyl}amine, triethanolamine [2-{2-(2-hydroxyethoxy)ethoxy}ethyl]amine, triethanolamine triacetate, etc.; triethanolamine triacetate is preferred.

[0421] Also, for component (D2), aromatic amines can be used. 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.

[0422] Of the above, (D2) component is preferably alkylamine, and more preferably trialkylamine with 5 to 10 carbon atoms.

[0423] (D2) ingredient can be used alone or in combination with two or more ingredients. When the inhibitor composition contains component (D2), the content of component (D2) in the inhibitor composition is preferably 0.01 to 5 parts by mass, more preferably 0.1 to 5 parts by mass, and even more preferably 0.5 to 5 parts by mass relative to 100 parts by mass of component (A1). If the content of component (D2) is above the lower limit of the optimal value, it is easy to obtain particularly good lithography properties and resist pattern shape. On the other hand, if it is below the upper limit value, sensitivity can be well maintained and flux is also excellent.

[0424] ≪Select at least one compound (E) from the group consisting of free organic carboxylic acids and oxyacids of phosphorus and their derivatives≫ In the resist composition of this embodiment, for the purpose of preventing sensitivity degradation, or improving the resist pattern shape and post-exposure stability, at least one compound (E) selected from the group consisting of organic carboxylic acids and phosphorus oxyacids and their derivatives (hereinafter referred to as "(E) component") may be included as an arbitrary component. Organic carboxylic acids, specifically acetic acid, malonic acid, citric acid, malic acid, succinic acid, benzoic acid, and salicylic acid, are among the most preferred. Oxyacids containing phosphorus include phosphoric acid, phosphonic acid, hypophosphoric acid, etc., among which phosphonic acid is particularly good. Derivatives of phosphorus-containing oxyacids, such as esters in which the hydrogen atoms of the aforementioned oxyacids are substituted with hydrocarbon groups, and the aforementioned hydrocarbon groups can be alkyl groups with 1 to 5 carbon atoms, aryl groups with 6 to 15 carbon atoms, etc. Derivatives of phosphoric acid include phosphate esters such as di-n-butyl phosphate and diphenyl phosphate. Phosphonic acid derivatives include dimethyl phosphonate, di-n-butyl phosphonate, phenylphosphonic acid, diphenyl phosphonate, dibenzyl phosphonate, and other phosphonate esters. Derivatives of hypophosphoric acid include hypophosphoric acid esters and phenyl hypophosphoric acid.

[0425] 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, and more preferably 0.05 to 3 parts by mass, relative to 100 parts by mass of component (A). By falling within the above range, the lithography properties will be further improved.

[0426] ≪Fluoride Additive Components (F)≫ The resist composition of this embodiment may also contain a fluorinated additive component (hereinafter referred to as "(F) component") as a hydrophobic resin. The (F) component is used to impart water-repellent properties to the resist film. By using it as a resin different from the (A) component, the lithography properties can be improved. (F) Components, for example, may include fluorinated polymers as described in Japanese Patent Application Publication Nos. 2010-002870, 2010-032994, 2010-277043, 2011-13569, and 2011-128226. As component (F), more specifically, polymers having constituent units (f1) represented by the following general formula (f1-1) can be listed. This polymer is preferably a polymer (homopolymer) composed solely of constituent units (f1) represented by the following formula (f1-1); a copolymer of the constituent unit (f1) with the aforementioned constituent unit (a1); a copolymer of the constituent unit (f1) with a constituent unit derived from acrylic acid or methacrylic acid and the aforementioned constituent unit (a1); more preferably, a copolymer of the constituent unit (f1) with the aforementioned constituent unit (a1). Here, the aforementioned constituent unit (a1) copolymerized with the constituent unit (f1) is preferably a constituent unit derived from 1-ethyl-1-cyclooctyl (meth)acrylate, a constituent unit derived from 1-methyl-1-adamantyl (meth)acrylate; more preferably, a constituent unit derived from 1-ethyl-1-cyclooctyl (meth)acrylate.

[0427] [In the formula, R is the same as above, Rf 102 and Rf 103 represent hydrogen atoms, halogen atoms, alkyl groups with 1 to 5 carbon atoms or alkyl halides with 1 to 5 carbon atoms, respectively. Rf 102 and Rf 103 can be the same or different. nf 1 is an integer from 0 to 5, and Rf 101 is an organic group containing fluorine atoms].

[0428] In formula (f1-1), the R bonded to the carbon atom at the α position is the same as described above. R is preferably a hydrogen atom or a methyl group. In formula (f1-1), the halogen atom in Rf 102 and Rf 103 is preferably a fluorine atom. The alkyl group having 1 to 5 carbon atoms in Rf 102 and Rf 103 can be the same as the alkyl group having 1 to 5 carbon atoms in R mentioned above, preferably methyl or ethyl. Specifically, the alkyl halide having 1 to 5 carbon atoms in Rf 102 and Rf 103 can be a group obtained by substituting some or all of the hydrogen atoms of an alkyl group having 1 to 5 carbon atoms with a halogen atom. This halogen atom is preferably a fluorine atom. Rf 102 and Rf 103 are particularly preferably hydrogen atoms, fluorine atoms, or alkyl groups having 1 to 5 carbon atoms; more preferably hydrogen atoms, fluorine atoms, methyl, or ethyl; and even more preferably hydrogen atoms. In formula (f1-1), nf1 is an integer from 0 to 5, preferably an integer from 0 to 3, and even more preferably 1 or 2.

[0429] In formula (f1-1), Rf 101 is an organic group containing fluorine atoms, preferably a hydrocarbon group containing fluorine atoms. The hydrocarbon group containing fluorine atoms can be any type, such as straight chain, branched chain, or cyclic chain, with a preferred number of carbon atoms of 1 to 20, more preferably 1 to 15, and even more preferably 1 to 10. Furthermore, the hydrocarbon group containing fluorine atoms preferably has more than 25% of the hydrogen atoms in the hydrocarbon group fluorinated, more preferably more than 50%, and especially more than 60% fluorinated, because the hydrophobicity of the resist film is improved during immersion exposure. Among them, Rf 101 is particularly preferred to be a fluorinated hydrocarbon group with 1 to 6 carbon atoms; especially preferred are trifluoromethyl, -CH 2-CF 3, -CH 2-CF 2-CF 3, and -CH(CF 3) 2. -CH 2-CH 2-CF 3, -CH 2-CH 2-CF 2-CF 2-CF 2-CF 3.

[0430] (F) The weight-average molecular weight (Mw) of the component (based on polystyrene conversion by gel permeation chromatography) is preferably 1,000 to 50,000, more preferably 5,000 to 40,000, and most preferably 10,000 to 30,000. If it is below the upper limit of this range, it has sufficient solubility in solvents for use as a resist; if it is above the lower limit of this range, the resist film has good water repellency. (F) The dispersion of the component (Mw / Mn) is preferably 1.0~5.0, more preferably 1.0~3.0, and most preferably 1.0~2.5.

[0431] 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, and more preferably 1 to 10 parts by mass, relative to 100 parts by mass of component (A).

[0432] ≪Organic solvent component (S)≫ The inhibitor composition of this embodiment can be manufactured by dissolving the inhibitor material in an organic solvent component (hereinafter referred to as "(S) component"). As component (S), any solvent that can dissolve all the components used to form a homogeneous solution may be used, and any appropriate solvent may be selected from those known in the past as components of chemically amplifying inhibitors. (S) Components, for example, include lactones such as γ-butyrolactone; ketones such as acetone, methyl ethyl ketone, cyclohexanone, methyl-n-pentyl ketone, methyl isopentyl ketone, and 2-heptanone; polyols such as ethylene glycol, diethylene glycol, propylene glycol, and dipropylene glycol; compounds containing ester bonds such as ethylene glycol monoacetate, diethylene glycol monoacetate, propylene glycol monoacetate, or dipropylene glycol monoacetate; and polyol derivatives such as monoalkyl ethers or monophenyl ethers containing ether bonds of the aforementioned polyols or compounds containing ester bonds, such as monomethyl ethers, monoethyl ethers, monopropyl ethers, monobutyl ethers, etc. [Among these, more...] Preferred organic 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, cresol methyl ether, diphenyl ether, dibenzyl ether, phenethyl ether, butyl phenyl ether, ethylbenzene, diethylbenzene, pentylbenzene, isopropylbenzene, toluene, xylene, isopropyltoluene, mesitylene, etc.; and dimethyl sulfoxide (DMSO). In the inhibitor composition of this embodiment, component (S) can be used alone or as a mixed solvent of two or more components. PGMEA, PGME, γ-butyrolactone, EL, and cyclohexanone are particularly preferred.

[0433] Furthermore, the (S) component is preferably a mixed solvent obtained by mixing PGMEA and a polar solvent. The mixing ratio (mass ratio) can be appropriately determined by taking into account the compatibility of PGMEA and the polar solvent, and is preferably in the range of 1:9 to 9:1, more preferably in the range of 2:8 to 8:2. More specifically, when EL or cyclohexanone is used as a polar solvent, the mass ratio of PGMEA to EL or cyclohexanone is preferably 1:9 to 9:1, more preferably 2:8 to 8:2. Furthermore, when PGME is used as a polar solvent, the mass ratio of PGMEA to PGME is preferably 1:9 to 9:1, more preferably 2:8 to 8:2, and even more preferably 3:7 to 7:3. A mixture of PGMEA, PGME, and cyclohexanone is also preferred. Furthermore, as component (S), the other solvent is preferably a mixture of at least one solvent selected from PGMEA and EL 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, but is appropriately set according to the coating film thickness based on the concentration that can be coated onto the substrate, etc. Generally speaking, component (S) is used in a manner in which the concentration of the solid component of the resist composition is in the range of 0.1 to 20% by mass, preferably in the range of 0.2 to 15% by mass.

[0434] In this embodiment, the resist composition may be further supplemented with appropriate additives that are miscible, such as additive resins, dissolution inhibitors, plasticizers, stabilizers, colorants, anti-halo agents, dyes, etc., to improve the performance of the resist film.

[0435] The inhibitor composition of this embodiment can also be used to remove impurities after dissolving the aforementioned inhibitor material in component (S) and then using a polyimide porous membrane, a polyamide-imide porous membrane, etc. For example, filters made of polyimide porous membranes, filters made of polyamide-imide porous membranes, filters made of both polyimide porous membranes and polyamide-imide 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.

[0436] The inhibitor composition of this embodiment described above contains a compound (B0) represented by the general formula (b0) ((B0) component). The (B0) component has a specific large-volume structure in its anionic portion (a condensed cyclic group obtained by the condensation of aromatic and alicyclic rings). This allows for appropriate control of the diffusion length of acids generated from the (B0) component during exposure. Furthermore, the anionic portion of the (B0) component, due to the presence of bromine or iodine atoms, exhibits enhanced hydrophobicity, thereby improving the uniformity of the (B0) component within the resistive film. Furthermore, the anionic portion of component (B0) contains a hydrocarbon group with a bromine atom or a hydrocarbon group with an iodine atom. Since bromine and iodine atoms have high absorption efficiency for EUV (extreme ultraviolet) and EB (electron beam), they can improve sensitivity to EUV or EB compared to conventional acid generators that do not contain bromine or iodine atoms. Therefore, the inhibitor composition of this embodiment containing (B0) component is presumably able to form an inhibitor pattern that achieves high sensitivity and good CDU.

[0437] (Method for forming inhibitor patterns) The method for forming a resist pattern in the second state of the present invention comprises the steps of forming a resist film on a support using the resist composition of the first state of the present invention, exposing the resist film, and developing the exposed resist film to form a resist pattern. One embodiment of this resist pattern formation method is, for example, a resist pattern formation method performed as follows.

[0438] First, the resist composition of the above embodiment is coated onto a support using a spinner or the like, and then baked (post-coating baking (PAB)) at a temperature of 80 to 150°C for 40 to 120 seconds, preferably 60 to 90 seconds, to form a resist film. Next, the resist film is selectively exposed by an exposure apparatus such as an electron beam drawing apparatus or an ArF exposure apparatus, by exposing it through a mask (mask pattern) with a specific pattern or by drawing it by direct irradiation with an electron beam without using a mask pattern. Then, it is baked (post-exposure baking (PEB)) at a temperature of 80 to 150°C for 40 to 120 seconds, preferably 60 to 90 seconds. Next, the aforementioned resist film is subjected to a development process. In terms of development, an alkaline developer is used in the alkaline development process, while an organic developer (organic developer) is used in the solvent development process.

[0439] After development, it is preferable to perform a rinsing process. For rinsing, it is preferable to use pure water for rinsing during alkaline development processes, and to use a rinsing solution containing organic solvents for solvent development processes. During solvent development, after the aforementioned development or rinsing treatment, the developer or rinsing solution adhering to the pattern can also be removed by supercritical fluid. After development or rinsing, the product is dried. Alternatively, depending on the circumstances, baking (post-baking) may be performed after the aforementioned development process. In this way, a resist pattern can be formed.

[0440] The support is not particularly limited and can use conventionally known materials, such as substrates for electronic components or substrates on which specific wiring patterns are formed. More specifically, substrates made of metals such as silicon wafers, copper, chromium, iron, and aluminum, or glass substrates can be used. The material for the wiring pattern can be, for example, copper, aluminum, nickel, or gold. Furthermore, the support may also be a substrate on which an inorganic and / or organic film is disposed. Inorganic films may include inorganic antireflective films (inorganic BARC). Organic films may include organic antireflective 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 of forming the lower organic film and the upper resist film on a substrate, using the resist pattern formed on the upper resist film as a mask, and then patterning the lower organic film. This method is considered capable of forming patterns with high aspect ratios. In other words, according to the multilayer resist method, the required thickness can be ensured by the lower organic film, thus allowing the resist film to be thinned and forming fine patterns with high aspect ratios. In the multilayer resist method, it is basically divided into a two-layer structure of an upper resist film and a lower organic film (2-layer resist method), and a three-layer or more multilayer structure of having one or more intermediate layers (such as metal thin film) between the upper resist film and the lower organic film (3-layer resist method).

[0441] The wavelength used for exposure is not particularly limited, and radiation such as ArF excimer laser, KrF excimer laser, F2 excimer laser, EUV (extreme ultraviolet), VUV (vacuum ultraviolet), EB (electron beam), X-rays, and soft X-rays can be used. The aforementioned resist composition is highly useful for KrF excimer lasers, ArF excimer lasers, EB, or EUV; even more useful for ArF excimer lasers, EB, or EUV; and exceptionally useful for EB or EUV. That is, the resist pattern forming method of this embodiment is particularly useful when the step of exposing the resist film includes exposing the aforementioned resist film to EUV (extreme ultraviolet) or EB (electron beam).

[0442] The exposure method for the resist film can be either conventional exposure (dry exposure) in an inert gas such as air or nitrogen, or liquid immersion lithography, with liquid immersion lithography being preferred. Immersion exposure is an exposure method in which the space between the resist film and the lens at the lowest position of the exposure device is filled with a solvent (immersion medium) with a refractive index greater than that of air, and exposure is performed under this state (immersion exposure). The preferred immersion medium is a solvent with a refractive index that is greater than that of air and smaller than that of the resist film being exposed. The refractive index of the solvent is not particularly limited as long as it falls within the aforementioned range. Solvents with a refractive index greater than that of air and smaller than that of the aforementioned resist film include, for example, water, fluorine-based inactive liquids, silicon-based solvents, and hydrocarbon-based solvents. Specific examples of fluorine-based inert liquids include liquids with fluorine compounds as the main component, such as C3HCl2F5, C4F9OCH3, C4F9OC2H5, and C5H3F7, preferably with a boiling point of 70-180°C, and more preferably 80-160°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. Fluorine-based inert liquids, particularly perfluoroalkyl compounds in which all hydrogen atoms of the alkyl group are replaced by fluorine atoms. Specifically, perfluoroalkyl compounds include perfluoroalkyl ethers and perfluoroalkylamines. Furthermore, specifically, the aforementioned perfluoroalkyl ether compounds may include perfluoro(2-butyltetrahydrofuran) (boiling point 102°C), and the aforementioned perfluoroalkyl amine compounds may include perfluorotributylamine (boiling point 174°C). From the perspectives of cost, safety, environmental issues, and versatility, water is the preferred choice as a liquid immersion medium.

[0443] Alkaline developing solutions used in alkaline developing processes include, for example, 0.1-10% by mass tetramethylammonium hydroxide (TMAH) aqueous solutions. In solvent-based developing processes, the organic solvents contained in the organic developing solution used for developing can be any solvent capable of dissolving component (A) (the component (A) before exposure), and can be appropriately selected from known organic solvents. Specifically, polar solvents such as ketone solvents, ester solvents, alcohol solvents, nitrile solvents, amide solvents, and ether solvents, as well as hydrocarbon solvents, can be listed. Ketone solvents are organic solvents whose structure contains CC(=O)-C. Ester solvents are organic solvents whose structure contains CC(=O)-OC. Alcohol solvents are organic solvents whose structure contains an alcoholic hydroxyl group. "Alcoholic hydroxyl group" refers to a hydroxyl group bonded to a carbon atom of an aliphatic hydrocarbon group. Nitrile solvents are organic solvents whose structure contains a nitrile group. Acrylamine solvents are organic solvents whose structure contains an acetamine group. Ether solvents are organic solvents whose structure contains COC. Among organic solvents, there are also organic solvents whose structures contain multiple functional groups that impart characteristics to the aforementioned solvents. In this case, they are equivalent to all solvent species that contain the functional groups possessed by the organic solvent. For example, diethylene glycol monomethyl ether is equivalent to any of the alcohol-based solvents and ether-based solvents in the above classification. Hydrocarbon solvents are composed of halogenable hydrocarbons and are hydrocarbon solvents without substituents other than halogen atoms. The halogen atom is preferably a fluorine atom. The organic solvent contained in the organic developer is preferably a polar solvent; more preferably a ketone solvent, ester solvent, or nitrile solvent.

[0444] Examples of ketone solvents include 1-octanone, 2-octanone, 1-nonanone, 2-nonanone, acetone, 4-heptanone, 1-hexanone, 2-hexanone, diisobutyl ketone, cyclohexanone, methylcyclohexanone, phenylacetone, methyl ethyl ketone, methyl isobutyl ketone, acetoacetone, acetone-based acetone, ionone, diacetone alcohol, acetoethanol, acetophenone, methyl naphthyl ketone, isoflavone, propylene carbonate, γ-butyrolactone, and methylpentyl ketone (2-heptanone). Among these, methylpentyl ketone (2-heptanone) is particularly preferred.

[0445] Ester solvents, such as methyl acetate, butyl acetate, ethyl acetate, isopropyl acetate, amyl acetate, isoamyl acetate, ethyl methoxy, ethyl ethoxy, ethylene glycol monoethyl ether acetate, ethylene glycol monopropyl ether acetate, ethylene glycol monobutyl ether acetate, ethylene glycol monophenyl ether acetate, diethylene glycol monomethyl ether acetate, diethylene glycol monopropyl ether acetate, diethylene glycol monophenyl ether acetate, diethylene glycol monobutyl ether acetate, diethylene glycol monoethyl ether acetate, 2-methoxybutyl acetate, 3-methoxybutyl acetate, 4-methoxybutyl acetate, 3-methyl-3-methoxybutyl acetate, 3-ethyl-3-methoxybutyl acetate, propylene glycol monomethyl ether acetate, propylene glycol monoethyl ether acetate, propylene glycol monopropyl ether acetate, 2-ethoxybutyl acetate, 4-ethoxybutyl acetate, and acetic acid. 4-Propoxybutyl ester, 2-Methoxypentyl acetate, 3-Methoxypentyl acetate, 4-Methoxypentyl acetate, 2-Methyl-3-Methoxypentyl acetate, 3-Methyl-3-Methoxypentyl acetate, 3-Methyl-4-Methoxypentyl acetate, 4-Methyl-4-Methoxypentyl acetate, Propylene glycol diacetate, Methyl formate, Ethyl formate, Butyl formate, Propyl formate, Ethyl lactate, Butyl lactate, Propyl lactate Esters, ethyl carbonate, propyl carbonate, butyl carbonate, methyl pyruvate, ethyl pyruvate, propyl pyruvate, butyl pyruvate, methyl acetoacetate, ethyl acetoacetate, methyl propionate, ethyl propionate, propyl propionate, isopropyl propionate, methyl 2-hydroxypropionate, ethyl 2-hydroxypropionate, methyl-3-methoxy propionate, ethyl-3-methoxy propionate, ethyl-3-ethoxy propionate, propyl-3-methoxy propionate, etc. Among these, butyl acetate is particularly preferred as an ester solvent.

[0446] Nitrile solvents, such as acetonitrile, propionitrile, valerate, and butyronitrile, are examples.

[0447] Organic developers may incorporate known additives as needed. Examples of such additives include surfactants. The surfactant is not particularly limited; for example, ionic or nonionic fluorinated and / or silicone surfactants may be used. Preferably, the surfactant is nonionic, more preferably a nonionic fluorinated surfactant, or a nonionic silicone surfactant. When a surfactant is incorporated, the amount incorporated relative to the total amount of the organic developer is usually 0.001 to 5% by mass, preferably 0.005 to 2% by mass, and even more preferably 0.01 to 0.5% by mass.

[0448] 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 certain time (immersion method), the method of allowing the developing solution to rise on the surface of the support due to surface tension and then remain still for a certain time (coating method), the method of spraying the developing solution onto the surface of the support (spraying method), and the method of continuously applying the developing solution to a support rotating at a certain speed while scanning through a nozzle at a certain speed (dynamic coating method), etc.

[0449] The organic solvent contained in the rinsing solution used in the rinsing process after development in the solvent developing process can be, for example, selected from the organic solvents listed above used in organic-based developers, and is 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 selected from hydrocarbon solvents, ketone solvents, ester solvents, alcohol solvents, and amide solvents is preferred; more preferably, at least one selected from alcohol solvents and ester solvents; and most preferably, an alcohol solvent. The alcohol solvent used in the rinsing solution is preferably a monohydric alcohol with 6 to 8 carbon atoms, which can 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 particularly preferred; 1-hexanol and 2-hexanol are even more preferred. These organic solvents can be used alone or in combination of two or more. They can also be mixed with other organic solvents or water. However, considering the developing characteristics, the amount of water in 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 more preferably 5% by mass or less, and particularly preferably 3% by mass or less. The washing solution may be mixed with known additives as needed. Examples of such additives include surfactants. Surfactants may be those similar to those described above, preferably nonionic surfactants, more preferably nonionic fluorinated surfactants, or nonionic silicone surfactants. When surfactants are incorporated, the amount incorporated relative to the total amount of the washing solution is usually 0.001 to 5% by mass, preferably 0.005 to 2% by mass, and even more preferably 0.01 to 0.5% by mass.

[0450] The rinsing treatment (cleaning treatment) using a rinsing solution can be carried out by known rinsing methods. Examples of such rinsing methods include continuously applying rinsing solution to a support rotating at a certain speed (rotation coating), immersing the support in the rinsing solution for a certain period of time (immersion method), and spraying rinsing solution onto the surface of the support (spraying method).

[0451] The resist pattern forming method of this embodiment described above, since it uses the above-mentioned resist composition, can form a resist pattern that achieves high sensitivity and good CDU.

[0452] The resist composition of the above-described embodiments, and the various materials used in the pattern forming method of the above-described embodiments (e.g., resist solvent, developer, rinse solution, composition for forming antireflective film, composition for forming surface coating, etc.), preferably do not contain impurities such as metals, halogen-containing metal salts, acids, alkalis, or components containing sulfur or phosphorus atoms. Here, impurities containing metal atoms may include Na, K, Ca, Fe, Cu, Mn, Mg, Al, Cr, Ni, Zn, Ag, Sn, Pb, Li, or salts of these. The content of impurities in these materials is preferably 200 ppb or less, more preferably 1 ppb or less, even more preferably 100 ppt (parts per trillion) or less, particularly preferably 10 ppt or less, and most preferably substantially free (below the detection limit of the measuring device).

[0453] (compound) The third state of the compound of the present invention is represented by the following general formula (b0).

[0454] [In the formula, Rb0 is a condensed cyclic group obtained by the condensation of an aromatic ring and an alicyclic ring. The alicyclic ring in the aforementioned condensed cyclic group has substituents, and at least one of the substituents contains a hydrocarbon group having an iodine atom. Yb0 is a divalent linked group or a single bond. However, Yb0 is bonded to the alicyclic ring in the aforementioned condensed cyclic group. Vb0 is a single bond, an alkyl group, or a fluorinated alkyl group. R0 is a fluorinated alkyl group or a fluorine atom with 1 to 5 carbon atoms. Mm+ represents an m-valent organic cation. m is an integer greater than or equal to 1].

[0455] The compound represented by the above general formula (b0) is the same as the (B0) component in the inhibitor composition of the first state sample of the present invention.

[0456] [Method for manufacturing compounds represented by general formula (b0)] (B0) component can be manufactured using known methods. As a specific manufacturing method of component (B0), the following shows a method for manufacturing a compound represented by the general formula (b'0) of component (B0).

[0457] First, the compound X1 represented by the following general formula (X-1) is reacted with the desired compound Alc1 represented by the following general formula (Alc-1) having a hydrocarbon group with a bromine atom or a hydrocarbon group with an iodine atom (Rbi) to obtain the compound X2 represented by the following general formula (X-2) (Step 1). Next, compound X2 is reacted with the desired compound I1, which has an anionic group and is represented by the following general formula (I-1), to obtain the precursor Bpre, represented by the following general formula (Bpre) (step 2). Next, by subjecting the precursor Bpre to a salt exchange reaction with compound S1 represented by the following general formula (S-1), a compound represented by the general formula (b'0) of one example of component (B0) can be obtained (step 3). Furthermore, in the following reaction formula, it is conveniently represented as "RbiO-C=O-Rb 00", but "RbiO-C=O-Rb 00" is one example of "Rb 0" in the general formula (b0).

[0458] [In the formula, Rb 00 is a condensed cyclic group obtained by the condensation of an aromatic ring and an alicyclic ring. Yb 001 is a single bond or a divalent linkage. Rbi is a hydrocarbon group with a bromine atom or a hydrocarbon group with an iodine atom. Yb 002 is a single bond or a divalent linkage. Vb 0 is a single bond, an alkyl group, or a fluorinated alkyl group. R 0 is a fluorinated alkyl group or a fluorine atom with 1 to 5 carbon atoms. (M 1” m+) 1 / m is an ammonium cation. Yb' 0 is a divalent linkage. Z - is a non-nucleophilic ion. (M m+) 1 / m represents an organic cation with a valence of m. m is an integer greater than or equal to 1].

[0459] Step 1: Step 1 involves, for example, dissolving compound X1 and compound Alc1 in an organic solvent (THF, etc.) and reacting them in the presence of a base to obtain compound X2.

[0460] Specifically, examples of such bases include sodium hydride, K₂CO₃, Cs₂CO₃, lithium diisopropylamide (LDA), triethylamine, and 4-dimethylaminopyridine. The reaction temperature is, for example, 0~50℃, and the reaction time is, for example, more than 10 minutes and less than 24 hours.

[0461] In the above formula, Rb 00 is a condensed cyclic group obtained by the condensation of an aromatic ring and an alicyclic ring, which is the same as the condensed cyclic group obtained by the condensation of an aromatic ring and an alicyclic ring in Rb 0 in the above general formula (b0).

[0462] In the above formula, Yb 001 is a single bond or a divalent linkage. Examples of divalent linkages include -CO-, -NH-, alkyl groups with -CO-, and alkyl groups with -NH-.

[0463] Step 2: The second step involves, for example, dissolving compound X2 and compound I1 in an organic solvent (such as dichloromethane) and carrying out a condensation reaction in the presence of a base to obtain the precursor Bpre.

[0464] Specifically, the base can be listed as an organic base such as triethylamine, 4-dimethylaminopyridine, pyridine, ethyl diisopropylaminocarbodiimide (EDCI) hydrochloride, dicyclohexylcarboxylimide (DCC), N,N'-diisopropylcarbodiimide, and carbodiimidazole; and an inorganic base such as sodium hydride, K₂CO₃, and Cs₂CO₃.

[0465] In the above formula, Vb 0 and R 0 are the same as Vb 0 and R 0 in the above general formula (b0). In the above formula, Yb 002 is a single bond or a divalent linkage. Examples of divalent linkages include -CO-, -NH-, alkyl groups with -CO-, and alkyl groups with -NH-.

[0466] In the above formula, Yb'0 is a divalent linkage group, specifically, it is a group generated by the reaction of -Yb 001-OH of compound X2 and -Yb 002-OH of compound I1, specifically, it is a -Yb 001-O-Yb 002- group. For example, compound X2 is a carboxylic acid and compound I1 is an alcohol.

[0467] In the above formula, (M 1” m+) 1 / m is an ammonium cation, which can be an ammonium cation derived from aliphatic amines or an ammonium cation derived from aromatic amines.

[0468] The amount of compound I1 used relative to compound X2 is, for example, 0.5 to 3 equivalents. The reaction temperature is, for example, 0~50℃, and the reaction time is, for example, more than 10 minutes and less than 24 hours.

[0469] Step 3: The third step is, for example, reacting the precursor Bpre with the salt exchange compound S1 in a solvent such as water, dichloromethane, acetonitrile or chloroform, thereby exchanging the cations of the precursor Bpre with the cations of the compound S1 to obtain a compound represented by the general formula (b'0) as an example of the (B0) component.

[0470] In the above formula, Z- can be listed as an acid ion that is less acidic than the precursor Bpre. Specifically, it can be listed as a halide ion such as bromide ion and chloride ion; BF4-, AsF6-, SbF6-, PF6-, ClO4-, etc. The reaction temperature is, for example, 0~100℃, and the reaction time is, for example, more than 10 minutes and less than 24 hours.

[0471] In the above formula, (M m+) 1 / m is the same as (M m+) 1 / m in the above general formula (b0).

[0472] After the salt exchange reaction is complete, the compounds in the reaction solution can be isolated and purified. Isolation and purification can be performed using known methods, such as appropriate combinations of concentration, solvent extraction, distillation, crystallization, recrystallization, and chromatography. The structures of the compounds obtained as described above can be identified by general organic analytical methods such as 1H-nuclear magnetic resonance (NMR) spectroscopy, 13C-NMR spectroscopy, 19F-NMR spectroscopy, infrared absorption (IR) spectroscopy, mass spectrometry (MS), elemental analysis, and X-ray crystallization diffraction.

[0473] The raw materials used in each step can be commercially available or synthetic. For example, when synthesizing compound X1, compound X1 can be obtained by reacting an aromatic compound (e.g., anthracene) with an alkene (e.g., maleic anhydride) via a Diels-Alder reaction.

[0474] The compound of the third state of the present invention described above is a compound used as an acid generating agent in the inhibitor composition of the first state of the present invention described above.

[0475] (Acid generating agent) The acid generating agent of the fourth state of the present invention is a compound containing the above-mentioned third state. This acid generator contains an acid generator component for use as a component in chemically amplified resistors. By using this acid generator component in the chemically amplified resistor component, high sensitivity can be achieved during resistor pattern formation, and the CDU is further improved. By using this acid generator component, especially when forming resistor patterns using EB or EUV light sources, high sensitivity can be achieved, and the CDU is further improved. [Example]

[0476] The present invention will be described in more detail below by way of examples, but the present invention is not limited to these examples.

[0477] <The Manufacturing of Compound X1> (Manufacturing Example 1) Anthracene (20.0 g, 112.2 mmol), maleic anhydride (16.6 g, 168.3 mmol), aluminum chloride (1.50 g, 11.2 mmol), and toluene (200 g) were added to a 300 mL three-necked flask and reacted at 80 °C for 4 hours with stirring. After cooling, ultrapure water (155 g) was added, and the mixture was stirred for 30 minutes. The precipitated solid was then filtered. The filtrate was dissolved in a mixed solvent of THF (93 g) and dichloromethane (680 g), washed three times with ultrapure water (155 g), and the organic layer was concentrated using a rotary evaporator. The concentrate was recrystallized with ethyl acetate to give compound (X-1-1).

[0478]

[0479] <The Manufacturing of Compound X2> (Manufacturing Example 2-1) Sodium hydride (60%, in oil) (4.3 g, 106.0 mmol) and dehydrated THF (73.2 g) were added to a 300 mL three-necked flask and cooled to below 10 °C. 2,4,6-Triiodophenol (25.0 g, 53.0 mmol) was added to the suspension, and the mixture was stirred directly for 30 minutes. Then, compound (X-1-1) (14.6 g, 53.0 mmol) was added, and the mixture was brought back to room temperature (25 °C). After 6 hours, the reaction mixture was added dropwise to 5% hydrochloric acid (91.1 g, 127.2 mmol) cooled to below 10 °C. After stirring for 1 hour, the mixture was separated, and the organic layer was concentrated using a rotary evaporator. Dichloromethane (79 g) was added to the concentrate, and the mixture was stirred at room temperature (25 °C) for 2 hours. The precipitated solid was filtered. Acetonitrile (337 g) was added to the obtained solid, dissolved at 60 °C, and the mixture was brought back to room temperature (25 °C). Ultrapure water (337 g) was added, and the mixture was cooled to below 10 °C. Two hours later, the precipitated solid was filtered to obtain compound (X-2-1).

[0480]

[0481] (Manufacturing Example 2-2) By replacing 2,4,6-triiodophenol (25.0 g, 53.0 mmol) with 2,4-diiodophenol (18.3 g, 52.9 mmol), compound (X-2-2) was obtained in the same manner as in the preparation example of compound (X-2-1).

[0482]

[0483] (Manufacturing Example 2-3) By replacing 2,4,6-triiodophenol (25.0 g, 53.0 mmol) with 4-iodophenol (11.7 g, 53.2 mmol), compound (X-2-3) was obtained in the same manner as in the preparation example of compound (X-2-1).

[0484]

[0485] (Manufacturing Examples 2-4) The 2,4,6-triiodophenol (25.0 g, 53.0 mmol) was replaced with 2-fluoro-4-iodophenol (12.6 g, 52.9 mmol), and the compound (X-2-4) was obtained in the same manner as the compound (X-2-1) in the preparation example.

[0486]

[0487] <The Manufacturing of Precursor Bpre> (Manufacturing Example 3-1) Compound (X-2-1) (15.0 g, 20.1 mmol), compound (I-1-1) (6.9 g, 22.1 mmol), and dichloromethane (200 g) were added to a 500 mL three-necked flask and stirred at room temperature (25 °C) for 10 minutes. Next, N,N'-diisopropylcarbodiimide (2.8 g, 22.1 mmol) and dimethylaminopyridine (0.031 g, 0.3 mmol) were added, and the mixture was reacted at room temperature (25 °C) for 12 hours. The reaction mixture was washed four times with ultrapure water (100 g), and the organic layer was concentrated using a rotary evaporator. Ethyl acetate (100 g) was added to the concentrate, and the mixture was stirred at room temperature (25 °C) for 2 hours. The precipitated solid was filtered off. Methanol (50 g) was added to the obtained solid, and the mixture was dissolved at 60 °C and concentrated using a rotary evaporator. Ethyl acetate (100 g) was added to the concentrate, and the mixture was stirred at room temperature for 2 hours. The precipitated solid was filtered off. Repeat this operation twice to obtain the precursor (Bpre-01).

[0488]

[0489] (Manufacturing Example 3-2) Compound (I-1-1) (6.9 g, 22.1 mmol) was changed to compound (I-1-2) (8.4 g, 22.1 mmol), except that the precursor (Bpre-02) was obtained by the same method as the precursor (Bpre-01).

[0490]

[0491] (Manufacturing Example 3-3) Compound (X-2-1) (15.0 g, 20.1 mmol) was changed to compound (X-2-2) (12.5 g, 20.1 mmol), except that the precursor (Bpre-03) was obtained by the same method as the precursor (Bpre-01).

[0492]

[0493] (Manufacturing Examples 3-4) Compound (X-2-1) (15.0 g, 20.1 mmol) was changed to compound (X-2-3) (10.0 g, 20.1 mmol), except that the precursor (Bpre-04) was obtained by the same method as the precursor (Bpre-01).

[0494]

[0495] (Manufacturing Example 3-5) Compound (X-2-1) (15.0 g, 20.1 mmol) was changed to compound (X-2-4) (10.3 g, 20.0 mmol), except that the precursor (Bpre-05) was obtained by the same method as the precursor (Bpre-01).

[0496]

[0497] <Example of manufacturing compound (B0-01)> The precursor (Bpre-01) (15.0 g, 14.4 mmol) and the salt exchange compound (S-1-1) (4.94 g, 14.4 mmol) were dissolved in dichloromethane (170 g) and ultrapure water (170 g), and reacted at room temperature (25 °C) for 30 minutes. After the reaction was complete, the aqueous layer was removed, and the organic layer was washed four times with ultrapure water (85 g). The organic layer was concentrated and dried using a rotary evaporator to obtain compound (B0-01).

[0498]

[0499] The combination of precursor (Bpre-01) and salt exchange compound (S-1-1) in the above-mentioned "Example of Manufacturing Compound (B0-01)" was changed to the above-mentioned precursor (Bpre-01) to (Bpre-05) and salt exchange compound (S-1-1) to (S-1-4), respectively. Otherwise, the compounds (B0-02) to (B0-09) shown below were obtained in the same manner as in the above-mentioned "Example of Manufacturing Compound (B0-01)". The structures of compounds (B0-01) to (B0-09) are shown below.

[0500]

[0501]

[0502]

[0503]

[0504] Furthermore, the structures of the aforementioned compounds (BO-01) to (BO-09) were identified by the analytical results of 1H-NMR determination shown below.

[0505] Compound (B0-01): A combination of precursor (Bpre-01) and salt exchange compound (S-1-1). 1H-NMR (DMSO, 400MHz): δ (ppm) = 8.00 (d, I-ArH, 2H), 7.90-7.74 (m, ArH, 15H), 7.50-7.44 (m, ArH, 3H), 7.31-7.29 (m, ArH, 1H), 7.18-7.12 (m, ArH, 4H), 5.02(d, CH, 1H), 4.84(d, CH, 1H), 4.66-4.38(m, -CH 2CF 2-, 2H), 3.58-3.57(m, -OCO-CH-CH-COO, 1H), 3.42-3.40 (m, -OCO-CH-CH-COO, 1H)

[0506] Compound (B0-02): A combination of precursor (Bpre-02) and salt exchange compound (S-1-1). 1H-NMR (DMSO, 400MHz): δ (ppm) = 8.00 (d, I-ArH, 2H), 7.90-7.74 (m, ArH, 15H), 7.50-7.44 (m, ArH, 3H), 7.31-7.29 (m, ArH, 1H), 7.18-7.12 (m, ArH, 4H), 5.90(m, -CF 3CHCF 2-), 5.02(d, CH, 1H), 4.84(d, CH, 1H), 3.58-3.57(m, -OCO-CH-CH-COO, 1H), 3.42-3.40 (m, -OCO-CH-CH-COO, 1H)

[0507] Compound (B0-03): A combination of precursor (Bpre-03) and salt exchange compound (S-1-1). 1H-NMR(DMSO,400MHz): δ(ppm)=7.99(d, I-ArH, 1H), 7.90-7.74(m, ArH, I-ArH, 16H), 7.50-7.44(m, ArH, 3H), 7.31-7.29(m, ArH, 1H), 7.18-7.12(m, ArH, 4H), 6.90(dd, I-ArH, 1H), 5.02(d, CH, 1H), 4.84(d, CH, 1H), 4.66-4.38(m, -CH 2CF 2-, 2H), 3.58-3.57(m, -OCO-CH-CH-COO, 1H), 3.42-3.40 (m, -OCO-CH-CH-COO, 1H)

[0508] Compound (B0-04): A combination of precursor (Bpre-04) and salt exchange compound (S-1-1). 1H-NMR(DMSO,400MHz): δ(ppm)=7.90-7.74(m, ArH, I-ArH, 17H), 7.50-7.44(m, ArH, 3H), 7.31-7.29(m, ArH, 1H), 7.18-7.12(m, ArH, 4H), 6.89(dd, I-ArH, 2H), 5.02(d, CH, 1H), 4.84(d, CH, 1H), 4.66-4.38(m, -CH 2CF 2-, 2H), 3.58-3.57(m, -OCO-CH-CH-COO, 1H), 3.42-3.40 (m, -OCO-CH-CH-COO, 1H)

[0509] Compound (B0-05): A combination of precursor (Bpre-05) and salt exchange compound (S-1-1). 1H-NMR(DMSO,400MHz): δ(ppm)=7.90-7.74(m, ArH, 15H), 7.50-7.40(m, ArH, I-ArH, 5H), 7.31-7.29(m, ArH, 1H), 7.18-7.12(m, ArH, 4H), 7.02-7.00(m, I-ArH, 1H), 5.02(d, CH, 1H), 4.84(d, CH, 1H), 4.66-4.38(m, -CH 2CF 2-, 2H), 3.58-3.57(m, -OCO-CH-CH-COO, 1H), 3.42-3.40 (m, -OCO-CH-CH-COO, 1H)

[0510] Compound (B0-06): A combination of precursor (Bpre-01) and salt exchange compound (S-1-2). 1H-NMR(DMSO,400MHz): δ(ppm)=8.50(d, ArH, 2H), 8.37(d, ArH, 2H), 8.00(d, I-ArH, 2H), 7.93(t, ArH, 2H), 7.75-7.55(m, Ar, 7H), 7.50-7.44(m, ArH, 3H), 7.31-7.29(m, ArH, 1H), 7.18-7.12(m, ArH, 4H), 5.02(d, CH, 1H), 4.84(d, CH, 1H), 4.66-4.38(m, -CH 2CF 2-, 2H), 3.58-3.57(m, -OCO-CH-CH-COO, 1H), 3.42-3.40 (m, -OCO-CH-CH-COO, 1H)

[0511] Compound (B0-07): A combination of precursor (Bpre-01) and salt exchange compound (S-1-3). 1H-NMR(DMSO,400MHz): δ(ppm)=8.22-7.70(m, ArH, I-ArH, 16H), 7.50-7.44(m, ArH, 3H), 7.31-7.29(m, ArH, 1H), 7.18-7.12(m, ArH, 4H), 5.02(d, CH, 1H), 4.84(d, CH, 1H), 4.66-4.38(m, -CH 2CF 2-, 2H), 3.58-3.57(m, -OCO-CH-CH-COO, 1H), 3.42-3.40 (m, -OCO-CH-CH-COO, 1H), 2.77(m, cyclohexyl, 1H), 2.11-1.12(m, chclohexyl, 10H)

[0512] Compound (B0-08): A combination of precursor (Bpre-01) and salt exchange compound (S-1-4). 1H-NMR(DMSO,400MHz): δ(ppm)=8.00(d, I-ArH, 2H), 7.98-7.77(m, ArH, 11H), 7.50-7.44(m, ArH, 3H), 7.31-7.29(m, ArH, 1H), 7.18-7.12(m, ArH, 4H), 5.02(d, CH, 1H), 4.84(d, CH, 1H), 4.66-4.38(m, -CH 2CF 2-, 2H), 3.58-3.57(m, -OCO-CH-CH-COO, 1H), 3.42-3.40 (m, -OCO-CH-CH-COO, 1H)

[0513] Compound (B0-09): A combination of precursor (Bpre-04) and salt exchange compound (S-1-4). 1H-NMR(DMSO,400MHz): δ(ppm)=7.98-7.77(m, ArH, I-ArH, 13H), 7.50-7.44(m, ArH, 3H), 7.31-7.29(m, ArH, 1H), 7.18-7.12(m, ArH, 4H), 6.89(dd, I-ArH, 2H), 5.02(d, CH, 1H), 4.84(d, CH, 1H), 4.66-4.38(m, -CH 2CF 2-, 2H), 3.58-3.57(m, -OCO-CH-CH-COO, 1H), 3.42-3.40 (m, -OCO-CH-CH-COO, 1H)

[0514] <Preparation of Inhibitor Composition> (Examples 1-18, Comparative Examples 1-4) Mix and dissolve the components shown in Tables 1-3 to prepare the inhibitor compositions for each example.

[0515]

[0516]

[0517]

[0518] In Tables 1-3, each abbreviation has the following meaning. The value in [ ] is the amount of blending (parts by mass).

[0519] (A)-1: The polymer represented by the chemical formula (A1)-1. The weight-average molecular weight (Mw) of this polymer (A1)-1, determined by GPC and converted to standard polystyrene, is 7100, and the molecular weight dispersion (Mw / Mn) is 1.69. The copolymer composition ratio (the proportion of each constituent unit in the structural formula (molar ratio)) determined by 13C-NMR is 1 / m = 50 / 50.

[0520] (A)-2: The polymer represented by the chemical formula (A1)-2. The weight-average molecular weight (Mw) of this polymer (A1)-2, converted to standard polystyrene by GPC determination, is 7000, and the molecular weight dispersion (Mw / Mn) is 1.72. The copolymer composition ratio (the proportion of each constituent unit in the structural formula (molar ratio)) obtained by 13C-NMR is 1 / m = 50 / 50.

[0521] (A)-3: The polymer represented by the chemical formula (A1)-3. The weight-average molecular weight (Mw) of this polymer (A1)-3, converted to standard polystyrene by GPC determination, is 6900, and the molecular weight dispersion (Mw / Mn) is 1.68. The copolymer composition ratio (the proportion of each constituent unit in the structural formula (molar ratio)) obtained by 13C-NMR is 1 / m = 50 / 50.

[0522] (A)-4: The polymer represented by the chemical formula (A1)-4. The weight-average molecular weight (Mw) of this polymer (A1)-4, determined by GPC and converted to standard polystyrene, is 7000, and the molecular weight dispersion (Mw / Mn) is 1.70. The copolymer composition ratio (the proportion of each constituent unit in the structural formula (molar ratio)) determined by 13C-NMR is 1 / m = 50 / 50.

[0523] (A)-5: The polymer represented by the chemical formula (A1)-5. The weight-average molecular weight (Mw) of this polymer (A1)-5, converted to standard polystyrene by GPC determination, is 6800, and the molecular weight dispersion (Mw / Mn) is 1.68. The copolymer composition ratio (the proportion of each constituent unit in the structural formula (molar ratio)) obtained by 13C-NMR is 1 / m = 50 / 50.

[0524] (A)-6: The polymer represented by the chemical formula (A1)-6. The weight-average molecular weight (Mw) of this polymer (A1)-6, converted to standard polystyrene by GPC determination, is 6800, and the molecular weight dispersion (Mw / Mn) is 1.69. The copolymer composition ratio (the proportion of each constituent unit in the structural formula (molar ratio)) obtained by 13C-NMR is 1 / m = 50 / 50.

[0525]

[0526] (B0)-1~(B0)-8: Each of the above compounds (B0-01)~(B0-08) is an acid-generating agent.

[0527] (B1)-1: An acid-generating agent composed of the following compound (B1-1). (B1)-2: An acid-generating agent composed of the following compound (B1-2). (B1)-3: An acid-generating agent composed of the following compounds (B1-3). (B1)-4: An acid-generating agent composed of the following compounds (B1-4).

[0528]

[0529] (D)-1: An acid diffusion control agent consisting of a compound represented by the following chemical formula (D1-1). (S)-1: A mixed solvent of propylene glycol monomethyl ether acetate / propylene glycol monomethyl ether = 60 / 40 (mass ratio).

[0530]

[0531] <Formation of Inhibitor Patterns> On an 8-inch silicon substrate that has undergone hexamethyldisilazane (HMDS) treatment, each example of the resist composition was coated using a spinner and dried by pre-baking (PAB) at 110°C for 60 seconds on a heated plate to form a resist film with a thickness of 50 nm. Next, the aforementioned resist film was exposed using an electron beam mapping apparatus JEOL-JBX-9300FS (manufactured by Japan Electronics Corporation) at an accelerating voltage of 100kV to create a contact hole pattern (hereinafter referred to as "CH pattern") with 32nm diameter holes spaced at equal intervals (64nm spacing). After that, a post-exposure heating (PEB) treatment was performed at 110°C for 60 seconds. Next, alkaline development was performed at 23°C for 60 seconds using a 2.38% by mass tetramethylammonium hydroxide (TMAH) aqueous solution "NMD-3" (trade name, manufactured by Tokyo Ohka Kogyo Co., Ltd.). Afterwards, rinse with pure water for 15 seconds. As a result, a CH pattern was formed with holes of 32 nm in diameter arranged at equal intervals (64 nm spacing).

[0532] [Evaluation of Optimal Exposure (Eop)] The optimal exposure value Eop (μC / cm 2) for forming the CH pattern of the target size using the above-mentioned <Resistant Pattern Formation> was determined. It is shown as "Eop (μC / cm 2)" in Tables 4 and 5.

[0533] [Evaluation of In-Plane Uniformity (CDU) of Graphic Dimensions] For the CH pattern formed by the above-mentioned <formation of resistive pattern>, a length-measuring SEM (scanning electron microscope, accelerating voltage 500V, trade name: CG5000, manufactured by Hitachi Advanced Technology Co., Ltd.) was used to observe the CH pattern from above and measure the diameter (nm) of each hole. Then, three times the standard deviation (σ) calculated from the measurement results (3σ) was obtained. The result is presented as "CDU (nm)" in Tables 4 and 5. The smaller the value of 3σ obtained in this way, the higher the uniformity of the size (CD) of the complex pores formed in the resist film.

[0534]

[0535]

[0536] As shown in Tables 4 and 5, the resist composition of the embodiments, compared with the resist composition of the comparative examples, can be confirmed to have higher sensitivity when forming resist patterns and better CDU.

[0537] The inhibitor compositions of Examples 1, 3, and 4 all contain the same (BO) component in their main framework, but the number of iodine atoms in the anionic portion of the (BO) component differs from one another. The inhibitor composition of Example 1 contains compound (BO-01) with 3 iodine atoms, the inhibitor composition of Example 3 contains compound (BO-03) with 2 iodine atoms, and the inhibitor composition of Example 4 contains compound (BO-04) with 1 iodine atom. Compared to the inhibitor compositions of Examples 3 and 4, the inhibitor composition of Example 1 has better sensitivity and CDU. Therefore, it can be confirmed that by increasing the number of iodine atoms in the anionic portion of the (BO) component from 1 to 3, the sensitivity and CDU are improved. Furthermore, a comparison between the inhibitor composition of Example 4 and the inhibitor composition of Example 5 shows that the presence or absence of fluorine atoms in the anionic portion of the (B0) component does not lead to differences in sensitivity and CDU.

[0538] The inhibitor compositions of Examples 1, 6-8 each contain (BO) components with the same anionic portion and different cationic portions. Compared to the inhibitor composition of Example 1, the inhibitor compositions of Examples 6-8 exhibit better sensitivity and CDU. Therefore, it can be seen that if the decomposability of the cationic portion of the (BO) component is improved, the sensitivity and CDU will be improved.

[0539] The inhibitor composition of Comparative Example 3 contains an acid-generating agent composed of compounds (B1-3) having polycyclic aromatic hydrocarbon groups. The inhibitor composition of Comparative Example 4 contains an acid-generating agent composed of compounds (B1-4) having polycyclic aliphatic hydrocarbon groups. These inhibitor compositions, unlike the inhibitor compositions of the examples, do not contain an acid-generating agent having a condensed cyclic group obtained by the condensation of an aromatic ring and an aliphatic ring; therefore, their CDU is inferior to that of the inhibitor compositions of the examples.

[0540] 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 may be made to the structure without departing from the spirit of the present invention. The present invention is not limited by the foregoing description, but only by the appended claims.

Claims

1. A resist composition that generates acid upon exposure and whose solubility in a developer changes due to the action of the acid, comprising a substrate component (A) whose solubility in a developer changes due to the action of the acid, and an acid-generating agent component (B) that generates acid upon exposure, wherein the aforementioned acid-generating agent component (B) comprises a compound (B0) represented by the following general formula (b0); [wherein, Rb0 is a condensed cyclic group obtained by the condensation of an aromatic ring and an alicyclic ring, except that the following formula (L-4) is excluded from the aforementioned condensed cyclic group.] The divalent hydrocarbon group is represented; the alicyclic ring in the aforementioned condensed cyclic group has substituents, and at least one of the substituents includes a hydrocarbon group having a bromine atom or a hydrocarbon group having an iodine atom; Yb0 is a divalent linker or a single bond; however, Yb0 is bonded to the alicyclic ring in the aforementioned condensed cyclic group; Vb0 is a single bond, an alkyl group or a fluorinated alkyl group; R0 is a fluorinated alkyl group or a fluorine atom having 1 to 5 carbon atoms; Mm+ represents an m-valent organic cation; m is an integer greater than or equal to 1).

2. The inhibitor composition as claimed in claim 1, wherein the aromatic ring in the aforementioned Rb0 is a benzene ring.

3. The inhibitor composition of claim 1, wherein the aforementioned compound (B0) comprises a compound represented by the following general formula (b0-1); [wherein, Rx1 to Rx4 each independently represent a hydrocarbon group or hydrogen atom that may have substituents, or two or more that may be bonded together to form a ring structure; Ry1 to Ry2 each independently represent a hydrocarbon group or hydrogen atom that may have substituents, or that may be bonded together to form a ring structure;] It is a double bond or a single bond; Rz1 to Rz4, when the atomic valence allows, each independently represents a hydrocarbon group or hydrogen atom that can have substituents, or two or more can be bonded together to form a ring structure; however, two or more of Rx1 to Rx4, Ry1 to Ry2, or at least one of two or more of Rz1 to Rz4 are bonded together to form an aromatic ring; furthermore, at least one of Rx1 to Rx4, Ry1 to Ry2, and Rz1 to Rz4 has an anionic group represented by the following general formula (b0-r-an1), with the entire anionic part becoming an n-valent anion; furthermore, at least one of Rx1 to Rx4, Ry1 to Ry2, and Rz1 to Rz4 contains a hydrocarbon group with a bromine atom or a hydrocarbon group with an iodine atom; n is an integer of 1 or more; m is an integer of 1 or more, and Mm+ represents an m-valent organic cation]; [In the formula, Yb0 is a divalent linker or a single bond; Vb0 is a single bond, an alkyl group, or a fluorinated alkyl group; R0 is a fluorinated alkyl group or a fluorine atom with 1 to 5 carbon atoms; * indicates the bonding site].

4. In any of the inhibitor compositions in claims 1 to 3, the hydrocarbon groups having bromine atoms and the hydrocarbon groups having iodine atoms mentioned above are aromatic hydrocarbon groups.

5. A method for forming a resist pattern, comprising the steps of forming a resist film on a support using a resist composition as claimed in claim 1, exposing the resist film, and developing the exposed resist film to form a resist pattern.

6. A compound represented by the following general formula (b0); [wherein, Rb0 is a condensed cyclic group obtained by condensation of an aromatic ring and an alicyclic ring, except that the divalent hydrocarbon group represented by the following formula (L-4) is excluded from the aforementioned condensed cyclic group; the alicyclic ring in the aforementioned condensed cyclic group has substituents, and at least one of the aforementioned substituents includes a hydrocarbon group having a bromine atom or a hydrocarbon group having an iodine atom; Yb0 is a divalent linker or a single bond; however, Yb0 is bonded to the alicyclic ring in the aforementioned condensed cyclic group; Vb0 is a single bond, an alkyl group or a fluorinated alkyl group; R0 is a fluorinated alkyl group or a fluorine atom having 1 to 5 carbon atoms; Mm+ represents an m-valent organic cation; m is an integer of 1 or more].

7. An acid generating agent comprising the compound of claim 6.

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