Resistor composition, resistor pattern formation method, and compound

Abstract

An inhibitor composition comprising a resin component (A1) having a constituent unit (a01) derived from a compound of general formula (a0-1). In the formula, R01 is a hydrogen atom, etc. L01 is a divalent linker. Ra01 and Ra02 are each independently a hydrocarbon group that may have substituents. Ar01 is an aryl group, etc., in which one or all of the hydrogen atoms are replaced by iodine atoms. The aforementioned aryl group may also have substituents other than iodine atoms.

Description

Technical Field

[0001] This invention relates to inhibitor compositions, inhibitor pattern formation methods, and compounds. This case asserts priority based on Japanese Patent Application No. 2022-007875, filed in Japan on January 21, 2022, and the contents of that application are incorporated herein by reference. Prior Technology

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

[0003] The resist material is required to have photolithography properties such as sensitivity to the exposure light source and the ability to reproduce the resolution of fine-sized patterns. As a resist material that meets this requirement, chemically amplified resist compositions have been used in the past. These compositions contain a substrate component that changes the solubility of the developer due to the action of acid, and an acid-generating agent component that generates acid due to exposure.

[0004] In chemically amplified inhibitor compositions, resins with multiple constituent units are generally used to improve lithography properties. For example, Patent Document 1 discloses a resist composition containing a resin component (A1) having: specific constituent units (a01) with acid-dissociable groups, constituent units (a02) containing cyclic groups (a01) forming part of a -OC (=O)- ring backbone (but excluding those forming cross-linked structures), and specific constituent units (a03) having hydroxyl groups. This resist composition is disclosed to control acid diffusion, thereby improving affinity for developer, and also exhibiting excellent sensitivity, roughness reduction, and resolution. [Previous Technical Documents] [Patent Literature]

[0005] [Patent Document 1] Japanese Patent Application Publication No. 2020-085916 Summary of the Invention

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

[0007] With the advancement of lithography technology and the expansion of its application areas, it is rapidly moving towards miniaturization of patterns. Consequently, in the manufacture of semiconductor devices, there is a demand for technologies capable of forming fine patterns with precise shapes. However, for this requirement, the conventional resist composition described in Patent Document 1 does not necessarily have sufficient sensitivity to resist pattern formation and roughness reduction at the same time, but rather requires a higher degree of coexistence.

[0008] The present invention was made in view of the above circumstances, and its object is to provide a resist composition that can achieve high sensitivity and form a resist pattern with good roughness reduction, a method for forming a resist pattern using the resist composition, and a compound that can be used to make the resin contained in the resist composition. [Methods used to solve problems]

[0009] To address the aforementioned issues, the present invention employs the following configuration. That is, the first state sample of the present invention is a resist composition, which is a resist composition that generates acid due to exposure and changes the solubility of the developer due to the action of the acid, and contains a resin component (A1), which has a constituent unit (a01) derived from the compound shown in the following general formula (a0-1).

[0010] [In the formula, R01 is a hydrogen atom, an alkyl group having 1 to 10 carbon atoms, or a haloalkyl group having 1 to 10 carbon atoms. L01 is a divalent linkage. Ra01 and Ra02 are each independently a hydrocarbon group that can have substituents. Ar01 is an aryl group in which one or all of the hydrogen atoms are replaced by iodine atoms, or a heteroaryl group in which one or all of the hydrogen atoms are replaced by iodine atoms. The aforementioned aryl and heteroaryl groups may also have substituents other than iodine atoms.]

[0011] 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 a resist composition as described in the first state, exposing the resist film, and developing the exposed resist film to form a resist pattern.

[0012] The third state of the present invention is a compound represented by the above general formula (a0-1). [Invention Effects]

[0013] According to the present invention, a resist composition for achieving high sensitivity and forming a resist pattern with good roughness reduction can be provided, a method for forming a resist pattern using the resist composition, and a compound capable of forming a resin contained in the resist composition. Implementation

[0014] In this specification and the scope of this patent application, "aliphatic" is a relative concept compared to aromatic, and is defined as meaning a base, compound, etc. that does not have aromatic properties. Unless otherwise defined, "alkyl" is considered to include monovalent saturated hydrocarbon groups that are linear, branched, or cyclic. The same applies to alkyl groups in alkoxy groups. Unless otherwise defined, "alkyl" is considered to include divalent saturated hydrocarbon groups in the form of straight chains, branches, and rings. Examples of "halogen atoms" include fluorine, chlorine, bromine, and iodine atoms. "Constituted unit" refers to the monomer unit (monomer unit) that makes up a polymer compound (resin, polymer, copolymer). The cases described as "may have substituents" include both cases where a hydrogen atom (-H) is replaced by a monovalent group and cases where a methylene group (-CH 2-) is replaced by a divalent group. "Exposure" is considered to include exposure to various types of radiation.

[0015] "Acid-decomposable group" is a group that has acid-decomposable properties, meaning that at least a portion of the bonds in its structure can be broken by the action of an acid. Examples of acid-decomposing groups that increase in polarity due to the action of acids include groups that decompose due to the action of acids and generate polar groups. Examples of polar groups include carboxyl, hydroxyl, amino, and sulfonic acid groups (-SO 3H). More specifically, examples of acid-dissociable groups include those polar groups that are protected by acid-dissociable groups (e.g., those polar groups containing OH whose hydrogen atoms are protected by acid-dissociable groups).

[0016] "Acid-dissociable group" refers to (i) an acid-dissociable group whose bonds with adjacent atoms can be broken by the action of an acid, or (ii) a group whose bonds can be broken by a decarbonation reaction after a portion of the bonds are broken by the action of an acid. The acid-dissociating group constituting the acid-dissociating group must be a group with lower polarity than the polar group generated by the dissociation of the acid-dissociating group. Therefore, when the acid-dissociating group dissociates due to the action of the acid, a polar group with higher polarity than the acid-dissociating group is generated, thus increasing the polarity. The result is an increase in the overall polarity of the (A1) component. This increase in polarity relatively alters the solubility of the developer; solubility increases when the developer is alkaline, and decreases when the developer is organic.

[0017] "Substrate component" refers to an organic compound with film-forming ability. Organic compounds used as substrate components are broadly classified into non-polymers and polymers. Non-polymers typically have a molecular weight of 500 or higher but less than 4000. The term "low molecular weight compound" below 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" below refer to polymers with a molecular weight of 1000 or higher. The molecular weight of a polymer is considered to be the weight average molecular weight converted to polystyrene using GPC (gel permeation chromatography).

[0018] "Derived constituent units" refers to the constituent units formed by the multiple bonds between carbon atoms, such as the cleavage of vinyl double bonds. The hydrogen atom bonded to the α-carbon atom in "acrylate" can also be replaced by a substituent. The substituent (Rαx) replacing the hydrogen atom bonded to the α-carbon atom can be an atom or group other than the hydrogen atom. Furthermore, this also includes isoconic acid diesters substituted with a substituent (Rαx) containing an ester bond, or α-hydroxy acrylates substituted with a hydroxyalkyl group or a group modified with that hydroxyl group. Moreover, unless otherwise defined, the α-carbon atom in acrylate refers to the carbon atom bonded to the carbonyl group of acrylic acid. The following refers to acrylates in which the hydrogen atom bonded to the carbon atom at the α-position is replaced by a substituent as α-substituted acrylates.

[0019] "Derivative" is considered to include compounds in which the α-hydrogen atom is replaced by other substituents such as alkyl groups or halogenated alkyl groups, and such derivatives. Examples of such derivatives include compounds in which the α-hydrogen atom can be replaced by a substituent, and compounds in which a substituent other than a hydroxyl group is bonded to the α-hydrogen atom. Furthermore, when not specifically defined, the α-position refers to the first carbon atom adjacent to the functional group. Examples of substituents that replace the α-hydrogen atom of hydroxystyrene include those identical to Rαx.

[0020] In this specification and the claims, based on the structure represented by the chemical formula, there may be asymmetric carbon, and these may be enantiomers or diastereomers. In this case, a single chemical formula is used to represent these isomers. These isomers can be used alone or as mixtures.

[0021] (Inhibitor composition) The resist component in this embodiment is an acid that is generated upon exposure and whose solubility in the developer changes due to the action of the acid. The inhibitor composition contains: substrate component (A) which changes the solubility of the developer due to the action of acid (hereinafter also referred to as "(A) component").

[0022] In the resist composition of this embodiment, component (A) may generate acid upon exposure, or it may be an additive component that is blended with a different component (A) and generates acid upon exposure. Specifically, the resist composition of this embodiment may (1) contain an acid-generating agent component (B) (hereinafter referred to as "(B) component") that generates acid due to exposure; (2) may contain component (A) that generates acid due to exposure; and (3) may contain component (A) that generates acid due to exposure, and also contain component (B). That is, in the cases of (2) and (3) above, component (A) becomes "a substrate component that generates acid due to exposure and whose solubility in the developer changes due to the action of the acid". In the case where component (A) is a substrate component that generates acid due to exposure and whose solubility in the developer changes due to the action of the acid, component (A1) described later is preferably a resin that generates acid due to exposure and whose solubility in the developer changes due to the action of the acid. As such a resin, a polymer compound having constituent units that generate acid due to exposure can be used. Known constituent units that generate acid due to exposure can be used.

[0023] The inhibitor composition of this embodiment is preferably as described in (1) above. That is, the inhibitor composition of this embodiment is preferably one containing components (A) and (B).

[0024] When a resist film is formed using the resist composition of this embodiment and selectively exposed, an acid is generated from component (B) in the exposed portion of the resist film, and the solubility of component (A) in the developer changes due to the action of the acid. On the other hand, the solubility of component (A) in the developer does not change in the unexposed portion of the resist film. Therefore, a difference in solubility in the developer occurs between the exposed and unexposed portions. Thus, when developing the resist film, if the resist composition is positive, the exposed portion of the resist film is dissolved and removed to form a positive resist pattern; if the resist composition is negative, the unexposed portion of the resist film is dissolved and removed to form a negative resist pattern.

[0025] The resist composition of this embodiment can be either a positive or 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 of resist pattern formation, or in a solvent development process where a developer containing an organic solvent (organic developer) is used during the development process.

[0026] <(A)Component> In the resist composition of this embodiment, component (A) includes a resin component (A1) that changes the solubility of the developer due to the action of acid (hereinafter also referred to as "(A1) component"). By using the (A1) component, the polarity of the substrate components 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), it can also be used together with other high molecular weight compounds and / or low molecular weight compounds.

[0027] In the inhibitor composition of this embodiment, component (A) can be used alone or in combination with two or more components.

[0028] Regarding component (A1) (A1) is a resin component whose solubility in the developer changes due to the action of acid. (A1) The component has: a constituent unit (a01) derived from the compound shown in the following general formula (a0-1). (A1) In addition to the constituent unit (a01), the component may also have other constituent units as necessary.

[0029] [In the formula, R01 is a hydrogen atom, an alkyl group having 1 to 10 carbon atoms, or a haloalkyl group having 1 to 10 carbon atoms. L01 is a divalent linkage. Ra01 and Ra02 are each independently a hydrocarbon group that can have substituents. Ar01 is an aryl group in which one or all of the hydrogen atoms are replaced by iodine atoms, or a heteroaryl group in which one or all of the hydrogen atoms are replaced by iodine atoms. The aforementioned aryl and heteroaryl groups may also have substituents other than iodine atoms.]

[0030] In the above general formula (a0-1), R 01 is a hydrogen atom, an alkyl group having 1 to 10 carbon atoms, or a haloalkyl group having 1 to 10 carbon atoms. In R 01, the alkyl group having 1 to 10 carbon atoms is preferably a straight-chain or branched alkyl group having 1 to 10 carbon atoms, and a straight-chain or branched alkyl group having 1 to 5 carbon atoms is even more preferred. Specific examples include methyl, ethyl, propyl, isopropyl, n-butyl, isobutyl, tert-butyl, pentyl, isopentyl, neopentyl, etc. The alkyl halide with 1 to 10 carbon atoms is a group in which one or all of the hydrogen atoms of the aforementioned alkyl group with 1 to 10 carbon atoms are replaced by halogen atoms. The halogen atom is preferably a fluorine atom. As R 01, it is preferred to have hydrogen atoms, alkyl groups with 1 to 5 carbon atoms, or fluorinated alkyl groups with 1 to 5 carbon atoms. From an industrial availability perspective, hydrogen atoms or methyl groups are preferred.

[0031] In the above general formula (a0-1), examples of divalent linkages of L 01 include divalent hydrocarbon groups with substituents and divalent linkages containing heteroatoms.

[0032] • Can have divalent hydrocarbon groups with substituents: L 01 represents a divalent hydrocarbon group that can have substituents. This hydrocarbon group can be an aliphatic hydrocarbon group or an aromatic hydrocarbon group.

[0033] Aliphatic hydrocarbon groups in L 01 Aliphatic hydrocarbon groups refer to hydrocarbon groups that do not possess aromatic properties. These aliphatic hydrocarbon groups can be saturated or unsaturated, but saturation is generally preferred. Examples of aliphatic hydrocarbon groups mentioned above include straight-chain or branched aliphatic hydrocarbon groups, or aliphatic hydrocarbon groups whose structure contains rings.

[0034] ...linear or branched aliphatic hydrocarbon groups The linear aliphatic hydrocarbon system is preferably composed of 1 to 10 carbon atoms, preferably 1 to 6 carbon atoms, even better if it has 1 to 4 carbon atoms, and best if it has 1 to 3 carbon atoms. As a straight-chain aliphatic hydrocarbon group, a straight-chain alkyl group is preferred. Specific examples include methylene [-CH 2-], ethyl [-(CH 2) 2-], trimethylene [-(CH 2) 3-], tetramethylene [-(CH 2) 4-], and pentamethylene. [-(CH 2) 5-] etc. The branched aliphatic hydrocarbon system is preferably composed of 2 to 10 carbon atoms, preferably 3 to 6 carbon atoms, even better if it has 3 or 4 carbon atoms, and best if it has 3 carbon atoms. As a branched aliphatic hydrocarbon group, branched alkyl groups are preferred, specifically examples include -CH(CH 3)-, -CH(CH 2CH 3)-, 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 and other alkyl alkyl groups, such as -CH(CH 3)CH 2CH 2CH 2- and -CH 2CH(CH 3)CH 2CH 2-. Among alkyl alkyl groups, straight-chain alkyl groups with 1 to 5 carbon atoms are preferred.

[0035] The aforementioned straight-chain or branched aliphatic hydrocarbon groups may or may not have substituents. Examples of such substituents include fluorine atoms, fluorinated alkyl groups with 1 to 5 carbon atoms substituted by fluorine atoms, and carbonyl groups.

[0036] ...The structure contains cyclic aliphatic hydrocarbon groups Examples of aliphatic hydrocarbon groups containing a ring in this structure include, for example, cyclic aliphatic hydrocarbon groups containing substituents with heteroatoms (groups with two hydrogen atoms removed from the aliphatic hydrocarbon ring), groups where the aforementioned cyclic aliphatic hydrocarbon group is bonded to the end of a straight-chain or branched aliphatic hydrocarbon group, and groups where the aforementioned cyclic aliphatic hydrocarbon group exists in the middle of a straight-chain or branched aliphatic hydrocarbon group. Examples of the aforementioned straight-chain or branched aliphatic hydrocarbon groups are those similar to those described above. Cyclic aliphatic hydrocarbon groups are preferred with 3 to 20 carbon atoms, and even more preferred with 3 to 12 carbon atoms. Cyclic aliphatic hydrocarbon groups can be polycyclic or monocyclic. For monocyclic alicyclic hydrocarbon groups, it is preferable to use a group that has removed two hydrogen atoms from a monocyclic alkane. For such monocyclic alkanes, those with 3 to 6 carbon atoms are preferred; specific examples include cyclopentane and cyclohexane. For polycyclic alicyclic hydrocarbon groups, it is preferable to use a group that has removed two hydrogen atoms from a polycyclic alkane; for such polycyclic alkanes, those with 7 to 12 carbon atoms are preferred; specific examples include adamantane, norcamphene, isocamphene, tricyclodecane, and tetracyclododecane.

[0037] Cyclic aliphatic hydrocarbon groups may or may not have substituents. Examples of such substituents include alkyl groups, alkoxy groups, 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, with methyl, ethyl, propyl, n-butyl, and tert-butyl being more preferred. As for the alkoxy group used as the aforementioned substituent, an alkoxy group having 1 to 5 carbon atoms is preferred, and methoxy, ethoxy, n-propoxy, iso-propoxy, n-butoxy, and tert-butoxy are more preferred, with methoxy and ethoxy being even more preferred. The halogen atom used as the aforementioned substituent is preferably a fluorine atom. Examples of alkyl halides that can be used as substituents include those in which one or all of the hydrogen atoms of the aforementioned alkyl group are replaced by the aforementioned halogen atoms. The carbon atom in the ring structure of a cyclic aliphatic hydrocarbon group can also be replaced by a substituent containing a heteroatom. Preferred substituents containing heteroatoms are -O-, -C(=O)-O-, -S-, -S(=O)2-, and -S(=O)2-O-.

[0038] Furthermore, cyclic aliphatic hydrocarbon groups can also be lactone-containing cyclic groups as represented by the following general formulas (Lr-1) to (Lr-7).

[0039] [In the formula, Ra' 021 each independently represent a hydrogen atom, alkyl group, alkoxy group, halogen atom, alkyl halide, hydroxyl group, -COOR 0”, -OC(=O)R 0”, hydroxyalkyl group, or cyano group; R 0” is a hydrogen atom, alkyl group, or cyclic group containing lactone; A 0” 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-); n0' is an integer from 0 to 2; m0' is 0 or 1. * indicates the bonding site with the carbon atom bonded to R 01 in the above general formula (a0-1). ** indicates the bonding site with the carbon atom of the carbonyl group in the above general formula (a0-1).]

[0040] In the aforementioned general formulas (Lr-1) to (Lr-7), the alkyl group in Ra' 021 is preferably an alkyl group with 1 to 6 carbon atoms. The alkyl group is preferably straight-chain or branched. The alkoxy group in Ra' 021 is preferably an alkoxy group with 1 to 6 carbon atoms. The alkoxy group is preferably linear or branched. Specifically, examples include alkyl groups formed by linking an alkyl group to an oxygen atom (-O-) as mentioned above in Ra' 021. Fluorine atoms are preferred as halogen atoms in Ra'021. Examples of alkyl halides in Ra' 021 include groups in which one or all of the hydrogen atoms of the alkyl group in Ra' 021 are replaced by the aforementioned halogen atoms. Fluorinated alkyl groups are preferred as alkyl halides, and perfluoroalkyl groups are particularly preferred.

[0041] In Ra' 021, in -COOR 0” and -OC(=O)R 0”, R 0” are both hydrogen atoms, alkyl groups, and cyclic groups containing lactones. As an alkyl group in "R0", it can be any of straight-chain, branched, or cyclic, with 1 to 15 carbon atoms being preferred. When R 0” is a straight-chain or branched alkyl group, it is preferred to have 1 to 10 carbon atoms, more preferably 1 to 5 carbon atoms, and methyl or ethyl is especially preferred. When R0” is a cyclic alkyl group, it is preferred to have 3 to 15 carbon atoms, more preferably 4 to 12 carbon atoms, and ideally 5 to 10 carbon atoms. Examples of lactone-containing cyclic groups in R0” include those that are the same as the groups represented by the aforementioned general formulas (Lr-1) to (Lr-7). The hydroxyalkyl group in Ra' 021 is preferably one with 1 to 6 carbon atoms. Specifically, examples include groups in Ra' 021 in which at least one hydrogen atom is replaced by a hydroxyl group.

[0042] In the aforementioned general formulas (Lr-2), (Lr-3), and (Lr-5), the alkyl group having 1 to 5 carbon atoms in "A0" is preferably a straight-chain or branched alkyl group, such as methylene, ethyl alkyl, n-propyl alkyl, and isopropyl alkyl. Specific examples of this alkyl group containing oxygen or sulfur atoms include those present at the end of the aforementioned alkyl group or between carbon atoms. The bases -O- or -S- can be exemplified by, for example, -O-CH2-, -CH2-O-CH2-. -S-CH 2-, -CH 2-S-CH 2-, etc. As A 0”, it is preferred to be an alkyl group with 1 to 5 carbon atoms or -O-.

[0043] Aromatic hydrocarbon groups in L 01 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 is a cyclic conjugated system with 4n+2 π electrons; it can be monocyclic or polycyclic. The number of carbon atoms in the aromatic ring is preferably 5-30, more preferably 5-20, even more preferably 6-15, and particularly preferably 6-12. However, this carbon number range is considered to exclude the carbon atoms in the substituents. Examples of aromatic rings include aromatic hydrocarbon rings such as those of benzene, naphthalene, anthracene, and phenanthrene; and aromatic heterocycles in which a portion of the carbon atoms constituting the aforementioned aromatic hydrocarbon rings are replaced by heteroatoms. Examples of heteroatoms in aromatic heterocycles include oxygen atoms, sulfur atoms, and nitrogen atoms. Examples of aromatic heterocycles include pyridine rings and thiophene rings. Specifically, aromatic hydrocarbon groups can be exemplified by groups (aryl or heteroaryl) in which two hydrogen atoms have been removed from the aforementioned aromatic hydrocarbon ring or aromatic heterocycle; groups in which two hydrogen atoms have been removed from aromatic compounds containing two or more aromatic rings (e.g., biphenyl, benzo[a], etc.); and groups in which one hydrogen atom of an aryl or heteroaryl group in which one hydrogen atom has been removed from the aforementioned aromatic hydrocarbon ring or aromatic heterocycle is replaced by an alkyl group (e.g., removing one hydrogen atom from an aryl group in arylalkyl groups such as benzyl, phenethyl, 1-naphthylmethyl, 2-naphthylmethyl, 1-naphthylethyl, 2-naphthylethyl, etc.). The number of carbon atoms in the alkyl group bonded to the aforementioned aryl or heteroaryl group is preferably 1 to 4, more preferably 1 to 2, and particularly preferably 1.

[0044] The hydrogen atoms of the aforementioned aromatic hydrocarbon group can also be replaced by substituents. For example, the hydrogen atoms on the aromatic ring bonded to the aromatic hydrocarbon group can also be replaced by substituents. Examples of such substituents include alkyl groups, alkoxy groups, halogen atoms, alkyl halides, and hydroxyl groups. The alkyl group used as the aforementioned substituent is preferably an alkyl group having 1 to 5 carbon atoms, with methyl, ethyl, propyl, n-butyl, and tert-butyl being more preferred. Examples of alkoxy groups, halogen atoms, and alkyl halides that can be used as substituents include those that replace the hydrogen atoms of the aforementioned cyclic aliphatic hydrocarbon groups.

[0045] • Divalent linkages containing heteroatoms: L 01 represents a divalent linker containing heteroatoms. Preferred examples of such linkers include -O-, -C(=O)-O-, etc. -OC(=O)-, -C(=O)-, -OC(=O)-O-, -C(=O)-NH-, -NH-, -NH-C(=NH)- (H can also be replaced by alkyl, acetylated, etc. substituents), -S-, -S(=O)2-, -S(=O)2-O-, general formula -Y21-OY22-, -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- as shown in the formula [where Y 21 and Y 22 are each independently divalent hydrocarbon groups that can have substituents, O is an oxygen atom, and m” is an integer from 0 to 3] etc. The aforementioned divalent linkage containing heteroatoms is -C(=O)-NH-. In the cases of -C(=O)-NH-C(=O)-, -NH-, and -NH-C(=NH)-, the H group can also be replaced by substituents such as alkyl or acetyl groups. These substituents (alkyl, acetyl, etc.) are preferably composed of 1 to 10 carbon atoms, more preferably 1 to 8, and especially 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-, In -Y 21-OC(=O)-Y 22- or -Y 21-S(=O) 2-OY 22-, Y 21 and Y 22 are each independently a divalent hydrocarbon group that can have substituents. Examples of such divalent hydrocarbon groups include those exemplified in the description of divalent linking groups in L 01 above (divalent hydrocarbon groups that can have substituents). As for Y 21, a straight-chain aliphatic hydrocarbon group is preferred, a straight-chain alkyl group is even better, a straight-chain alkyl group with 1 to 5 carbon atoms is even better, and methylene or ethyl group is particularly preferred. Y22 is preferably a straight-chain or branched aliphatic hydrocarbon group, with methylene, ethyl, or alkylmethylene being more preferred. The alkyl group in 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 methyl is the most desirable. In the basis shown by equation -[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 especially preferably 1. That is, as the basis shown by equation -[Y 21-C(=O)-O] m”-Y 22-, with equation... The base shown in -Y 21-C(=O)-OY 22- is particularly good. Among them, the formula is also used... The base represented by -(CH 2) a'-C(=O)-O-(CH 2) b'- is preferred. In this formula, a' is an integer from 1 to 10, preferably an integer from 1 to 8, preferably an integer from 1 to 5, preferably 1 or 2, and 1 is the best. b' is an integer from 1 to 10, preferably an integer from 1 to 8, preferably an integer from 1 to 5, preferably 1 or 2, and 1 is the best.

[0046] In the above, L 01 is formed by ester bonds. [-C(=O)-O-, -OC(=O)-], aromatic hydrocarbon group, cyclic group containing lactone, or a divalent linkage group having a combination of these groups is preferred. More specifically, L 01 is preferably composed of a group consisting of an ester bond and an alkyl group, an aromatic hydrocarbon group, or a group consisting of an ester bond and a cyclic group containing a lactone.

[0047] As the alkyl group composed of ester bond and alkyl group, the alkyl group is preferably a straight-chain or branched alkyl group with 1 to 5 carbon atoms, the alkyl group with 1 to 5 carbon atoms is more preferred, and methylene or ethyl group is even more preferred. Furthermore, the alkyl group may also have substituents, such as alkoxy groups, halogen atoms, alkyl halides, hydroxyl groups, etc.

[0048] 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 is a cyclic conjugated system with 4n+2 π electrons; it can be monocyclic or polycyclic. The number of carbon atoms in the aromatic ring is preferably 5-30, more preferably 5-20, even more preferably 6-15, and particularly preferably 6-12. However, this carbon number range is considered to exclude the carbon atoms in the substituents. Examples of aromatic rings include aromatic hydrocarbon rings such as those of benzene, naphthalene, anthracene, and phenanthrene; and aromatic heterocycles in which a portion of the carbon atoms constituting the aforementioned aromatic hydrocarbon rings are replaced by heteroatoms. Examples of heteroatoms in aromatic heterocycles include oxygen atoms, sulfur atoms, and nitrogen atoms. Examples of aromatic heterocycles include pyridine rings and thiophene rings. Specifically, aromatic hydrocarbon groups can be exemplified by groups (aryl or heteroaryl) in which two hydrogen atoms have been removed from the aforementioned aromatic hydrocarbon ring or aromatic heterocycle; groups in which two hydrogen atoms have been removed from aromatic compounds containing two or more aromatic rings (e.g., biphenyl, benzo[a], etc.); and groups in which one hydrogen atom of an aryl or heteroaryl group in which one hydrogen atom has been removed from the aforementioned aromatic hydrocarbon ring or aromatic heterocycle is replaced by an alkyl group (e.g., removing one hydrogen atom from an aryl group in arylalkyl groups such as benzyl, phenethyl, 1-naphthylmethyl, 2-naphthylmethyl, 1-naphthylethyl, 2-naphthylethyl, etc.). The number of carbon atoms in the alkyl group bonded to the aforementioned aryl or heteroaryl group is preferably 1 to 4, more preferably 1 to 2, and particularly preferably 1. Furthermore, aromatic hydrocarbon groups may also have substituents. Examples of such substituents include alkyl groups, alkoxy groups, halogen atoms, alkyl halides, and hydroxyl groups.

[0049] Among the aromatic hydrocarbon groups mentioned above, it is preferable to have a substituent aryl group, more preferably a substituent aryl group, even more preferably a hydroxyl aryl group, and especially preferably a hydroxyl phenyl group.

[0050] As for the cyclic group containing lactone among the groups composed of ester bonds and lactone-containing cyclic groups, the groups represented by the above general formulas (Lr-1) to (Lr-7) are preferred, and the group shown by the above general formula (Lr-2) is even more preferred.

[0051] Of the above, L01 is preferably represented by the basis expressed by the following general formulas (L0-r-1) to (L0-r-5).

[0052] [In the formula, Rx 00 are each an alkyl group. Ar 00 is an aryl group that may have substituents. Lc 00 is a cyclic group containing lactone shown in any of the above general formulas (Lr-1) to (Lr-7). * indicates the bond site with the carbon atom bonded to R 01 in the above general formula (a0-1). ** indicates the bond site with the carbon atom of the carbonyl group in the above general formula (a0-1).]

[0053] Rx 00 series compounds are preferably alkyl groups with 1 to 5 carbon atoms. Ar 00 series is preferably an aryl group that can have substituents, preferably an aryl group that has hydroxyl groups, and preferably an phenyl group that has hydroxyl groups. Lc 00 is a cyclic group containing lactone as shown in any of the above general formulas (Lr-1) to (Lr-7), with the cyclic group containing lactone shown in the above general formula (Lr-2) being preferred.

[0054] Of the above, for L 01, it is preferable to use the basis shown in any of the above general formulas (L0-r-3) to (L0-r-5), and the basis shown in the above general formula (L0-r-3) is more preferred.

[0055] In the above general formula (a0-1), the hydrocarbon groups in Ra 01 and Ra 02 can be, for example, linear hydrocarbon groups, branched hydrocarbon groups, and cyclic hydrocarbon groups.

[0056] Examples of straight-chain or branched hydrocarbon groups include straight-chain or branched saturated hydrocarbon groups (alkyl groups) and straight-chain or branched unsaturated hydrocarbon groups.

[0057] Specific examples of such straight-chain or branched alkyl groups include methyl, ethyl, propyl, isopropyl, n-butyl, isobutyl, tert-butyl, pentyl, isopentyl, neopentyl, etc.

[0058] More specifically, examples of unsaturated hydrocarbon groups that are straight-chain or branched include alkenyl, alkadienyl, alkanetrienyl, etc., which are unsaturated hydrocarbon groups with double bonds; and unsaturated hydrocarbon groups with triple bonds, such as those formed by removing one hydrogen atom from alkynyl, diyne, or triyne.

[0059] Specific examples of straight-chain or branched alkenyl groups include straight-chain alkenyl groups such as vinyl, allyl, and 2-butenyl; and branched alkenyl groups such as 1-methylvinyl, 2-methylvinyl, 1-methylpropenyl, and 2-methylpropenyl.

[0060] Specific examples of this alkyldienyl group include alladienyl and butadienyl. Specific examples of this alkyltrienyl group include butadieneyl group, etc.

[0061] Specific examples of straight-chain or branched alkynyl groups include straight-chain alkynyl groups such as ethynyl, propynyl, and 3-pentynyl; and branched alkynyl groups such as 1-methylpropynyl.

[0062] As a specific example of a group that removes one hydrogen atom from a diacetylene, one could cite a group that removes one hydrogen atom from a diacetylene. As a specific example of a group that removes one hydrogen atom from a triyne, one could cite a group that removes one hydrogen atom from a hexa-1,3,5-triyne.

[0063] The cyclic hydrocarbon group can be aliphatic or aromatic, and can be either polycyclic or monocyclic. As a monocyclic aliphatic hydrocarbon group, it is preferable to be a group that has removed one hydrogen atom from a monocyclic alkane. As for the monocyclic alkane, it is preferable to have 3 to 6 carbon atoms, and cyclopropane is a specific example. As a polycyclic aliphatic hydrocarbon group, it is preferable to be a group that removes one hydrogen atom from a polycyclic alkane. As for the polycyclic alkane, it is preferable to have 7 to 12 carbon atoms. Specific examples include adamantane, norcamphene, isocamphene, tricyclodecane, tetracyclododecane, etc.

[0064] Examples of aromatic hydrocarbon groups include aryl or heteroaryl groups, specifically phenyl and naphthyl groups.

[0065] Examples of substituents that can be present in the hydrocarbon groups of Ra 01 and Ra 02 include -RP1, -RP2-ORP1, and -RP2-CO-RP1. -R P2-CO-OR P1, -R P2-O-CO-R P1, -R P2-OH, -R P2-CN or -R P2-COOH (hereinafter also collectively referred to as "Ra x5") etc. Here, RP1 is a monovalent chain saturated hydrocarbon group with 1 to 10 carbon atoms, a monovalent aliphatic cyclic saturated hydrocarbon group with 3 to 20 carbon atoms, or a monovalent aromatic hydrocarbon group with 6 to 30 carbon atoms. RP2 is a single bond, a divalent chain saturated hydrocarbon group with 1 to 10 carbon atoms, a divalent aliphatic cyclic saturated hydrocarbon group with 3 to 20 carbon atoms, or a divalent aromatic hydrocarbon group with 6 to 30 carbon atoms. However, some or all of the hydrogen atoms in the chain saturated hydrocarbon group, aliphatic cyclic saturated hydrocarbon group, and aromatic hydrocarbon group of RP1 and RP2 may be replaced by fluorine atoms. The aforementioned aliphatic cyclic hydrocarbon group may have one or more of the aforementioned substituents, or it may have one or more of each of the aforementioned substituents. Examples of monovalent chain saturated hydrocarbon groups with 1 to 10 carbon atoms include methyl, ethyl, propyl, butyl, pentyl, hexyl, heptyl, octyl, and decyl. Examples of monocyclic aliphatic saturated hydrocarbon groups with 3 to 20 carbon atoms include monocyclic aliphatic saturated hydrocarbon groups such as cyclopropyl, cyclobutyl, cyclopentyl, cyclohexyl, cycloheptyl, cyclooctyl, cyclodecyl, and cyclododecyl; and polycyclic aliphatic saturated hydrocarbon groups such as bicyclic [2.2.2]octyl, tricyclic [5.2.1.0 2,6]decyl, tricyclic [3.3.1.1 3,7]decyl, tetracyclic [6.2.1.1 3,6.0 2,7]dodecyl, and adamantyl. Examples of aromatic hydrocarbon groups with a carbon number of 6 to 30 and a valence of 1 include groups that remove one hydrogen atom from the aromatic hydrocarbon rings of benzene, biphenyl, fumonisin, naphthalene, anthracene, phenanthrene, etc.

[0066] In the above general formula (a0-1), Ra 01 and Ra 02 are preferably, respectively, straight-chain or branched saturated hydrocarbon groups or straight-chain or branched unsaturated hydrocarbon groups. It is more preferred to have straight-chain or branched saturated hydrocarbon groups with 1 to 5 carbon atoms or straight-chain or branched unsaturated hydrocarbon groups with 1 to 5 carbon atoms. It is even more preferred to have straight-chain saturated hydrocarbon groups with 1 to 5 carbon atoms or straight-chain unsaturated hydrocarbon groups with 1 to 5 carbon atoms. Methyl, ethyl, ethynyl, or vinyl are particularly preferred. More specifically, it is preferable that both Ra 01 and Ra 02 are methyl or ethyl, or that Ra 01 is methyl or ethyl, while Ra 02 is ethynyl or vinyl.

[0067] In the above general formula (a0-1), Ar 01 is an aryl group in which one or all of the hydrogen atoms are replaced by iodine atoms, or a heteroaryl group in which one or all of the hydrogen atoms are replaced by iodine atoms.

[0068] Aryl groups in Ar 01 can be exemplified by groups that have had one hydrogen atom removed from an aromatic ring. Examples of such aromatic rings include benzene, naphthalene, anthracene, and phenanthrene. As for the aryl group in Ar 01, phenyl is preferred.

[0069] Examples of heteroaryl groups in Ar 01 include groups that have had one hydrogen atom removed from an aromatic heterocycle. Examples of such aromatic heterocycles include pyridine rings and thiophene rings. As a heteroaryl group in Ar 01, thiophenyl is preferred.

[0070] In Ar 01, some or all of the hydrogen atoms of the aryl and heteroaryl groups are substituted with iodine atoms. The number of iodine atoms is preferably 1 to 5, 1 to 3 is better, 2 or 3 is even better, and 3 is the best.

[0071] The aryl and heteroaryl groups in Ar 01 can also have substituents other than iodine atoms. Examples of such substituents include alkyl groups, alkoxy groups, halogen atoms, alkyl halides, and hydroxyl groups.

[0072] In the above general formula (a0-1), Ar 01 is preferably an aryl group having 1 to 3 iodine atoms, or a heteroaryl group having 1 to 3 iodine atoms, more preferably an aryl group having 1 to 3 iodine atoms, and even more preferably a phenyl group having 1 to 3 iodine atoms.

[0073] In the above, the aforementioned constituent unit (a01) is preferably a constituent unit (a011) derived from the compound shown in the following general formula (a0-1-1).

[0074] [In the formula, R01 is a hydrogen atom, an alkyl group having 1 to 10 carbon atoms, or a haloalkyl group having 1 to 10 carbon atoms. L001 is an ester bond, an aromatic hydrocarbon group, a cyclic group containing a lactone, or a divalent linked group having a group composed of such combinations. Ra01 and Ra02 are each independently a hydrocarbon group that can have substituents. Ar01 is an aryl group in which one or all of the hydrogen atoms are replaced by iodine atoms, or a heteroaryl group in which one or all of the hydrogen atoms are replaced by iodine atoms. The aforementioned aryl and heteroaryl groups may also have substituents other than iodine atoms.]

[0075] In the above general formula (a0-1-1), R 01, Ra 01, Ra 02 and Ar 01 are the same as R 01, Ra 01, Ra 02 and Ar 01 in the above general formula (a0-1).

[0076] In the above general formula (a0-1-1), L 001 is an ester bond, an aromatic hydrocarbon group, a cyclic group containing a lactone, or a divalent linking group having a group composed of such combinations. Examples of such divalent linking groups include those that are the same as the ester bond, aromatic hydrocarbon group, cyclic group containing a lactone, or divalent linking group having a group composed of such combinations in L 01 of the above general formula (a0-1).

[0077] In the above general formula (a0-1-1), L 001 is preferably any of the bases represented by the above general formulas (L0-r-1) to (L0-r-5), and is more preferably any of the bases represented by the above general formulas (L0-r-3) to (L0-r-5), and is more preferably the base shown by the above general formula (L0-r-3).

[0078] The following are specific examples of compounds represented by the general formula (a0-1).

[0079]

[0080]

[0081] As a constituent unit (a01) in the inhibitor composition of this embodiment, it is preferable that the constituent unit is derived from any of the compounds shown in the above chemical formulas (a01-01-1) to (a01-01-17), it is even more preferable that the constituent unit is derived from any of the compounds shown in the above chemical formulas (a01-01-2) to (a01-01-9), it is even more preferable that the constituent unit is derived from the compounds shown in the above chemical formulas (a01-01-6), (a01-01-8), or (a01-01-9), and it is particularly preferable that the constituent unit is derived from the compounds shown in the above chemical formulas (a01-01-8) or (a01-01-9).

[0082] The proportion of constituent units (a01) in component (A1) is preferably 20-80 mol% relative to the total (100 mol%) of all constituent units constituting component (A1), preferably 30-70 mol%, and even more preferably 40-60 mol%. By making the proportion of the constituent unit (a01) above the lower limit of the aforementioned preferred range, the reduction in sensitivity and roughness will be further improved. On the other hand, when it is below the upper limit of the aforementioned preferred range, that is, when the (A1) component has other constituent units besides the constituent unit (a01), the lithography properties can be further improved by balancing with the other constituent units described later.

[0083] Other constituent units (A1) Components may also have the above-mentioned constituent units (a01), as well as other constituent units as necessary. Other constituent units include, for example, a constituent unit (a1) containing an acid-decomposing group whose polarity increases due to the action of an acid; a constituent unit (a10) shown in the general formula (a10-1) described later; a constituent unit (a2) containing a cyclic group containing a lactone; and a constituent unit (a8) derived from a compound shown in the general formula (a8-1) described later. Furthermore, among the other constituent units, those that should be equivalent to the aforementioned constituent unit (a01) are excluded.

[0084] ≪Constituted Unit (a1)≫ The constituent unit (a1) is a constituent unit containing an acid-decomposing group whose polarity increases due to the action of acid. However, this excludes those that are part of the aforementioned constituent unit (a01).

[0085] Examples of acid-dissociative groups include the acid-dissociative groups of matrix resins that have been proposed so far as components of chemically amplifying inhibitors. As examples of acid-dissociating groups in matrix resins that have been proposed as components of chemically amplifying inhibitors, specific examples include "acetal-type acid-dissociating groups", "third-order alkyl ester-type acid-dissociating groups", "third-order alkoxycarbonyl acid-dissociating groups", and "second-order alkyl ester-type acid-dissociating groups" as described below.

[0086] Acetal type acid dissociation group: As an acid-dissociating group that protects the carboxyl or hydroxyl groups among the aforementioned polar groups, examples include the acid-dissociating group shown in the following general formula (a1-r-1) (hereinafter referred to as "acetal-type acid-dissociating group").

[0087] [In the formula, Ra'1 and Ra'2 are hydrogen atoms or alkyl groups. Ra'3 is a hydrocarbon group, and Ra'3 can also combine with either Ra'1 or Ra'2 to form a ring.]

[0088] In formula (a1-r-1), it is preferable that at least one of Ra' 1 and Ra' 2 is a hydrogen atom, and it is even more preferable that both of them are hydrogen atoms. When Ra'1 or Ra'2 is an alkyl group, examples of such alkyl groups include those exemplified in the description of α-substituted acrylates above, which are substituents that can bond to the carbon atom at the α-position. Alkyl groups with 1 to 5 carbon atoms are preferred. Specifically, linear or branched alkyl groups are preferred. More specifically, examples include methyl, ethyl, propyl, isopropyl, n-butyl, isobutyl, tert-butyl, pentyl, isopentyl, neopentyl, etc., with methyl or ethyl being preferred, and methyl being the most preferred.

[0089] In formula (a1-r-1), the hydrocarbon group of Ra'3 can be a straight-chain or branched alkyl group or a cyclic hydrocarbon group. The linear alkyl group is preferably composed of 1 to 5 carbon atoms, more preferably 1 to 4 carbon atoms, and even more preferably 1 or 2 carbon atoms. Specific examples include methyl, ethyl, n-propyl, n-butyl, and n-pentyl. Among these, methyl, ethyl, or n-butyl are preferred, with methyl or ethyl being more preferred.

[0090] The branched alkyl group is preferably composed of 3 to 10 carbon atoms, with 3 to 5 carbon atoms being more preferred. Specific examples include isopropyl, isobutyl, tert-butyl, isopentyl, neopentyl, 1,1-diethylpropyl, and 2,2-dimethylbutyl, with isopropyl being the most preferred.

[0091] Ra'3 is a cyclic hydrocarbon group, which can be an aliphatic hydrocarbon group, an aromatic hydrocarbon group, a polycyclic group, or a monocyclic group. As a monocyclic aliphatic hydrocarbon group, it is preferable to remove one hydrogen atom from the monocyclic alkane. The monocyclic alkane is preferably one with 3 to 6 carbon atoms, and specific examples include cyclopentane and cyclohexane. As a polycyclic aliphatic hydrocarbon group, it is preferable to be a group that removes one hydrogen atom from a polycyclic alkane. As for the polycyclic alkane, it is preferable to have 7 to 12 carbon atoms. Specific examples include adamantane, norcamphene, isocamphene, tricyclic decane, tetracyclic dodecane, etc.

[0092] In the case of Ra' 3, the cyclic hydrocarbon group is an aromatic hydrocarbon group, which 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 5-30, more preferably 5-20, even better if it has 6-15, and especially preferably 6-12. Examples of aromatic rings include aromatic hydrocarbon rings such as those of benzene, naphthalene, anthracene, and phenanthrene; and aromatic heterocycles in which a portion of the carbon atoms constituting the aforementioned aromatic hydrocarbon rings are replaced by heteroatoms. Examples of heteroatoms in aromatic heterocycles include oxygen atoms, sulfur atoms, and nitrogen atoms. Examples of aromatic heterocycles include pyridine rings and thiophene rings. Specifically, the aromatic hydrocarbon group in Ra'3 can be exemplified by a group (aryl or heteroaryl) from which one hydrogen atom is removed from the aforementioned aromatic hydrocarbon ring or aromatic heterocycle; a group from which one hydrogen atom is removed from an aromatic compound containing two or more aromatic rings (e.g., biphenyl, benzoylene, etc.); or a group from which one hydrogen atom of the aforementioned aromatic hydrocarbon ring or aromatic heterocycle is replaced by an alkyl group (e.g., arylalkyl groups such as benzyl, phenethyl, 1-naphthylmethyl, 2-naphthylmethyl, 1-naphthylethyl, 2-naphthylethyl, etc.). The number of carbon atoms in the alkyl group bonded to the aforementioned aromatic hydrocarbon ring or aromatic heterocycle is preferably 1 to 4, more preferably 1 to 2, and particularly preferably 1.

[0093] The cyclic hydrocarbon group in Ra'3 may also have substituents. Examples of such substituents include Ra x5 mentioned above.

[0094] When Ra'3 combines with either Ra'1 or Ra'2 to form a ring, a 4-7 member ring is preferred, and a 4-6 member ring is even more preferred. Specific examples of such a cyclic group include tetrahydropyranyl and tetrahydrofuranyl.

[0095] Third-order alkyl ester type acid dissociative group: As an acid-dissociative group that protects the carboxyl group among the above-mentioned polar groups, examples include the acid-dissociative group shown in the following general formula (a1-r-2). Furthermore, there are cases where the acid-dissociating group shown in the following formula (a1-r-2) is composed of an alkyl group, which will be referred to below as "third-order alkyl ester type acid-dissociating group".

[0096] [In the formula, Ra'4~Ra'6 are each a hydrocarbon group, and Ra'5 and Ra'6 can also combine with each other to form a ring].

[0097] Examples of hydrocarbon groups that can be classified as Ra'4 include linear or branched alkyl groups, linear or cyclic alkenyl groups, or cyclic hydrocarbon groups. The linear or branched alkyl groups and cyclic hydrocarbon groups (monocyclic aliphatic hydrocarbon groups, polycyclic aliphatic hydrocarbon groups, and aromatic hydrocarbon groups) in Ra' 4 can be examples of those that are the same as those in Ra' 3 mentioned above. In Ra' 4, the chain or cyclic alkenyl group is preferably an alkenyl group with 2 to 10 carbon atoms. As hydrocarbon groups of Ra'5 and Ra'6, examples such as Ra'3 mentioned above are similar.

[0098] In the case where Ra' 5 and Ra' 6 combine to form a ring, appropriate examples can be given as the basis shown in the following general formula (a1-r2-1), the basis shown in the following general formula (a1-r2-2), and the basis shown in the following general formula (a1-r2-3). On the other hand, in cases where Ra'4 to Ra'6 are independent hydrocarbon groups that are not combined with each other, the following general formula (a1-r2-4) can be used as an example.

[0099] In formula (a1-r2-1), Ra' 10 represents a linear or branched alkyl group with 1 to 12 carbon atoms, which can be partially replaced by a halogen atom or a heteroatom-containing group. Ra' 11 represents a group that forms an aliphatic cyclic group together with the carbon atom bonded to Ra' 10. In formula (a1-r2-2), Ya is a carbon atom. Xa is a group that forms a cyclic hydrocarbon group together with Ya. Some or all of the hydrogen atoms in this cyclic hydrocarbon group can also be replaced. Ra 101 to Ra 103 are each independently a 1-valent chain saturated hydrocarbon group with 1 to 10 carbon atoms or a 1-valent aliphatic cyclic saturated hydrocarbon group with 3 to 20 carbon atoms. Some or all of the hydrogen atoms in this chain saturated hydrocarbon group and aliphatic cyclic saturated hydrocarbon group can also be replaced. Two or more of Ra 101 to Ra 103 can also combine to form a cyclic structure. In formula (a1-r2-3), Yaa is a carbon atom. Xaa is a group that forms an aliphatic cyclic group together with Yaa. Ra 104 is an aromatic hydrocarbon group that can have substituents. In formula (a1-r2-4), Ra' 12 and Ra' 13 are each independently a monovalent chain saturated hydrocarbon group with 1 to 10 carbon atoms. Some or all of the hydrogen atoms in this chain saturated hydrocarbon group can also be substituted. Ra' 14 is a hydrocarbon group that can have substituents. * indicates a bond (the same applies below)].

[0100] In the above formula (a1-r2-1), Ra' 10 is a linear or branched alkyl group with 1 to 12 carbon atoms that can be replaced by halogen atoms or heteroatom-containing groups.

[0101] As a straight-chain alkyl group in Ra' 10, it is preferred to have 1 to 12 carbon atoms, with 1 to 10 carbon atoms being the most desirable, and 1 to 5 carbon atoms being the most desirable. As branched alkyl groups in Ra' 10, examples include those that are the same as those in Ra' 3 mentioned above.

[0102] In Ra' 10, one of the alkyl groups can be replaced by halogen atoms or heteroatom-containing groups. For example, one of the hydrogen atoms constituting the alkyl group can be replaced by halogen atoms or heteroatom-containing groups. Also, one of the carbon atoms constituting the alkyl group (such as methylene groups) can be replaced by heteroatom-containing groups. Examples of heteroatoms, as referred to here, include oxygen, sulfur, and nitrogen atoms. Examples of radicals containing heteroatoms include (-O-) and -C(=O)-O-. , -OC(=O)-, -C(=O)-, -OC(=O)-O-, -C(=O)-NH-, -NH-, -S-, -S(=O) 2-, -S(=O) 2-O-, etc.

[0103] In formula (a1-r2-1), Ra' 11 (an aliphatic cyclic group formed together with the carbon atoms bonded to Ra' 10) is preferably an aliphatic hydrocarbon group (alicyclic hydrocarbon group) exemplified as a monocyclic or polycyclic group of Ra' 3 in formula (a1-r-1). Among them, monocyclic alicyclic hydrocarbon groups are preferred, specifically cyclopentyl and cyclohexyl are more preferred.

[0104] In formula (a1-r2-2), as a cyclic hydrocarbon group formed by Xa and Ya together, an example is a group that removes 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 include those that are the same as those that the cyclic hydrocarbon group in Ra' 3 described above may have. In formula (a1-r2-2), examples of monovalent chain saturated hydrocarbon groups with 1 to 10 carbon atoms in Ra 101 to Ra 103 include methyl, ethyl, propyl, butyl, pentyl, hexyl, heptyl, octyl, decyl, etc. Examples of monocyclic aliphatic saturated hydrocarbon groups with 3 to 20 carbon atoms in Ra 101 to Ra 103 include monocyclic aliphatic saturated hydrocarbon groups such as cyclopropyl, cyclobutyl, cyclopentyl, cyclohexyl, cycloheptyl, cyclooctyl, cyclodecyl, and cyclododecyl; and polycyclic aliphatic saturated hydrocarbon groups such as bicyclic [2.2.2]octyl, tricyclic [5.2.1.0 2,6]decyl, tricyclic [3.3.1.1 3,7]decyl, tetracyclic [6.2.1.1 3,6.0 2,7]dodecyl, and adamantyl. From the perspective of ease of synthesis, Ra 101~Ra 103 preferably have a single-valent chain saturated hydrocarbon group with 1 to 10 carbon atoms, with hydrogen atoms, methyl, and ethyl atoms being preferred, and hydrogen atoms being the most preferred.

[0105] Examples of substituents found in the chain-like saturated hydrocarbon groups or aliphatic cyclic saturated hydrocarbon groups shown in Ra 101 to Ra 103 above include, for example, groups identical to those in Ra x5 above.

[0106] Examples of groups containing carbon-carbon double bonds formed by the combination of two or more Ra 101 to Ra 103 to create a cyclic structure include cyclopentenyl, cyclohexenyl, methylcyclopentenyl, methylcyclohexenyl, cyclopentylenevinyl, and cyclohexylenevinyl. Among these, cyclopentenyl, cyclohexenyl, and cyclopentylenevinyl are preferred from the viewpoint of ease of synthesis.

[0107] In formula (a1-r2-3), the aliphatic cyclic group system formed by Xaa and Yaa together is preferably an aliphatic hydrocarbon group exemplified as a monocyclic or polycyclic group of Ra' 3 in formula (a1-r-1). In formula (a1-r2-3), the aromatic hydrocarbon group in Ra 104 can be a group that has removed one or more hydrogen atoms from an aromatic hydrocarbon ring with 5 to 30 carbon atoms. Among them, Ra 104 is preferably a group that has removed one or more hydrogen atoms from an aromatic hydrocarbon ring with 6 to 15 carbon atoms, more preferably a group that has removed one or more hydrogen atoms from benzene, naphthalene, anthracene or phenanthrene, even more preferably a group that has removed one or more hydrogen atoms from benzene, naphthalene or anthracene, particularly preferably a group that has removed one or more hydrogen atoms from benzene or naphthalene, and most preferably a group that has removed one or more hydrogen atoms from benzene.

[0108] Examples of substituents that Ra 104 in formula (a1-r2-3) may have include methyl, ethyl, propyl, hydroxyl, carboxyl, halogen atom, alkoxy (methoxy, ethoxy, propoxy, butoxy, etc.), alkoxy carbonyl, etc.

[0109] 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 include those identical to the monovalent chain saturated hydrocarbon groups with 1 to 10 carbon atoms 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. Among them, Ra' 12 and Ra' 13 are preferably alkyl groups with 1 to 5 carbon atoms, more preferably alkyl groups with 1 to 5 carbon atoms, and even more preferably methyl or ethyl, with methyl being the most preferred. In the case of substitution of the chain saturated hydrocarbon groups shown in Ra' 12 and Ra' 13 above, examples of substituents include groups identical to those in Ra x5 mentioned above.

[0110] In formula (a1-r2-4), Ra' 14 is a hydrocarbon group that may have substituents. Examples of hydrocarbon groups in Ra' 14 include linear or branched alkyl groups or cyclic hydrocarbon groups.

[0111] The linear alkyl group in Ra' 14 is preferably composed of 1 to 5 carbon atoms, more preferably 1 to 4, and even more preferably 1 or 2. Specific examples include methyl, ethyl, n-propyl, n-butyl, and n-pentyl. Among these, methyl, ethyl, or n-butyl are preferred, with methyl or ethyl being the most preferred.

[0112] The branched alkyl group in Ra' 14 is preferably composed of 3 to 10 carbon atoms, with 3 to 5 being more preferred. Specific examples include isopropyl, isobutyl, tert-butyl, isopentyl, neopentyl, 1,1-diethylpropyl, and 2,2-dimethylbutyl, with isopropyl being the most preferred.

[0113] Ra' 14 is a cyclic hydrocarbon group, which can be an aliphatic hydrocarbon group or an aromatic hydrocarbon group, and can be a polycyclic group or a monocyclic group. As a monocyclic aliphatic hydrocarbon group, it is preferable to be a group that removes one hydrogen atom from a monocyclic alkane. As for the monocyclic alkane, it is preferable to have 3 to 6 carbon atoms, and specific examples include cyclopentane and cyclohexane. As a polycyclic aliphatic hydrocarbon group, it is preferable to be a group that removes one hydrogen atom from a polycyclic alkane. As for the polycyclic alkane, it is preferable to have 7 to 12 carbon atoms. Specific examples include adamantane, norcamphene, isocamphene, tricyclic decane, tetracyclic dodecane, etc.

[0114] As for the aromatic hydrocarbon group in Ra' 14, examples can be those that are the same as the aromatic hydrocarbon group in Ra 104. Among them, Ra' 14 is preferably a group in which one or more hydrogen atoms have been removed from the aromatic hydrocarbon ring with 6 to 15 carbon atoms, a group in which one or more hydrogen atoms have been removed from benzene, naphthalene, anthracene or phenanthrene is more preferred, a group in which one or more hydrogen atoms have been removed from benzene, naphthalene or anthracene is even more preferred, a group in which one or more hydrogen atoms have been removed from naphthalene or anthracene is particularly preferred, and a group in which one or more hydrogen atoms have been removed from naphthalene is the best. Examples of substituents that Ra' 14 may have include those that are the same as those that Ra 104 may have.

[0115] In the case where Ra' 14 in formula (a1-r2-4) is a naphthyl group, the position of the bond between Ra' 14 and the third carbon atom in the aforementioned formula (a1-r2-4) can be either the 1st or 2nd position of the naphthyl group. In formula (a1-r2-4), Ra' 14 represents anthracene, and its position in relation to the third-order carbon atom in the aforementioned formula (a1-r2-4) can be any one of the 1, 2, or 9 positions of the anthracene group.

[0116] The following are specific examples of the basis shown in the aforementioned formula (a1-r2-1).

[0117]

[0118]

[0119]

[0120] The following are specific examples of the basis shown in the aforementioned formula (a1-r2-2).

[0121]

[0122]

[0123]

[0124] The following are specific examples of the basis shown in the aforementioned formula (a1-r2-3).

[0125]

[0126] The following are specific examples of the basis shown in the aforementioned formula (a1-r2-4).

[0127]

[0128] Third-order alkoxycarbonyl acid dissociation group: As an acid-dissociating group that protects the hydroxyl group in the aforementioned polar group, examples include the acid-dissociating group shown in the following general formula (a1-r-3) (hereinafter referred to as "third-order alkoxycarbonyl acid dissociating group" for convenience).

[0129] [In the formula, Ra' 7 to Ra' 9 are each alkyl groups].

[0130] In formula (a1-r-3), Ra' 7 to Ra' 9 are preferably alkyl groups with 1 to 5 carbon atoms, and are more preferably alkyl groups with 1 to 3 carbon atoms. Furthermore, the total number of carbon atoms of all alkyl groups is preferably 3 to 7, more preferably 3 to 5, and best preferably 3 to 4.

[0131] Examples of constituent units (a1) include: acrylates derived from which the hydrogen atom bonded to the carbon atom at the α-position can be replaced by a substituent; a unit derived from acrylamide; a unit derived from hydroxystyrene or hydroxystyrene derivatives in which at least a portion of the hydrogen atom in the hydroxyl group is protected by a substituent containing the aforementioned acid-degrading group; and a unit derived from vinyl benzoic acid or vinyl benzoic acid derivatives in which at least a portion of the hydrogen atom in the -C(=O)-OH group is protected by a substituent containing the aforementioned acid-degrading group.

[0132] Secondary alkyl ester type acid dissociative group: Among the aforementioned polar groups, examples of acid-dissociative groups that protect carboxyl groups include, for instance, the acid-dissociative group represented by the following general formula (a1-r-4).

[0133] [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 can also combine with Ra' 11a or Ra' 11b to form a ring. Ra' 11a or Ra' 11b can also combine with Ra' 12 to form a ring.]

[0134] In the formula, the hydrocarbon group in Ra' 10 and Ra' 12 can be the same as that in Ra' 3 mentioned above. In the formula, the alkyl group in Ra' 11a and Ra' 11b can be the same as the alkyl group in the aforementioned Ra' 1. 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.

[0135] Ra' 10 can also combine with Ra' 11a or Ra' 11b to form a ring. This ring can be polycyclic, monocyclic, alicyclic, or aromatic. The alicyclic and aromatic rings may also contain heteroatoms.

[0136] As Ra' 10 can be combined with Ra' 11a or Ra' 11b to form a ring, among the above, monocyclic alkenes, rings in which one part of the carbon atom of a monocyclic alkene is replaced by heteroatoms (oxygen atoms, sulfur atoms, etc.), monocyclic dienes are preferred, cycloalkenes with 3 to 6 carbon atoms are preferred, and cyclopentene or cyclohexene are preferred.

[0137] The ring formed by the combination of Ra' 10 and Ra' 11a or Ra' 11b can also be a condensation ring. Specific examples of such condensation rings include indene.

[0138] The ring formed by the combination of Ra' 10 and Ra' 11a or Ra' 11b can also have substituents. Examples of such substituents include Ra x5 mentioned above.

[0139] Ra' 11a or Ra' 11b and Ra' 12 can also combine to form a ring. Examples of such rings include those formed by combining Ra' 10 with Ra' 11a or Ra' 11b.

[0140] The following are specific examples of the basis shown in the aforementioned formula (a1-r-4).

[0141]

[0142] The following are specific examples of the constituent unit (a1). In the following formulas, Rα represents a hydrogen atom, a methyl group, or a trifluoromethyl group.

[0143]

[0144]

[0145]

[0146]

[0147]

[0148]

[0149]

[0150]

[0151] The constituent unit (a1) of component (A1) may be one or more types.

[0152] The proportion of constituent unit (a1) in component (A1) is preferably less than 50 mol% relative to the total (100 mol%) of all constituent units constituting component (A1), and preferably between 0 and 30 mol%.

[0153] Regarding the constituent unit (a10): The constituent unit (a10) is the constituent unit shown in the following general formula (a10-1). However, this excludes those that are part of the aforementioned constituent unit (a01).

[0154] [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].

[0155] 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. The R group is preferably composed of hydrogen atoms, alkyl groups with 1 to 5 carbon atoms, or fluorinated alkyl groups with 1 to 5 carbon atoms. From an industrial availability perspective, hydrogen atoms, methyl groups, or trifluoromethyl groups are preferred, hydrogen atoms or methyl groups are even better, and hydrogen atoms are the most preferred.

[0156] In the aforementioned formula (a10-1), Ya x1 is a single bond or a divalent linker. In the aforementioned chemical formula, there is no particular limitation on the divalent linking group in Ya x1. Suitable examples include divalent hydrocarbon groups that can have substituents and divalent linking groups that contain heteroatoms.

[0157] As Ya x1, it is composed of single bonds and ester bonds. [-C(=O)-O-, -OC(=O)-], ether bond (-O-), straight-chain or branched alkyl groups, or combinations thereof are preferred, with single bonds and ester bonds being the most common. [-C(=O)-O-, -OC(=O)-] are preferred.

[0158] In the aforementioned formula (a10-1), Wa x1 is an aromatic hydrocarbon group that may have substituents. Examples of aromatic hydrocarbon groups in Wa x1 include groups that remove (n ax1+1) hydrogen atoms from an aromatic ring that may have substituents. There are no particular limitations on the aromatic ring as long as it is 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. Specific examples of such aromatic rings include aromatic hydrocarbon rings of benzene, naphthalene, anthracene, and phenanthrene; and aromatic heterocycles in which a portion of the carbon atoms constituting the aforementioned aromatic hydrocarbon ring is replaced by heteroatoms. Examples of heteroatoms in aromatic heterocycles include oxygen, sulfur, and nitrogen atoms. Specific examples of aromatic heterocycles include pyridine rings and thiophene rings. Furthermore, as an aromatic hydrocarbon group in Wa x1, examples can be found such as a group that removes (n ax1+1) hydrogen atoms from an aromatic compound (e.g., biphenyl, fumonisin, etc.) containing an aromatic ring that may have two or more substituents. As Wa x1, it is preferable to have a group that has removed (n ax1+1) hydrogen atoms from benzene, naphthalene, anthracene or biphenyl, it is even preferable to have a group that has removed (n ax1+1) hydrogen atoms from benzene or naphthalene, and it is even more preferable to have a group that has removed (n ax1+1) hydrogen atoms from benzene.

[0159] The aromatic hydrocarbon group in Wa x1 may or may not have substituents. Examples of substituents include alkyl groups, alkoxy groups, halogen atoms, and alkyl halides. Examples of alkyl, alkoxy, halogen atoms, and alkyl halides that serve as substituents include those similar to those used as substituents for the cyclic aliphatic hydrocarbon group in Ya x1. The aforementioned substituents are preferably straight-chain or branched alkyl groups with 1 to 5 carbon atoms, more preferably straight-chain or branched alkyl groups with 1 to 3 carbon atoms, and even more preferably ethyl or methyl, with methyl being particularly preferred. The aromatic hydrocarbon group in Wa x1 is preferably unsubstituented.

[0160] In the aforementioned formula (a10-1), n ​​ax1 is an integer greater than or equal to 1, preferably an integer from 1 to 10, preferably an integer from 1 to 5, preferably 1, 2 or 3, and preferably 1 or 2.

[0161] The following are specific examples of the constituent unit (a10) shown in the aforementioned formula (a10-1). In the following formulas, Rα represents a hydrogen atom, a methyl group, or a trifluoromethyl group.

[0162]

[0163]

[0164]

[0165] (A1) The constituent unit (a10) of component (A1) may be one or more. When component (A1) has a constituent unit (a10), the proportion of constituent unit (a10) in component (A1) is preferably 20-80 mol% relative to the total (100 mol%) of all constituent units constituting component (A1), preferably 30-70 mol%, and even more preferably 30-60 mol%. By setting the proportion of the constituent unit (a10) above the lower limit, it becomes easier to increase sensitivity. On the other hand, by setting it below the upper limit, it becomes easier to balance with other constituent units.

[0166] Regarding the constituent units (a2): Component (A1) may also be a constituent unit (a2) containing a cyclic group containing lactone (but, removing the constituent units (a01) and (a1)). When the lactone-containing cyclic group of the constituent unit (a2) is used to form the resist film, it effectively improves the adhesion of the resist film to the substrate. Furthermore, by having the constituent unit (a2), the adhesion of the resist film to the substrate can be improved by appropriately adjusting the acid diffusion length, and the solubility during development can be appropriately adjusted, thereby improving the lithography properties.

[0167] "Lactone-containing cyclic groups" refers to cyclic groups whose ring skeleton contains a ring including -OC (=O)- (lactone ring). The lactone ring is counted as the first ring; if it contains only a lactone ring, it is a monocyclic group; if it has other ring structures, regardless of their structure, it is called a polycyclic group. Lactone-containing cyclic groups can be either monocyclic or polycyclic. There are no particular limitations on the lactone-containing cyclic group in the constituent unit (a2), and any group can be used. Specifically, examples can be given by the groups represented by the following general formulas (a2-r-1) to (a2-r-7).

[0168] [In the formula, Ra' 21 are each independently a hydrogen atom, alkyl group, alkoxy group, halogen atom, haloalkyl group, hydroxyl group, -COOR", -OC(=O)R", hydroxyalkyl group or cyano group; R" is a hydrogen atom, alkyl group, or cyclic group containing lactone; A" may contain alkyl group, oxygen atom or sulfur atom with 1 to 5 carbon atoms of oxygen atom (-O-) or sulfur atom (-S-), n' is an integer from 0 to 2, and m' is 0 or 1. * indicates the bonding position (the same applies below)].

[0169] In the aforementioned general formulas (a2-r-1) to (a2-r-7), the alkyl group in Ra' 21 is preferably an alkyl group with 1 to 6 carbon atoms. The alkyl group is preferably linear or branched. Specific examples include methyl, ethyl, propyl, isopropyl, n-butyl, isobutyl, tert-butyl, pentyl, isopentyl, neopentyl, and hexyl. Among these, methyl or ethyl is preferred, with methyl being particularly preferred. The alkoxy group in Ra' 21 is preferably an alkoxy group with 1 to 6 carbon atoms. The alkoxy group is preferably straight-chain or branched. Specifically, examples include alkyl groups formed by linking an alkyl group to an oxygen atom (-O-), as exemplified by the alkyl group in Ra' 21 mentioned above. Fluorine atoms are preferred as halogen atoms in Ra' 21. As a haloalkyl group in Ra' 21, examples include groups in which one or all of the hydrogen atoms of the alkyl group in Ra' 21 are replaced by the aforementioned halogen atoms. Fluorinated alkyl groups are preferred as such haloalkyl groups, and perfluoroalkyl groups are particularly preferred.

[0170] In Ra' 21, R” in -COOR” and -OC(=O)R” is a hydrogen atom, an alkyl group, or a cyclic group containing a lactone. As the alkyl group in "R", it can be any of the following: straight-chain, branched, or cyclic, with 1 to 15 carbon atoms being preferred. When R” is a straight-chain or branched alkyl group, it is preferred to have 1 to 10 carbon atoms, more preferably 1 to 5 carbon atoms, and methyl or ethyl is especially preferred. 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 ideally 5 to 10 carbon atoms. Specifically, examples include removing one or more hydrogen atoms from monocyclic alkanes that may or may not be replaced by fluorine atoms or fluorinated alkyl groups; and removing one or more hydrogen atoms from polycyclic alkanes such as bicyclic alkanes, tricyclic alkanes, and tetracyclic alkanes. More specifically, examples include removing one or more hydrogen atoms from monocyclic alkanes such as cyclopentane and cyclohexane; and removing one or more hydrogen atoms from polycyclic alkanes such as adamantane, norcamphene, isocamphene, tricyclic decane, and tetracyclic dodecane. Examples of lactone-containing cyclic groups in R” include those that are the same as the groups 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, examples include groups in Ra' 21 in which at least one hydrogen atom is replaced by a hydroxyl group.

[0171] As Ra' 21, each of the above-mentioned independent systems is preferably composed of a hydrogen atom or a cyano group.

[0172] In the aforementioned general formulas (a2-r-2), (a2-r-3), and (a2-r-5), the alkyl group having 1 to 5 carbon atoms in "A" is preferably a straight-chain or branched alkyl group, such as methylene, ethyl alkyl, n-propyl alkyl, and isopropyl alkyl. Specific examples of this alkyl group containing oxygen or sulfur atoms include those with oxygen atoms at the end of the aforementioned alkyl group or between carbon atoms. The bases -O- or -S- can be exemplified by, for example, -O-CH2-, -CH2-O-CH2-. -S-CH 2-, -CH 2-S-CH 2-, etc. As "A", it is preferred to be an alkyl group with 1 to 5 carbon atoms or -O-, with an alkyl group with 1 to 5 carbon atoms being more preferred, and methylene being the best.

[0173] The following are specific examples of the bases represented by the general formulas (a2-r-1) to (a2-r-7).

[0174]

[0175]

[0176] As a constituent unit (a2), it is preferable to use an acrylate derived from an acrylate in which the hydrogen atom bonded to the carbon atom at the α position can be replaced by a substituent. The constituent unit (a2) is preferably the constituent unit shown in the following general formula (a2-1).

[0177] [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 linker. La 21 is an -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 will not be -CO-. Ra 21 is a cyclic group containing a lactone.

[0178] In the aforementioned formula (a2-1), R is the same as described above. As R, hydrogen atom, alkyl group with 1 to 5 carbon atoms, or fluorinated alkyl group with 1 to 5 carbon atoms are preferred. From the viewpoint of ease of industrial acquisition, hydrogen atom or methyl group is particularly preferred.

[0179] In the aforementioned formula (a2-1), there is no particular limitation on the divalent linking group in Ya 21. Suitable examples include divalent hydrocarbon groups with substituents, divalent linking groups containing heteroatoms, etc.

[0180] As Ya 21, it is preferred to be a single bond, an ester bond [-C(=O)-O-], an ether bond (-O-), a straight-chain or branched alkyl group, or a combination thereof.

[0181] In the aforementioned equation (a2-1), Ya 21 is a single bond, and La 21 is a single bond. -COO- or -OCO- is preferred.

[0182] In the aforementioned formula (a2-1), Ra 21 is a cyclic group containing lactone. As lactone-containing cyclic groups in Ra 21, suitable examples include those represented by the general formulas (a2-r-1) to (a2-r-7) mentioned above. The bases represented by the aforementioned general formulas (a2-r-1), (a2-r-2), or (a2-r-6) are preferred, with the bases represented by the aforementioned general formulas (a2-r-1) or (a2-r-2) being more preferred. Specifically, the bases represented by any of the aforementioned chemical formulas (r-lc-1-1) to (r-lc-1-7), (r-lc-2-1) to (r-lc-2-18), and (r-lc-6-1) are preferred, with the bases represented by any of the aforementioned chemical formulas (r-lc-1-1), (r-lc-2-1), or (r-lc-2-7) being more preferred.

[0183] (A1) The constituent units (a2) of a component may be one or more. When component (A1) has a constituent unit (a2), the proportion of constituent unit (a2) relative to the total (100 mol%) of all constituent units constituting component (A1) is preferably 5-80 mol%, preferably 5-70 mol%, and preferably 5-60 mol%. When the proportion of the constituent unit (a2) is set above the optimal lower limit, the effects resulting from the inclusion of the constituent unit (a2) can be fully achieved through the aforementioned effects. Below the upper limit, a balance with other constituent units can be achieved, and various lithography properties become good.

[0184] Regarding the constituent units (a8): The constituent unit (a8) is a constituent unit derived from the compound shown in the following general formula (a8-1). However, this excludes those that constitute the unit (a0).

[0185] [In the formula, W2 is a polymerizable group. Yax2 is a single bond or a (nax2+1) valence linker. 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 combine with each other to form a ring structure. nax2 is an integer from 1 to 3].

[0186] The "polymerizable group" in W 2 refers to a group that can be used to polymerize compounds containing polymerizable groups through free radical polymerization, such as a group containing multiple bonds between carbon atoms, such as vinyl double bonds.

[0187] As a base containing a polymerizable group, it can be a base composed solely of a polymerizable group, or it can be a base composed of a polymerizable group and other groups besides that polymerizable group. Examples of other groups besides that polymerizable group include, for instance, a divalent hydrocarbon group having a substituent, or a divalent linker group containing a heteroatom. Examples of suitable bases containing polymerizable groups include, for instance, the base represented by the chemical formula: C(R X11)(R X12)=C(R X13)-Ya x0-. In this chemical formula, RX11, RX12 and RX13 are each hydrogen atoms, alkyl groups with 1 to 5 carbon atoms or alkyl halides with 1 to 5 carbon atoms, and Yax0 is a single bond or a divalent linker.

[0188] Examples of condensation rings formed by Yax2 and W2 include condensation rings formed by the polymerizable group at the W2 site and Yax2, and condensation rings formed by groups other than the polymerizable group at the W2 site and Yax2. The condensation ring formed by Ya x2 and W 2 can also have substituents.

[0189] The following shows a specific example of the constituent unit (a8). In the following formula, Rα represents a hydrogen atom, a methyl group, or a trifluoromethyl group.

[0190]

[0191] In the above examples, the constituent unit (a8) is preferably selected from at least one of the groups 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), and more preferably from at least one of the groups of constituent units represented by chemical formulas (a8-1-01) to (a8-1-04) and (a8-1-09).

[0192] (A1) The constituent units (a8) of the component may be one or more. The proportion of constituent unit (a8) in component (A1) is preferably less than 50 mol% relative to the total (100 mol%) of all constituent units constituting component (A1), and preferably between 0 and 30 mol%.

[0193] The inhibitor composition may contain a single (A1) component or two or more components in combination. In the inhibitor composition of this embodiment, the (A1) component can be exemplified by a polymer compound having a repeating structure of a constituent unit (a01). As a component of (A1), examples of polymeric compounds containing repeating structures of constituent units (a01) and (a10) can also be appropriately cited above.

[0194] More specifically, as a component of (A1), suitable examples include, for instance, polymeric compounds containing repeating structures of constituent units (a01) and (a10); polymeric compounds containing repeating structures of constituent units (a01) and (a2); and polymeric compounds containing repeating structures of constituent units (a01), (a10), and (a2).

[0195] In a polymer compound having a repeating structure of constituent units (a01) and constituent units (a10), the proportion of constituent units (a01) relative to the total number of constituent units constituting the polymer compound (100 mol%) is preferably 10-90 mol%, more preferably 20-80 mol%, even more preferably 30-70 mol%, and particularly preferably 40-60 mol%. Furthermore, relative to the total number of all constituent units constituting the polymer (100 mol%), the proportion of constituent units (a10) in the polymer is preferably 10-90 mol%, more preferably 20-80 mol%, even more preferably 30-70 mol%, and particularly preferably 40-60 mol%.

[0196] In a polymer compound having a repeating structure of constituent units (a01) and constituent units (a2), the proportion of constituent units (a01) relative to the total number of constituent units constituting the polymer compound (100 mol%) is preferably 10-90 mol%, more preferably 20-80 mol%, even more preferably 30-70 mol%, and particularly preferably 40-60 mol%. Furthermore, relative to the total number of all constituent units constituting the polymer (100 mol%), the proportion of constituent units (a2) in the polymer is preferably 10-90 mol%, more preferably 20-80 mol%, even more preferably 30-70 mol%, and particularly preferably 40-60 mol%.

[0197] In a polymer compound having a repeating structure of constituent units (a01), (a10), and (a2), the proportion of constituent units (a01) relative to the total number of constituent units constituting the polymer compound (100 mol%) is preferably 10-90 mol%, more preferably 20-80 mol%, even more preferably 30-70 mol%, and particularly preferably 40-60 mol%. Furthermore, relative to the total number of all constituent units constituting the polymer (100 mol%), the proportion of constituent units (a10) in the polymer is preferably 5-80 mol%, more preferably 10-70 mol%, even more preferably 20-60 mol%, and particularly preferably 30-50 mol%. Furthermore, relative to the total number of all constituent units constituting the polymer (100 mol%), the proportion of constituent units (a2) in the polymer is preferably 1 to 30 mol%, more preferably 3 to 20 mol%, even more preferably 5 to 20 mol%, and particularly preferably 5 to 15 mol%.

[0198] The (A1) component can be manufactured by dissolving the monomers from which each constituent unit is derived in a polymerization solvent and then adding a free radical polymerization initiator such as azobisisobutyronitrile (AIBN) or dimethyl azobisisobutyrate (e.g., V-601) to polymerize it. Alternatively, the (A1) component can be manufactured by dissolving the monomer that derives the constituent unit (a01) and the monomer that derives the constituent unit other than (a01) as necessary (e.g., constituent unit (a10)) in a polymerization solvent, adding a free radical polymerization initiator as described above, and then carrying out a deprotection reaction. Furthermore, during aggregation, it is also possible to use them in combination, for example, Chain transfer agents such as HS-CH 2-CH 2-CH 2-C(CF 3) 2-OH are introduced at the end with -C(CF 3) 2-OH groups. In this way, copolymers with hydroxyalkyl groups in which one of the hydrogen atoms of the alkyl group is partially replaced by fluorine atoms effectively reduce development defects or reduce LER (line edge roughness: unevenness of the line sidewalls).

[0199] (A1) The weight average molecular weight (Mw) of the component (based on gel permeation chromatography (GPC) and converted to polystyrene) is not particularly limited, but is preferably 1,000 to 50,000, more preferably 2,000 to 30,000, and even more preferably 3,000 to 20,000. When the Mw of component (A1) is below the upper limit of the preferred range, it has sufficient solubility in the solvent required for use as a resist; when it is above the lower limit of the preferred range, it has good resistance to dry etching or good resist pattern profile shape. (A1) The dispersion (Mw / Mn) of the component is not particularly limited, but 1.0~4.0 is preferred, 1.0~3.0 is better, and 1.0~2.0 is especially preferred. Furthermore, Mn represents the number average molecular weight.

[0200] 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 (A) component. As for component (A2), there are no particular limitations; it may be selected from the majority of previously known base material components used as chemically amplifying inhibitors. (A2) The components can be a single high molecular weight compound or a low molecular weight compound, or a combination of two or more.

[0201] The proportion of component (A1) in component (A) relative to the total mass of component (A) is preferably 25% by mass or more, preferably 50% by mass or more, and even more preferably 75% by mass or more, and can also be 100% by mass. When the proportion is 25% by mass or more, it becomes easier to form resist patterns with excellent lithography properties such as high sensitivity or improved resolution and roughness.

[0202] In the resist composition of this embodiment, the content of component (A) can be adjusted according to the desired resist film thickness, etc.

[0203] <Other Ingredients> In addition to component (A) mentioned above, the inhibitor composition of this embodiment may also contain other components. Examples of other components include components (B), (D), (E), (F), and (S) as shown below.

[0204] ≪Acid-generating component (B)≫ The resist composition of this embodiment is preferably an acid-generating agent component (B) that produces acid due to exposure. As for component (B), there are no particular limitations, and any acid generator that has been proposed to be used as a chemical amplification inhibitor component can be used. Examples of such acid-generating agents include, for instance, onium salt acid-generating agents such as monazite or strontium salts, oxime sulfonate acid-generating agents; diazomethane acid-generating agents such as dialkyl or diarylsulfonyldiazomethanes and poly(disulfonyl)diazomethanes; nitrobenzyl sulfonate acid-generating agents, imino sulfonate acid-generating agents, and disulfonate acid-generating agents, among many others.

[0205] Examples of compounds that can be used as onium salt acid generators include, for example, compounds represented by general formula (b-1) (hereinafter also referred to as "(b-1) component"), compounds represented by general formula (b-2) (hereinafter also referred to as "(b-2) component"), or compounds represented by general formula (b-3) (hereinafter also referred to as "(b-3) component").

[0206] Examples of compounds that can be used as onium salt acid generators include, for example, compounds represented by general formula (b-1) (hereinafter also referred to as "(b-1) component"), compounds represented by general formula (b-2) (hereinafter also referred to as "(b-2) component"), or compounds represented by general formula (b-3) (hereinafter also referred to as "(b-3) component").

[0207] [In the formula, R101 and R104~R108 are each independently a cyclic group that may have substituents, a chain-like alkyl group that may have substituents, or a chain-like alkenyl group that may have substituents. R104 and R105 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 or a single bond containing an oxygen atom. V101~V103 are each independently a single bond, an alkyl group, or a fluorinated alkyl group. L101~L102 are each independently a single bond or an oxygen atom. L103~L105 are each independently a single bond, -CO-, or -SO2-. m is an integer greater than or equal to 1, and M'm+ is an onium cation with an m valence.]

[0208] {Anion Section} Anions in component (b-1) 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.

[0209] Cyclic groups that may have substituents: The cyclic group system is preferably composed of cyclic hydrocarbon groups, which can be aromatic or aliphatic. Aliphatic hydrocarbon groups refer to hydrocarbon groups that do not possess aromaticity. Furthermore, aliphatic hydrocarbon groups can be saturated or unsaturated, but saturated groups are generally preferred.

[0210] 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 3-30, more preferably 5-30, even more preferably 5-20, particularly preferably 6-15, and best preferably 6-10. However, this number of carbon atoms refers to the number of carbon atoms excluding those in the substituents. Aromatic rings, which are aromatic hydrocarbon groups in R 101, can be specifically exemplified by benzene, naphthalene, anthracene, phenanthrene, biphenyl, or aromatic heterocycles in which a portion of the carbon atom constituting the aromatic ring is replaced by a heteroatom. Heteroatoms in aromatic heterocycles can be exemplified by oxygen, sulfur, and nitrogen atoms. Specifically, the aromatic hydrocarbon group in R 101 can be exemplified by groups in which one hydrogen atom is removed from the aforementioned aromatic ring (aryl: for example, phenyl, naphthyl, etc.), or groups in which one hydrogen atom of the aforementioned aromatic ring is replaced by an alkyl group (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 (the alkyl chain in the arylalkyl group) is preferably 1 to 4, more preferably 1 to 2, and particularly preferably 1.

[0211] Examples of cyclic aliphatic hydrocarbon groups in R 101 include aliphatic hydrocarbon groups whose structures contain rings. Examples of aliphatic hydrocarbon groups containing a ring in this structure include alicyclic hydrocarbon groups (groups that remove one hydrogen atom from an aliphatic hydrocarbon ring), alicyclic hydrocarbon groups bonded to the end of a straight-chain or branched aliphatic hydrocarbon group, and alicyclic hydrocarbon groups present in the middle of a straight-chain or branched aliphatic hydrocarbon group. The aforementioned alicyclic hydrocarbon system is preferably composed of 3 to 20 carbon atoms, with 3 to 12 being more preferred. The aforementioned alicyclic hydrocarbon group can be either a polycyclic or monocyclic group. For monocyclic alicyclic hydrocarbon groups, it is preferable to have a group from which one or more hydrogen atoms have been removed from the monocyclic alkane. For the monocyclic alkane, a group with 3 to 6 carbon atoms is preferred; specific examples include cyclopentane and cyclohexane. For polycyclic alicyclic hydrocarbon groups, it is preferable to have a group from which one or more hydrogen atoms have been removed from the polycyclic alkane; for the polycyclic alkane, a group with 7 to 30 carbon atoms is preferred. Among these, polycyclic alkanes with a cross-linked ring system, such as adamantane, norcamphene, isocamphene, tricyclodecane, and tetracyclododecane, and polycyclic alkanes with a condensed ring system, such as cyclic groups with a steroid skeleton, are also preferred.

[0212] Among them, the cyclic aliphatic hydrocarbon group in R 101 is preferably a group that has removed one or more hydrogen atoms from a monocyclic alkane or polycyclic alkane, and is more preferably a group that has removed one hydrogen atom from a polycyclic alkane. It is more preferably adamantyl or norbornel, and is especially preferred to be adamantyl.

[0213] The linear aliphatic hydrocarbon group that can be bonded to an alicyclic hydrocarbon group preferably has 1 to 10 carbon atoms, more preferably 1 to 6, even better 1 to 4, and most preferably 1 to 3. As a linear aliphatic hydrocarbon group, a linear alkyl group is preferred; specific examples include methylene [-CH 2-] and ethyl groups. [-(CH 2) 2-], trimethylene [-(CH 2) 3-], tetramethylene [-(CH 2) 4-], pentamethylene [-(CH 2) 5-], etc. Branched aliphatic hydrocarbon groups that can bond to alicyclic hydrocarbon groups are preferably composed of 2 to 10 carbon atoms, more preferably 3 to 6, and even more preferably 3 or 4, with 3 being the most desirable. As branched aliphatic hydrocarbon groups, branched alkyl groups are preferred, specifically including -CH(CH 3)-, -CH(CH 2CH 3)-, and -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 and other alkyl alkyl groups, such as -CH(CH 3)CH 2CH 2CH 2- and -CH 2CH(CH 3)CH 2CH 2-. Among alkyl alkyl groups, straight-chain alkyl groups with 1 to 5 carbon atoms are preferred.

[0214] Furthermore, the cyclic hydrocarbon group in R 101 can also contain heteroatoms, just like 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 following general formulas (b5-r-1) to (b5-r-4), and other heterocyclic groups represented by the following chemical formulas (r-hr-1) to (r-hr-16). In the formulas, * indicates a bond at the Y 101 bond in formula (b-1).

[0215] In the formula, 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; R" is a hydrogen atom, alkyl group, cyclic group containing lactone, or containing -SO 2- cyclic group; B” is an alkyl group with 1 to 5 carbon atoms, which may contain oxygen or sulfur atoms, and n' is an integer from 0 to 2. * indicates the bonding site.

[0216] 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, which may contain oxygen atoms or sulfur atoms. As B”, an alkyl group with 1 to 5 carbon atoms or -O- is preferred, an alkyl group with 1 to 5 carbon atoms is more preferred, and methylene is even more preferred.

[0217] In the aforementioned general formulas (b5-r-1) to (b5-r-4), each of 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, with each being preferably an independently hydrogen atom or cyano group.

[0218] The following are specific examples of the bases represented by the general formulas (b5-r-1) to (b5-r-4). In the formulas, "Ac" represents the acetyl group.

[0219]

[0220]

[0221]

[0222]

[0223] Examples of substituents in the cyclic group of R 101 include alkyl, alkoxy, halogen atom, alkyl halide, hydroxyl, carbonyl, nitro, etc. As for the alkyl group used as a substituent, it is preferred to be an alkyl group with 1 to 5 carbon atoms, and methyl, ethyl, propyl, n-butyl, and tert-butyl are the best. Alkoxy groups used as substituents are preferably alkoxy groups with 1 to 5 carbon atoms, with methoxy, ethoxy, n-propoxy, iso-propoxy, n-butoxy, and tert-butoxy being more preferred, and methoxy and ethoxy being the best. Halogen atoms that can be used as substituents include fluorine, chlorine, bromine, and iodine atoms, with fluorine atoms being preferred. Examples of alkyl halogens that can be used as substituents include alkyl groups with 1 to 5 carbon atoms, such as methyl, ethyl, propyl, n-butyl, tert-butyl, etc., in which one or all of the hydrogen atoms are replaced by the aforementioned halogen atoms. The carbonyl group that serves as the substituent is the methylene group that forms the cyclic hydrocarbon group. (-CH 2-) is a base that is replaced by a substance.

[0224] The cyclic hydrocarbon group in R 101 can also be a condensed cyclic group comprising a condensed ring of an aliphatic hydrocarbon ring and an aromatic ring. Examples of the aforementioned condensed ring include, for instance, a polycyclic alkane having one or more aromatic rings condensed onto a cross-linked polycyclic skeleton. Specific examples of the aforementioned cross-linked polycyclic alkane include bicyclic alkanes such as bicyclic [2.2.1]heptane (norbornene) and bicyclic [2.2.2]octane. As for the aforementioned condensed cyclic group, a group comprising a condensed ring of two or three aromatic rings condensed onto a bicyclic alkane is preferred, and a group comprising a condensed cyclic group of two or three aromatic rings condensed onto bicyclic [2.2.2]octane is more preferred. Specific examples of the condensed cyclic group in R 101 include those shown in formulas (r-br-1) to (r-br-2) below. In this case, * indicates the bonding point with Y 101 in equation (b-1).

[0225]

[0226] Examples of substituents that can be present in the condensed cyclic group of R 101 include alkyl, alkoxy, halogen atom, haloalkyl, hydroxyl, carbonyl, nitro, aromatic hydrocarbon group, alicyclic hydrocarbon group, etc. Examples of alkyl, alkoxy, halogen atom, or haloalkyl groups that can be used as substituents for the aforementioned condensed cyclic group include those that are the same as those used as substituents for the cyclic group in R 101 above. Examples of aromatic hydrocarbon groups that can be used as substituents for the aforementioned condensed cyclic groups include groups that have one hydrogen atom removed from the aromatic ring (aryl: for example, phenyl, naphthyl, etc.), groups that have one hydrogen atom of the aforementioned aromatic ring replaced by an alkyl group (for example, arylalkyl groups such as benzyl, phenethyl, 1-naphthylmethyl, 2-naphthylmethyl, 1-naphthylethyl, 2-naphthylethyl, etc.), and heterocyclic groups represented by the formulas (r-hr-1) to (r-hr-6) above. Examples of alicyclic hydrocarbon groups that can be used as substituents for the aforementioned condensed cyclic groups include: groups that remove one hydrogen atom from monocyclic alkanes such as cyclopentane and cyclohexane; groups that remove one hydrogen atom from polycyclic alkanes such as adamantane, norcamphene, isocamphene, tricyclic decane, and tetracyclic dodecane; cyclic groups containing lactones represented by the aforementioned general formulas (a2-r-1) to (a2-r-7); cyclic groups containing -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).

[0227] Alkyl groups that may have substituents in a chain: As a chain alkyl group of R 101, it can be either straight-chain or branched. As a straight-chain alkyl group, it is preferred to have 1 to 20 carbon atoms, more preferably 1 to 15, and ideally 1 to 10. As a branched alkyl group, it is preferred to have 3 to 20 carbon atoms, more preferably 3 to 15, and most preferably 3 to 10. Specific examples include 1-methylethyl, 1-methylpropyl, 2-methylpropyl, 1-methylbutyl, 2-methylbutyl, 3-methylbutyl, 1-ethylbutyl, 2-ethylbutyl, 1-methylpentyl, 2-methylpentyl, 3-methylpentyl, 4-methylpentyl, etc.

[0228] Alkenes that can have substituents in a chain-like structure: The chain-like alkenyl group of R 101 can be either linear or branched, preferably with 2 to 10 carbon atoms, more preferably with 2 to 5 carbon atoms, even more preferably with 2 to 4 carbon atoms, and especially preferably with 3 carbon atoms. Examples of linear alkenyl groups include vinyl, allyl, and butynyl. Examples of branched alkenyl groups include 1-methylvinyl, 2-methylvinyl, 1-methylpropenyl, and 2-methylpropenyl. As for the chain-like alkenyl group, the linear alkenyl group is preferred among the above-mentioned groups, with vinyl and propenyl groups being more preferred, and vinyl being particularly preferred.

[0229] Examples of substituents in the chain-like alkyl or alkenyl groups of R 101 include alkoxy groups, halogen atoms, halogenated alkyl groups, hydroxyl groups, carbonyl groups, nitro groups, amino groups, and cyclic groups in the aforementioned R 101.

[0230] Of the above, R 101 is preferably a cyclic group that can have substituents, and preferably a cyclic hydrocarbon group that can have substituents. More specifically, the cyclic hydrocarbon group is preferably a group that has removed one or more hydrogen atoms from phenyl, naphthyl, or polycyclic alkyl groups; a cyclic group containing lactones 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). It is more preferably a group that has removed one or more hydrogen atoms from polycyclic alkyl groups, and adamantyl alkyl groups are even more preferred.

[0231] In formula (b-1), Y 101 is a single bond or a divalent linkage containing an oxygen atom. Y 101 is a divalent bonding group containing an oxygen atom. Y 101 can also contain atoms other than oxygen atoms. Examples of atoms other than oxygen atoms include carbon atoms, hydrogen atoms, sulfur atoms, and nitrogen atoms. Examples of divalent linkages containing an oxygen atom include: oxygen atom (ether bond: -O-), ester bond (-C(=O)-O-), oxygen carbonyl group (-OC(=O)-), amide bond (-C(=O)-NH-), carbonyl group (-C(=O)-), and carbonate bond. Non-hydrocarbon oxygen-containing linkages such as (-OC(=O)-O-); combinations of such non-hydrocarbon oxygen-containing linkages with alkyl groups, etc. These combinations may also be further linked with sulfonyl groups (-SO 2-). Examples of such divalent linkages containing oxygen atoms include those represented by the following general formulas (y-al-1) to (y-al-7). Furthermore, in this case, in the following general formulas (y-al-1) to (y-al-7), the one bonded to R 101 in formula (b-1) is V' 101 in the following general formulas (y-al-1) to (y-al-7).

[0232] [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].

[0233] In V' 102, the divalent saturated hydrocarbon group 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.

[0234] As for the alkyl groups in V' 101 and V' 102, they can be either straight-chain or branched, with straight-chain alkyl groups being preferred. Examples of alkyl groups in V' 101 and V' 102 include 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-]; Alkyltrimethylbenzenes such as -CH(CH3)CH2CH2- and -CH2CH(CH3)CH2-; tetramethylene [-CH2CH2CH2CH2-]; -CH(CH3)CH2CH2CH2- Alkyl tetramethylene, pentamethylene, etc. [-CH 2CH 2CH 2CH 2CH 2-] etc. Furthermore, one of the methylene groups in the aforementioned alkyl group of V' 101 or V' 102 can also be replaced by a divalent aliphatic cyclic group with 5 to 10 carbon atoms. This aliphatic cyclic group is preferably a divalent group formed by removing one hydrogen atom from the cyclic aliphatic hydrocarbon group (monocyclic or polycyclic) of Ra' 3 in the aforementioned formula (a1-r-1), with cyclohexyl, 1,5-adamantyl, or 2,6-adamantyl being more preferred.

[0235] Y 101 is preferably a divalent linker containing an ester bond or a divalent linker containing an ether bond, and is more preferably a linker represented by the formulas (y-al-1) to (y-al-5) above.

[0236] In formula (b-1), V 101 is a single bond, an alkyl group, or a fluorinated alkyl group. The alkyl group or fluorinated alkyl group in V 101 is preferably composed of 1 to 4 carbon atoms. Examples of fluorinated alkyl groups in V 101 include groups in which one or all of the hydrogen atoms of the alkyl group are replaced by fluorine atoms. V 101 is preferably a single bond or a fluorinated alkyl group with 1 to 4 carbon atoms, and is more preferably a single bond or a straight-chain fluorinated alkyl group with 1 to 4 carbon atoms.

[0237] 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, with fluorine atoms being more preferred.

[0238] As specific examples of the anionic part shown in the aforementioned formula (b-1), for example, when Y 101 is a single bond, fluorinated alkyl sulfonate anions such as trifluoromethane sulfonate anion or perfluorobutane sulfonate anion can be cited; when Y 101 is a divalent linkage containing an oxygen atom, anions shown in any of the following formulas (an-1) to (an-3) can be cited.

[0239] [In the formula, R” 101 is an aliphatic cyclic group that may have substituents, a monovalent heterocyclic group represented by the above chemical formulas (r-hr-1) to (r-hr-6) respectively, a condensed cyclic group represented by the above formulas (r-br-1) or (r-br-2) respectively, or a chain-like alkyl group that may have substituents. R” 102 is an aliphatic cyclic group that may have substituents, a condensed cyclic group represented by the above formulas (r-br-1) and (r-br-2) respectively, a cyclic group containing lactone represented by the above general formulas (a2-r-1), (a2-r-3) to (a2-r-7) respectively, or a cyclic group containing SO 2- represented by the above general formulas (b5-r-1) to (b5-r-4) respectively.] R” 103 is an aromatic cyclic group that may have substituents, an aliphatic cyclic group that may have substituents, or a chain-like alkenyl group that may have substituents. V” 101 is a single bond, an alkyl group with 1 to 4 carbon atoms, or a fluorinated alkyl group with 1 to 4 carbon atoms. R 102 is a fluorine atom or a fluorinated alkyl group with 1 to 5 carbon atoms. v” is an independent integer from 0 to 3, q” is an independent integer from 0 to 20, and n” is 0 or 1.

[0240] The aliphatic cyclic groups of R” 101, R” 102 and R” 103 that may have substituents are preferably the groups exemplified by the cyclic aliphatic hydrocarbon group of R 101 in the aforementioned formula (b-1). As the aforementioned substituents, examples can be those that are the same as the substituents that can replace the cyclic aliphatic hydrocarbon group of R 101 in the aforementioned formula (b-1).

[0241] The aromatic cyclic group in R” 103 that may have substituents is preferably the aromatic hydrocarbon group exemplified in the cyclic hydrocarbon group of R 101 in the aforementioned formula (b-1). As the aforementioned substituent, examples can be those that are the same as the substituents that can replace the aromatic hydrocarbon group of R 101 in the aforementioned formula (b-1).

[0242] The chain alkyl group in R” 101 that may have substituents is preferably the group exemplified by the chain alkyl group of R 101 in the aforementioned formula (b-1). The chain alkenyl group in R” 103 that may have substituents is preferably the same as the chain alkenyl group exemplified by R 101 in the aforementioned formula (b-1).

[0243] • (b-2) component anions In formula (b-2), R104 and R105 are each independently a cyclic group that can have substituents, a chain alkyl group that can have substituents, or a chain alkenyl group that can have substituents, and examples of such groups are the same as R101 in formula (b-1). However, R104 and R105 can also combine with each other to form a ring. R 104 and R 105 are preferably chain alkyl groups that can have substituents, and are more preferably straight-chain or branched alkyl groups, or straight-chain or branched fluorinated alkyl groups. The number of carbon atoms in the chain alkyl group is preferably 1 to 10, more preferably 1 to 7, and even more preferably 1 to 3. For the chain alkyl groups of R 104 and R 105, a smaller number of carbon atoms within the above-mentioned range is preferred due to good solubility in solvents used as inhibitors. Furthermore, the more hydrogen atoms replaced by fluorine atoms in the chain alkyl groups of R 104 and R 105, 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 each independently a single bond, an enyl group, or a fluorinated enyl group, and examples of the same type as V 101 in formula (b0-1-an) can be given. In equation (b-2), L 101 and L 102 are each independently a single bond or an oxygen atom.

[0244] • (b-3) component anions In formula (b-3), R106 to R108 are each independently a cyclic group that may have substituents, a chain alkyl group that may have substituents, or a chain alkenyl group that may have substituents. Examples of such groups are the same as R101 in formula (b-1). In equation (b-3), the L 103 to L 105 series are each independently a single bond, -CO-, or -SO 2-.

[0245] Of the above, the anionic portion of component (B) is preferably the anionic portion of component (b-1).

[0246] {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 preferred. m is an integer greater than or equal to 1.

[0247] As a preferred cation portion ((M' m+) 1 / m), examples include organic cations represented by the general formulas (ca-1) to (ca-3) as described below.

[0248] [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 combine with each other to form a ring together with the sulfur atom in the formula. R 208~R 209 each independently represent a hydrogen atom or an alkyl group having 1~5 carbon atoms. R 210 represents 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-].

[0249] In the above general formulas (ca-1) to (ca-3), aryl groups in R 201 to R 207 can be exemplified by unsubstituted aryl groups with 6 to 20 carbon atoms, with phenyl and naphthyl being preferred. As for the alkyl group in R 201 to R 207, it is preferred to be a chain or cyclic alkyl group with 1 to 30 carbon atoms. For alkenyl groups in R 201 to R 207, the number of carbon atoms is preferably 2 to 10. Examples of substituents that can be present in R 201 to R 207 and R 210 include, for example, alkyl, halogen atom, alkyl halide, carbonyl, cyano, amino, aryl, and groups represented by the following general formulas (ca-r-1) to (ca-r-7).

[0250] [In the formula, R' 201 can be a hydrogen atom, a cyclic group that may have substituents, a chain alkyl group that may have substituents, or a chain alkenyl group that may have substituents].

[0251] Cyclic groups that may have substituents: The cyclic group system is preferably composed of cyclic hydrocarbon groups, which can be aromatic or aliphatic. Aliphatic hydrocarbon groups refer to hydrocarbon groups that do not possess aromaticity. Furthermore, aliphatic hydrocarbon groups can be saturated or unsaturated, but saturated groups are generally preferred.

[0252] The aromatic hydrocarbon group in R' 201 is a hydrocarbon group having an aromatic ring. The number of carbon atoms in this aromatic hydrocarbon group is preferably 3 to 30, more preferably 5 to 30, even more preferably 5 to 20, particularly preferably 6 to 15, and best preferably 6 to 10. However, this number of carbon atoms refers to the number of carbon atoms excluding those in the substituents. Aromatic rings, which are the aromatic hydrocarbon groups in R' 201, can be specifically exemplified by benzene, naphthalene, anthracene, phenanthrene, biphenyl, or aromatic heterocycles in which a portion of the carbon atom constituting the aromatic ring is replaced by a heteroatom. Heteroatoms in aromatic heterocycles can be exemplified by oxygen, sulfur, and nitrogen atoms. Specifically, the aromatic hydrocarbon group in R' 201 can be exemplified by groups in which one hydrogen atom is removed from the aforementioned aromatic ring (aryl: for example, phenyl, naphthyl, etc.), or groups in which one hydrogen atom of the aforementioned aromatic ring is replaced by an alkyl group (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.

[0253] Examples of cyclic aliphatic hydrocarbon groups in R' 201 include aliphatic hydrocarbon groups whose structures contain rings. Examples of aliphatic hydrocarbon groups containing a ring in this structure include alicyclic hydrocarbon groups (groups that remove one hydrogen atom from an aliphatic hydrocarbon ring), alicyclic hydrocarbon groups bonded to the end of a straight-chain or branched aliphatic hydrocarbon group, and alicyclic hydrocarbon groups present in the middle of a straight-chain or branched aliphatic hydrocarbon group. The aforementioned alicyclic hydrocarbon system is preferably composed of 3 to 20 carbon atoms, with 3 to 12 being more preferred. The aforementioned alicyclic hydrocarbon group can be either a polycyclic or monocyclic group. For monocyclic alicyclic hydrocarbon groups, it is preferable to have a group from which one or more hydrogen atoms have been removed from the monocyclic alkane. For the monocyclic alkane, it is preferable to have 3 to 6 carbon atoms, specifically examples include cyclopentane and cyclohexane. For polycyclic alicyclic hydrocarbon groups, it is preferable to have a group from which one or more hydrogen atoms have been removed from the polycyclic alkane, and for the polycyclic alkane, it is preferable to have 7 to 30 carbon atoms. Among these, polycyclic alkanes with a cross-linked ring system polycyclic skeleton, such as adamantane, norcamphene, isocamphene, tricyclodecane, and tetracyclododecane, and polycyclic alkanes with a condensed ring system polycyclic skeleton, such as cyclic groups with a steroid skeleton, are more preferred.

[0254] Among them, the cyclic aliphatic hydrocarbon group in R' 201 is preferably a group that has removed one or more hydrogen atoms from a monocyclic alkane or polycyclic alkane, and a group that has removed one hydrogen atom from a polycyclic alkane is more preferred. Adamantyl and norbenzene are particularly preferred, with adamantyl being the best.

[0255] The aliphatic hydrocarbon system that can be bonded to the alicyclic hydrocarbon group is preferably of 1 to 10 carbon atoms, more preferably of 1 to 6 carbon atoms, even more preferably of 1 to 4 carbon atoms, and especially preferably of 1 to 3 carbon atoms. As a straight-chain aliphatic hydrocarbon group, a straight-chain alkyl group is preferred. Specific examples include methylene [-CH 2-], ethyl [-(CH 2) 2-], trimethylene [-(CH 2) 3-], tetramethylene [-(CH 2) 4-], and pentamethylene. [-(CH 2) 5-] etc. As a branched aliphatic hydrocarbon group, branched alkyl groups are preferred, specifically examples include -CH(CH 3)-, -CH(CH 2CH 3)-, and -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 and other alkyl alkyl groups, such as -CH(CH 3)CH 2CH 2CH 2- and -CH 2CH(CH 3)CH 2CH 2-. Among alkyl alkyl groups, straight-chain alkyl groups with 1 to 5 carbon atoms are preferred.

[0256] Furthermore, the cyclic hydrocarbon groups in R' 201 can contain heteroatoms, just like 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 other heterocyclic groups represented by the aforementioned chemical formulas (r-hr-1) to (r-hr-16).

[0257] Examples of substituents in the cyclic group of R'201 include alkyl, alkoxy, halogen atom, haloalkyl, hydroxyl, carbonyl, nitro, etc. As for the alkyl group used as a substituent, it is preferred to be an alkyl group with 1 to 5 carbon atoms, and methyl, ethyl, propyl, n-butyl, and tert-butyl are the best. Alkoxy groups used as substituents are preferably alkoxy groups with 1 to 5 carbon atoms, with methoxy, ethoxy, n-propoxy, iso-propoxy, n-butoxy, and tert-butoxy being more preferred, and methoxy and ethoxy being the best. When used as a substituent, fluorine atoms are preferred. Examples of alkyl halogens that can be used as substituents include alkyl groups with 1 to 5 carbon atoms, such as methyl, ethyl, propyl, n-butyl, tert-butyl, etc., in which one or all of the hydrogen atoms are replaced by the aforementioned halogen atoms. The carbonyl group that serves as the substituent is the methylene group that forms the cyclic hydrocarbon group. (-CH 2-) is a base that is replaced by a substance.

[0258] Alkyl groups that may have substituents in a chain: As a chain alkyl group of R' 201, it can be either straight-chain or branched. As a straight-chain alkyl group, it is preferred to have 1 to 20 carbon atoms, more preferably 1 to 15 carbon atoms, and most preferably 1 to 10 carbon atoms. As a branched alkyl group, it is preferred to have 3 to 20 carbon atoms, more preferably 3 to 15 carbon atoms, and most preferably 3 to 10 carbon atoms. Specific examples include 1-methylethyl, 1-methylpropyl, 2-methylpropyl, 1-methylbutyl, 2-methylbutyl, 3-methylbutyl, 1-ethylbutyl, 2-ethylbutyl, 1-methylpentyl, 2-methylpentyl, 3-methylpentyl, 4-methylpentyl, etc.

[0259] Alkenes that can have substituents in a chain-like structure: The chain-like alkenyl group of R'201 can be either linear or branched, preferably with 2 to 10 carbon atoms, more preferably with 2 to 5 carbon atoms, even more preferably with 2 to 4 carbon atoms, and especially preferably with 3 carbon atoms. Examples of linear alkenyl groups include vinyl, allyl, and butynyl. Examples of branched alkenyl groups include 1-methylvinyl, 2-methylvinyl, 1-methylpropenyl, and 2-methylpropenyl. As for the chain-like alkenyl group, the linear alkenyl group is preferred among the above-mentioned groups, with vinyl and propenyl groups being more preferred, and vinyl being particularly preferred.

[0260] Examples of substituents in the chain-like alkyl or alkenyl groups of R' 201 include alkoxy groups, halogen atoms, halogenated alkyl groups, hydroxyl groups, carbonyl groups, nitro groups, amino groups, and cyclic groups in the aforementioned R' 201.

[0261] In addition to the above, R' 201 can be a cyclic group with substituents, a chain alkyl group with substituents, or a chain alkenyl group with substituents. Other examples of cyclic groups with substituents or chain alkyl groups with substituents that are the same as the acid-dissociable groups shown in the above formula (a1-r-2) can also be cited as cyclic groups with substituents or chain alkyl groups with substituents.

[0262] Among them, R' 201 is preferably a cyclic group that can have substituents, and is more preferably a cyclic hydrocarbon group that can have substituents. More specifically, it is preferably a phenyl, naphthyl, or a group that has removed one or more hydrogen atoms from a polycyclic alkane; a cyclic group containing lactones represented by the aforementioned general formulas (a2-r-1) to (a2-r-7); or a cyclic group containing -SO 2- represented by the aforementioned general formulas (b5-r-1) to (b5-r-4).

[0263] In the above general formulas (ca-1) to (ca-3), where R 201 to R 203 and R 206 to R 207 are bonded together with the sulfur atom in the formula to form a ring, the bonds can also be formed through heteroatoms such as sulfur, oxygen, 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 formed ring, it is preferable that the sulfur atom in the formula is included in one ring of its ring skeleton, and a 3 to 10-membered ring including the sulfur atom is preferred, with a 5 to 7-membered ring being particularly preferred. Specific examples of the rings formed include thiophene rings, thiazole rings, benzothiophene rings, dibenzothiophene rings, 9H-thioxanthium rings, thioxanone rings, thiathrone rings, phenoxathiin rings, tetrahydrothiophenonium rings, and tetrahydrothiaranonium rings.

[0264] R 208~R 209 each independently represent an alkyl group having 1 to 5 hydrogen atoms or carbon atoms, with alkyl groups having 1 to 3 hydrogen atoms being preferred. When forming alkyl groups, they can also combine with each other to form a ring.

[0265] R 210 can be an aryl group that may have substituents, an alkyl group that may have substituents, an alkenyl group that may have substituents, or a group containing substituents. -SO₂- cyclic base. Aryl groups in R 210 can be unsubstituted aryl groups with 6 to 20 carbon atoms, with phenyl and naphthyl groups being preferred. As for the alkyl group in R 210, it is preferred to be a chain or cyclic alkyl group with 1 to 30 carbon atoms. For alkenyl groups in R 210, a carbon number of 2 to 10 is preferred. As for the SO2-containing cyclic group that can have substituents in R 210, "a polycyclic group containing -SO2-" is preferred, and the group shown in the above general formula (b5-r-1) is more preferred.

[0266] As suitable cations as shown in the aforementioned formula (ca-1), examples include the cations represented by the following chemical formulas (ca-1-1) to (ca-1-70).

[0267]

[0268]

[0269] [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].

[0270]

[0271]

[0272] [In the formula, R” 201 is a hydrogen atom or a substituent, and the substituent is the same as the substituent that can be present in the aforementioned R 201~R 207 and R 210~R 212].

[0273] In the inhibitor composition of this embodiment, component (B) can be used alone or in combination with two or more components. When the inhibitor composition contains component (B), the content of component (B) in the inhibitor composition is preferably less than 50 parts by mass relative to 100 parts by mass of component (A), preferably 10 to 40 parts by mass, and even more preferably 20 to 40 parts by mass. By setting the content of component (B) within the aforementioned preferred range, sufficient pattern formation can be achieved. Furthermore, it is preferable that when each component of the inhibitor composition is dissolved in an organic solvent, a homogeneous solution can be easily obtained, and the storage stability of the inhibitor composition becomes good.

[0274] ≪Alkali component (D)≫ The resist composition of this embodiment contains component (A) and an alkaline component (hereinafter also referred to as "component (D)") that captures acid generated by exposure (i.e., controls acid diffusion). Component (D) acts as a quencher (acid diffusion control agent) in the resist composition to capture acid generated by exposure. Examples of components (D) include, for instance, photodegradable alkalis (D1) that lose their acid diffusion control due to decomposition upon exposure (hereinafter referred to as "(D1) component"), and nitrogen-containing organic compounds (D2) that should not be included in the (D1) component (hereinafter referred to as "(D2) component"). Among these, photodegradable alkalis ((D1) component) are preferred because they readily improve roughness reduction. Furthermore, by containing the (D1) component, the properties of high sensitivity and suppression of coating defects are readily improved.

[0275] Regarding component (D1) By creating a resist composition containing (D1), the contrast between the exposed and unexposed areas of the resist film can be further enhanced during the formation of the resist pattern. As for component (D1), there are no particular limitations as long as it loses its acid diffusion control due to decomposition during exposure. It is preferred to select one or more compounds from the group consisting of the compounds shown in general formula (d1-1) (hereinafter referred to as "(d1-1) component"), the compounds shown in general formula (d1-2) (hereinafter referred to as "(d1-2) component"), and the compounds shown in general formula (d1-3) (hereinafter referred to as "(d1-3) component"). Components (d1-1) to (d1-3) will decompose and lose their acid diffusion control (alkalinity) in the exposed part of the resist film, so they will not act as quenchers. However, they will act as quenchers in the unexposed part of the resist film.

[0276] [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 formula (d1-2), the carbon atom adjacent to the S atom in Rd2 is a non-bonded fluorine atom. Yd1 is a single bond or a divalent linked group. m is an integer greater than or equal to 1, and Mm+ are each an independent organic cation with an m valence.]

[0277] {(d1-1)Component} Anion section In formula (d1-1), Rd1 is a cyclic group that may have substituents, a chain alkyl group that may have substituents, or a chain alkenyl group that may have substituents, and examples of the same as R'201 mentioned above can be given. Of these, Rd 1 is preferably an aromatic hydrocarbon group that can have substituents, an aliphatic cyclic group that can have substituents, or a chain alkyl group that can have substituents. Examples of substituents that can be present in these groups include hydroxyl groups, oxo groups, alkyl groups, aryl groups, fluorine atoms, fluorinated alkyl groups, lactone-containing cyclic groups represented by the above general formulas (a2-r-1) to (a2-r-7), ether bonds, ester bonds, or combinations thereof. When an ether bond or ester bond is present as a substituent, it can also be separated from the alkyl group by 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 bond of the aromatic hydrocarbon group, aliphatic cyclic group, or chain alkyl group in the above general formulas (y-al-1) to (y-al-7) with Rd 1 in formula (d3-1) is V' 101 in the above general formulas (y-al-1) to (y-al-7). Examples of the aforementioned aromatic hydrocarbon groups include phenyl, naphthyl, and polycyclic structures containing a bicyclic octane skeleton (polycyclic structures consisting of a bicyclic octane skeleton and other ring structures). As the aforementioned aliphatic cyclic group, it is preferable to use a group that has removed one or more hydrogen atoms from polycyclic alkanes such as adamantane, norcamphene, isocamphene, tricyclic decane, and tetracyclic dodecane. As for the aforementioned chain-like alkyl group, it is preferred to have 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.

[0278] When the aforementioned chain-like alkyl group is a fluorinated alkyl group having a fluorine atom or a fluorinated alkyl group as a substituent, the number of carbon atoms in the fluorinated alkyl group is preferably 1 to 11, more preferably 1 to 8, and even more preferably 1 to 4. The fluorinated alkyl group may also contain atoms other than fluorine atoms. Examples of atoms other than fluorine atoms include, for example, oxygen atoms, sulfur atoms, and nitrogen atoms.

[0279] The following is a preferred example of the anionic portion of component (d1-1).

[0280]

[0281] • Cation section In formula (d1-1), M m+ is an organic cation with a valence of m. As an organic cation of M m+, suitable examples include those that are the same as the cations represented by the aforementioned general formulas (ca-1) to (ca-3), with the cation represented by the aforementioned general formula (ca-1) being preferred, and the cations represented by the aforementioned formulas (ca-1-1) to (ca-1-113) being even more preferred. (d1-1) Components can be used alone or in combination of two or more.

[0282] {(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, such as the same as R'201 mentioned above. However, the carbon atoms adjacent to the S atom in Rd2 are unbonded fluorine atoms (unsubstituted with fluorine). As a result, the anion of the (d1-2) component becomes a moderately weak acid anion, and its quenching ability as the (D) component is enhanced. As Rd2, it is preferably a chain alkyl group that may have substituents or an aliphatic cyclic group that may have substituents, with the aliphatic cyclic group that may have substituents being more preferred.

[0283] The alkyl group in this chain is preferably composed of 1 to 10 carbon atoms, and more preferably 3 to 10 carbon atoms. As the aliphatic cyclic group, it is preferable to have a group that has removed one or more hydrogen atoms from adamantane, norcamphene, isocamphene, tricyclodecane, tetracyclododecane, etc. (substituents may also be present); it is preferable to have a group that has removed one or more hydrogen atoms from camphor.

[0284] The hydrocarbon group of Rd 2 may also have substituents. Examples of such substituents include those that are the same as those that can be present in the hydrocarbon group (aromatic hydrocarbon group, aliphatic cyclic group, chain alkyl group) of Rd 1 in the aforementioned formula (d1-1).

[0285] The following are preferred examples of the anionic portion of component (d1-2).

[0286]

[0287] • 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.

[0288] {(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 similar to R'201 mentioned above, with cyclic groups containing fluorine atoms, chain alkyl groups, or chain alkenyl groups being preferred. Fluorinated alkyl groups are also preferred, and those similar to the fluorinated alkyl groups in Rd1 mentioned above are even more preferred.

[0289] 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, such as the same as R'201 mentioned above. Alkyl, alkoxy, alkenyl, and cyclic groups that can have substituents are preferred. The alkyl group in Rd 4 is preferably a straight-chain or branched alkyl group with 1 to 5 carbon atoms, such as methyl, ethyl, propyl, isopropyl, n-butyl, isobutyl, tert-butyl, pentyl, isopentyl, neopentyl, etc. Part of the hydrogen atom of the alkyl group in Rd 4 can also be replaced by hydroxyl, cyano, etc. In Rd 4, alkoxy groups with 1 to 5 carbon atoms are preferred. Specific 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 preferred.

[0290] Examples of alkenyl groups in Rd 4 include those identical to those in R' 201, with vinyl, allyl (allyl), 1-methylpropenyl, and 2-methylpropenyl being preferred. These groups may also have alkyl groups with 1 to 5 carbon atoms or haloalkyl groups with 1 to 5 carbon atoms as substituents.

[0291] Examples of cyclic groups in Rd 4 include those identical to those in R' 201, such as alicyclic groups with one or more hydrogen atoms removed from cycloalkanes like cyclopentane, cyclohexane, adamantane, norcamphene, isocamphene, tricyclodecane, and tetracyclododecane, or aromatic groups like phenyl or naphthyl. When Rd 4 is an alicyclic group, the resist composition dissolves well in organic solvents, resulting in good lithography properties. Furthermore, when Rd 4 is an aromatic group, the resist composition exhibits excellent light absorption efficiency in lithography using EUV or similar exposure sources, leading to good sensitivity and lithography properties.

[0292] In equation (d1-3), Yd1 is a single bond or a divalent linker. The divalent linker in Yd 1 is not particularly limited, and examples include divalent hydrocarbon groups (aliphatic hydrocarbon groups, aromatic hydrocarbon groups) that may have substituents, and divalent linkers containing heteroatoms. Examples of these include divalent hydrocarbon groups that may have substituents and divalent linkers containing heteroatoms that are the same as those mentioned in the description of divalent linkers in Ya 21 of the above formula (a2-1). As Yd 1, it is preferably a carbonyl group, an ester bond, an amide bond, an alkyl group, or a combination thereof. As an alkyl group, a straight-chain or branched alkyl group is preferred, and a methylene or ethyl group is even more preferred.

[0293] The following are preferred examples of the anionic portion of components (d1-3).

[0294]

[0295]

[0296] • 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.

[0297] (D1) can be any one of the above (d1-1) to (d1-3) components, or it can be 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 25 parts by mass relative to 100 parts by mass of component (A1), preferably 1 to 20 parts by mass, and even more preferably 3 to 15 parts by mass. When the content of component (D1) is above the lower limit of the optimal value, it is particularly easy to obtain good photolithography properties and resist pattern shape. On the other hand, when it is below the upper limit value, sensitivity can be well maintained and the yield is also excellent.

[0298] In the inhibitor composition of this embodiment, component (D1) is preferably composed of the above-mentioned component (d1-1). Of the total amount of component (D) contained in the inhibitor composition of this embodiment, the content of component (d1-1) is preferably 50% by mass or more, preferably 70% by mass or more, and preferably 90% by mass or more. Component (D) may also be composed solely of compound component (d1-1).

[0299] (D1) Manufacturing method of component: There are no particular limitations on the manufacturing methods of the aforementioned components (d1-1) and (d1-2), and they can be manufactured using known methods. Furthermore, there are no particular limitations on the manufacturing method of components (d1-3), for example, it can be manufactured by operating in the same manner as described in US 2012-0149916.

[0300] Regarding component (D2) As component (D), it may also contain nitrogen-containing organic compounds that are not appropriate to component (D1) above (hereinafter referred to as "component (D2)"). As for component (D2), as long as it functions as an acid diffusion control agent and is not equivalent to component (D1), there are no particular limitations, and it can be used freely from the known sources. Aliphatic amines are preferred, especially secondary or tertiary aliphatic amines. Aliphatic amines refer to amines having one or more aliphatic groups, preferably with 1 to 12 carbon atoms. Examples of aliphatic amines include amines (alkylamines or alkylolamines) in which at least one hydrogen atom of ammonia NH 3 is replaced by an alkyl or hydroxyalkyl group having 12 or fewer carbon atoms. Specific examples of alkylamines and alkylolamines include monoalkylamines such as n-hexylamine, n-heptylamine, n-octylamine, n-nonylamine, and n-decylamine; dialkylamines such as diethylamine, di-n-propylamine, di-n-heptylamine, di-n-octylamine, and dicyclohexylamine; trialkylamines such as trimethylamine, triethylamine, tri-n-propylamine, tri-n-butylamine, tri-n-pentylamine, tri-n-hexylamine, tri-n-heptylamine, tri-n-octylamine, tri-n-nonylamine, tri-n-decylamine, and tri-n-dodecylamine; and alkylolamines such as diethanolamine, triethanolamine, diisopropanolamine, triisopropanolamine, di-n-octanolamine, and tri-n-octanolamine. Among these, trialkylamines with 6 to 30 carbon atoms are preferred, with tri-n-pentylamine or tri-n-octylamine being particularly preferred.

[0301] Examples of cyclic amines include heterocyclic compounds containing a nitrogen atom as a heteroatom. These heterocyclic compounds can be monocyclic (aliphatic monocyclic amines) or polycyclic (aliphatic polycyclic amines). Examples of aliphatic monocyclic amines include piperidine and piperazine. As aliphatic polycyclic amines, those with 6 to 10 carbon atoms are preferred. Specific examples include 1,5-diacrylbicyclo[4.3.0]-5-nonene, 1,8-diacrylbicyclo[5.4.0]-7-undecene, hexamethylenetetramine, and 1,4-diacrylbicyclo[2.2.2]octane.

[0302] Other aliphatic amines include triethanolamine (2-methoxymethoxyethyl)amine, triethanolamine {2-(2-methoxyethoxy)ethyl}amine, triethanolamine {2-(2-methoxyethoxymethoxy)ethyl}amine, triethanolamine {2-(1-methoxyethoxy)ethyl}amine, triethanolamine {2-(1-ethoxyethoxy)ethyl}amine, triethanolamine {2-(1-ethoxypropoxy)ethyl}amine, triethanolamine [2-{2-(2-hydroxyethoxy)ethoxy}ethyl]amine, triethanolamine triacetate, etc., with triethanolamine triacetate being the preferred choice.

[0303] Furthermore, aromatic amines can also be used as (D2) components. Examples of aromatic amines include 4-dimethylaminopyridine, pyrrole, indole, pyrazole, imidazole or derivatives thereof, tribenzylamine, 2,6-diisopropylaniline, N-tert-butoxycarbonylpyrrolidine, 2,6-di-tert-butylpyridine, etc.

[0304] Of the above, alkylamines are preferred for (D2) component, and trialkylamines with 6 to 30 carbon atoms are preferred.

[0305] (D2) Components can be used alone or in combination of two or more. When the inhibitor composition contains component (D2), the content of component (D2) in the inhibitor composition is preferably 0.01 to 5 parts by mass relative to 100 parts by mass of component (A1), preferably 0.1 to 5 parts by mass, and even more preferably 0.5 to 5 parts by mass. When the content of component (D2) is above the lower limit of the optimal value, it is particularly easy to obtain good photolithography properties and resist pattern shape. On the other hand, when it is below the upper limit value, sensitivity can be maintained well and the yield is also excellent.

[0306] ≪Select at least one compound (E) from the group consisting of free organic carboxylic acids and oxyacids of phosphorus and their derivatives≫ In order to prevent sensitivity degradation, improve the shape of the resist pattern, or enhance stability over time, the resist composition of this embodiment may contain at least one compound (E) selected from organic carboxylic acids and oxyacids of phosphorus and their derivatives (hereinafter referred to as "(E) component") as an arbitrary component. Examples of organic carboxylic acids include acetic acid, malonic acid, citric acid, malic acid, succinic acid, benzoic acid, and salicylic acid, with salicylic acid being the preferred choice. Examples of oxyacids of phosphorus include phosphoric acid, phosphonic acid, and phosphonic acid, among which phosphonic acid is particularly preferred.

[0307] 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 achieving the above range, the lithography properties will be further improved.

[0308] ≪Fluoride Additive Components (F)≫ The resist composition of this embodiment may also contain a fluorinated additive component (hereinafter referred to as "(F) component") hydrophobic resin. The (F) component is used to impart water-repellent properties to the resist film. By using a resin that is different from the (A) component, the lithography properties can be improved. As component (F), for example, Japanese Patent Application Publication No. 2010-002870, Japanese Patent Application Publication No. 2010-032994, and Japanese Patent Application Publication No. 2010-032994 may be used. Fluorine-containing polymers described in Japanese Patent Application Publication No. 2010-277043, Japanese Patent Application Publication No. 2011-13569, and Japanese Patent Application Publication No. 2011-128226. As component (F), more specifically, a polymer having a constituent unit (f1) as shown in the following general formula (f1-1) can be cited. As such a polymer, a known polymer (homopolymer) composed solely of a constituent unit (f1) as shown in the following formula (f1-1); a copolymer of the constituent unit (f1) with the aforementioned constituent unit (a1); or a copolymer of the constituent unit (f1) with a constituent unit derived from acrylic acid or methacrylic acid and the aforementioned constituent unit (a1), with a copolymer of the constituent unit (f1) with the aforementioned constituent unit (a1) being more preferred. Here, as the aforementioned constituent unit (a1) copolymerized with the constituent unit (f1), a constituent unit derived from 1-ethyl-1-cyclooctyl (meth)acrylate, a constituent unit derived from 1-methyl-1-adamantyl (meth)acrylate, and a constituent unit derived from 1-ethyl-1-cyclooctyl (meth)acrylate are more preferred.

[0309] [In the formula, R is the same as above, Rf 102 and Rf 103 each independently represent hydrogen atoms, halogen atoms, alkyl groups with 1 to 5 carbon atoms or alkyl halides with 1 to 5 carbon atoms, and 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].

[0310] In formula (f1-1), the R group bonded to the carbon atom at the α-position is the same as described above. Hydrogen atoms or methyl groups are preferred as R. In formula (f1-1), fluorine atoms are preferred as halogen atoms in Rf 102 and Rf 103. Examples of alkyl groups having 1 to 5 carbon atoms in Rf 102 and Rf 103 include those identical to the alkyl groups having 1 to 5 carbon atoms in R, preferably methyl or ethyl. Specifically, examples of alkyl halides having 1 to 5 carbon atoms in Rf 102 and Rf 103 include groups in which one or all of the hydrogen atoms of an alkyl group having 1 to 5 carbon atoms are replaced by halogen atoms. Fluorine atoms are preferred as halogen atoms. Among these, hydrogen atoms, fluorine atoms, or alkyl groups having 1 to 5 carbon atoms are preferred as Rf 102 and Rf 103, with hydrogen atoms, fluorine atoms, methyl, or ethyl being more preferred, and hydrogen atoms being even more preferred. In formula (f1-1), nf1 is an integer from 0 to 5, preferably an integer from 0 to 3, and preferably 1 or 2.

[0311] In formula (f1-1), Rf 101 is an organic group containing fluorine atoms, preferably a hydrocarbon group containing fluorine atoms. As a hydrocarbon group containing fluorine atoms, it can be any of straight-chain, branched, or cyclic, with 1 to 20 carbon atoms being preferred, 1 to 15 carbon atoms being more preferred, and 1 to 10 carbon atoms being especially preferred. Furthermore, it is preferable for hydrocarbon groups containing fluorine atoms to have more than 25% of their hydrogen atoms fluorinated, with more than 50% being even better. Since this increases the hydrophobicity of the resist film during immersion and exposure, more than 60% fluorination is particularly desirable. Among them, as Rf 101, fluorinated hydrocarbon groups with 1 to 6 carbon atoms are preferred, and trifluoromethyl, -CH 2-CF 3, -CH 2-CF 2-CF 3, -CH(CF 3) 2, -CH 2-CH 2-CF 3, -CH 2-CH 2-CF 2-CF 2-CF 3 are particularly preferred.

[0312] (F) The weight-average molecular weight (Mw) of the component (based on polystyrene conversion using gel permeation chromatography) is preferably 1,000 to 50,000, more preferably 5,000 to 40,000, and optimally 10,000 to 30,000. Below the upper limit of this range, there is sufficient solubility in the solvent required for use as a resisting agent; above the lower limit of this range, the water-repellent properties of the resisting film are good. (F) The dispersion of the component (Mw / Mn) is preferably 1.0~5.0, preferably 1.0~3.0, and best of all is 1.0~2.5.

[0313] In the inhibitor composition of this embodiment, component (F) can be used alone or in combination with two or more components. When the inhibitor composition contains component (F), the content of component (F) is preferably 0.5 to 10 parts by mass relative to 100 parts by mass of component (A), and more preferably 1 to 10 parts by mass.

[0314] ≪Organic solvent component (S)≫ The inhibitor composition system of this embodiment can be manufactured by dissolving the inhibitor material in an organic solvent component (hereinafter referred to as "(S) component"). As for component (S), any known solvent that can dissolve all the components used to form a homogeneous solution may be selected from those known to be used as components of chemically amplifying inhibitors. As components (S), examples include lactones such as γ-butyrolactone; ketones such as acetone, methyl ethyl ketone, cyclohexanone, methyl-n-pentyl ketone, methyl isopentyl ketone, and 2-heptanone; polyvalent alcohols such as ethylene glycol, diethylene glycol, propylene glycol, and dipropylene glycol; compounds containing ester bonds such as ethylene glycol monoacetate, diethylene glycol monoacetate, propylene glycol monoacetate, or dipropylene glycol monoacetate; polyvalent alcohol derivatives such as monomethyl ether, monoethyl ether, monopropyl ether, monobutyl ether, etc., or monoalkyl ether or monophenyl ether of the aforementioned polyvalent alcohols or compounds containing ester bonds [among these are...]. Preferred solvents include propylene glycol monomethyl ether acetate (PGMEA) and propylene glycol monomethyl ether (PGME); cyclic ethers such as dioxane; or esters such as methyl lactate, ethyl lactate (EL), methyl acetate, ethyl acetate, butyl acetate, methyl pyruvate, ethyl pyruvate, methyl methoxypropionate, ethyl ethoxypropionate, etc.; aromatic organic solvents such as anisole, ethyl benzyl ether, cresol methyl ether, diphenyl ether, dibenzyl ether, phenethyl ether, butyl phenyl ether, ethylbenzene, diethylbenzene, pentylbenzene, isopropylbenzene, toluene, xylene, p-isopropyltoluene, mesitylene, etc.; and dimethyl sulfoxide (DMSO). In the inhibitor composition of this embodiment, component (S) can be used alone or as a mixed solvent of two or more components. Among them, PGMEA is used... PGME, γ-butyrolactone, EL, and cyclohexanone are preferred.

[0315] Furthermore, as component (S), a mixed solvent consisting of PGMEA and a polar solvent is preferred. The mixing ratio (mass ratio) should be appropriately determined after taking into account the compatibility of PGMEA and the polar solvent, with a ratio of 1:9 to 9:1 being preferred, and a ratio of 2:8 to 8:2 being even more preferred. More specifically, when EL or cyclohexanone is used as a polar solvent, the mass ratio of PGMEA:EL or cyclohexanone is preferably 1:9 to 9:1, more preferably 2:8 to 8:2. Furthermore, when PGME is used as a polar solvent, the mass ratio of PGMEA:PGME is preferably 1:9 to 9:1, more preferably 2:8 to 8:2, and even more preferably 3:7 to 7:3. Moreover, a mixture of PGMEA and PGME with cyclohexanone is also preferred. Furthermore, as component (S), it is preferable that at least one of PGMEA and EL, along with γ-butyrolactone, is used as a mixed solvent. In this case, the mass ratio of the former to the latter is preferably 70:30 to 95:5. There is no particular limitation on the amount of component (S) used. The concentration should be set appropriately according to the coating thickness, so that it can be coated onto the substrate. Generally speaking, component (S) is used in a way that makes the concentration of solid components of the resist composition in the range of 0.1 to 20% by mass, preferably 0.2 to 15% by mass.

[0316] The inhibitor composition of this embodiment, after dissolving the aforementioned inhibitor material in component (S), uses a polyimide porous membrane, a polyamide-imide porous membrane, etc., to remove impurities. For example, a filter made of a polyimide porous membrane, a filter made of a polyamide-imide porous membrane, or a filter made of both polyimide porous membranes can be used as the filtration 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.

[0317] The inhibitor composition of this embodiment described above contains: a resin component (A1) having the above-described constituent unit (a01). The constituent unit (a01) has either an aryl group in which one or all of the hydrogen atoms are replaced by iodine atoms, or a heteroaryl group in which one or all of the hydrogen atoms are replaced by iodine atoms. Because the constituent unit (a01) contains iodine atoms, it has high absorption efficiency for EUV (extreme ultraviolet) and EB (electron beam) wavelengths. Furthermore, the constituent unit (a01) has a divalent linker in its side chain. Therefore, the resin component (A1) having this constituent unit (a01) has a different three-dimensional structure compared to a resin component having a constituent unit that does not have a divalent linker in its side chain, thereby improving the solubility of the developer. Therefore, it is speculated that the resist composition of the present embodiment containing resin component (A1) can achieve high sensitivity and form a resist pattern with good roughness reduction.

[0318] (Method for forming inhibitor patterns) The method for forming a resist pattern of the second state sample of the present invention is a method comprising: a step of forming a resist film on a support using the resist composition of the first state sample of the present invention; a step of exposing the resist film; and a step of developing the exposed resist film to form a resist pattern. As one embodiment of the resist pattern forming method, an example of a resist pattern forming method performed by the following operations can be cited.

[0319] First, the resist composition of the above embodiment is applied to the support using a spinner, and then baked (post-coating baking (PAB)) at a temperature of, for example, 80 to 150°C for 40 to 120 seconds, preferably for 60 to 90 seconds, to form a resist film. Secondly, the resist film is selectively exposed by an exposure apparatus such as an electron line drawing apparatus or an ArF exposure apparatus, either by exposure through a mask (mask pattern) with a pre-formed pattern or by direct irradiation of electron lines without a mask pattern. Then, it is baked (post-exposure baking (PEB)) at a temperature of, for example, 80 to 150°C for 40 to 120 seconds, preferably 60 to 90 seconds. Next, the aforementioned resist film is subjected to a developing process. In the case of an alkaline developing process, an alkaline developer is used; in the case of a solvent developing process, a developer containing organic solvents (organic developer) is used.

[0320] After development, a rinsing process is preferable. In alkaline development processes, rinsing with pure water is preferred, while in solvent development processes, a rinsing solution containing organic solvents is preferred. In the case of solvent development processes, after the aforementioned development or rinsing treatments, a process can also be performed to remove the developer or rinsing solution adhering to the pattern using supercritical fluid. Drying is performed after development or rinsing. Alternatively, depending on the circumstances, baking (post-baking) may be performed after the above-mentioned development process. This operation allows for the formation of a resist pattern.

[0321] There are no particular limitations on the support structure; previously known materials can be used, such as substrates for electronic components, or substrates on which a specific wiring pattern has already been formed. More specifically, examples include metal substrates such as silicon wafers, copper, chromium, iron, and aluminum, or glass substrates. Materials used for the wiring pattern include, for example, copper, aluminum, nickel, and gold.

[0322] 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; relatively 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 the operation of exposing the aforementioned resist film to EUV (extreme ultraviolet) or EB (electron beam).

[0323] 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. Immersion exposure is an exposure method in which a solvent (immersion medium) with a higher refractive index than air is filled between the resist film and the lens at the lowest position of the exposure device, and exposure is performed in this state (immersion exposure). As a liquid immersion medium, a solvent with a refractive index greater than that of air and less than that of the resist film being exposed is preferred. Examples include water, fluorine-based inert liquids, silicon-based solvents, and hydrocarbon-based solvents. Water is the preferred medium for immersion.

[0324] Examples of alkaline developing solutions used in alkaline developing processes include 0.1 to 10% by mass tetramethylammonium hydroxide (TMAH) aqueous solutions. As for the organic solvent contained in the organic developing solution used in the solvent developing process, it is acceptable as long as it can dissolve component (A) (component (A) before exposure), and it can be appropriately selected from known organic solvents. Specifically, polar solvents such as ketone solvents, ester solvents, alcohol solvents, nitrile solvents, amide solvents, ether solvents, and hydrocarbon solvents can be cited.

[0325] Examples of ester solvents include methyl acetate, butyl acetate, ethyl acetate, isopropyl acetate, amyl acetate, isoamyl acetate, amyl acetate, propylene glycol monomethyl ether acetate, ethylene glycol monoethyl ether acetate, diethylene glycol monobutyl ether acetate, diethylene glycol monoethyl ether acetate, ethyl-3-ethoxypropionate, 3-methoxybutyl acetate, 3-methyl-3-methoxybutyl acetate, methyl formate, ethyl formate, butyl formate, propyl formate, ethyl lactate, butyl lactate, propyl lactate, butyl butyrate, methyl 2-hydroxyisobutyrate, isoamyl acetate, isobutyl isobutyrate, and butyl propionate.

[0326] Examples of nitrile solvents include acetonitrile, propionitrile, valerate, and butyronitrile.

[0327] Organic developers may incorporate known additives as necessary. Examples of such additives include surfactants. There are no particular limitations on the type of surfactant; ionic or nonionic fluorinated and / or silicone surfactants may be used. Nonionic surfactants are preferred, with nonionic fluorinated or silicone surfactants being particularly advantageous. When surfactants are incorporated, the amount incorporated relative to the total amount of organic developer is usually 0.001 to 5% by mass, preferably 0.005 to 2% by mass, and more preferably 0.01 to 0.5% by mass.

[0328] The developing process can be carried out using known developing methods, such as the method of immersing the support in the developing solution for a fixed time (immersion method), the method of using surface tension to make the developing solution float and remain still on the surface of the support for a fixed time (puddle method), the method of spraying the developing solution onto the surface of the support (spray method), and the method of scanning the developing solution ejection nozzle at a fixed speed on a support rotating at a fixed speed while continuously ejecting the developing solution (dynamic distribution method), etc.

[0329] The organic solvent contained in the rinsing solution used for rinsing after development in a solvent-based developing process can be suitably selected from among the organic solvents listed above that are not easily soluble in the inhibitor pattern. Typically, at least one solvent selected from hydrocarbon solvents, ketone solvents, ester solvents, alcohol solvents, amide solvents, and ether solvents is used. Among these, at least one solvent selected from hydrocarbon solvents, ketone solvents, ester solvents, alcohol solvents, and amide solvents is preferred, at least one solvent selected from alcohol solvents and ester solvents is more preferred, and alcohol solvents are particularly preferred. The alcohol solvent used in the washing solution is preferably a monovalent alcohol with 6 to 8 carbon atoms. This monovalent alcohol can be linear, branched, or cyclic. Specific examples include 1-hexanol, 1-heptanol, 1-octanol, 2-hexanol, 2-heptanol, 2-octanol, 3-hexanol, 3-heptanol, 3-octanol, 4-octanol, and benzyl alcohol. Among these, 1-hexanol, 2-heptanol, and 2-hexanol are preferred, with 1-hexanol and 2-hexanol being particularly favored. 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 rinse solution is preferably 30% by mass or less, preferably 10% by mass or less, more preferably 5% by mass or less, and especially preferably 3% by mass or less. The washing solution may be mixed with known additives as necessary. Examples of such additives include surfactants. Examples of surfactants include those as described above, with nonionic surfactants being preferred, particularly nonionic fluorinated surfactants or nonionic silicone surfactants. When surfactants are incorporated, the amount incorporated is usually 0.001 to 5% by mass relative to the total amount of the washing solution, preferably 0.005 to 2% by mass, and more preferably 0.01 to 0.5% by mass.

[0330] The rinsing treatment (cleaning treatment) using a rinsing solution can be carried out by known rinsing methods. Examples of such rinsing treatment methods include, for instance, continuously dispensing rinsing solution onto a support rotating at a fixed speed (rotation coating method), immersing the support in the rinsing solution for a fixed time (immersion method), and spraying rinsing solution onto the surface of the support (spraying method).

[0331] According to the resist pattern forming method of this embodiment described above, since the above-mentioned resist composition is used, high sensitivity can be achieved, and a resist pattern with good roughness reduction can be formed.

[0332] 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 top coating, etc.) are preferably free from impurities such as metals, metal salts containing halogens, acids, alkalis, and components containing sulfur or phosphorus atoms. Here, examples of impurities containing metal atoms include Na, K, Ca, Fe, Cu, Mn, Mg, Al, Cr, Ni, Zn, Ag, Sn, Pb, Li, or salts thereof. The content of these impurities in the material is preferably below 200 ppb, more preferably below 1 ppb, even better below 100 ppt (parts per trillion), particularly preferably below 10 ppt, and best of all is that they are substantially absent (below the detection limit of the measuring device).

[0333] (compound) The third state of the compound of the present invention is the compound shown in the following general formula (a0-1).

[0334] [In the formula, R01 is a hydrogen atom, an alkyl group having 1 to 10 carbon atoms, or a haloalkyl group having 1 to 10 carbon atoms. L01 is a divalent linkage. Ra01 and Ra02 are each independently a hydrocarbon group that can have substituents. Ar01 is an aryl group in which one or all of the hydrogen atoms are replaced by iodine atoms, or a heteroaryl group in which one or all of the hydrogen atoms are replaced by iodine atoms. The aforementioned aryl and heteroaryl groups may also have substituents other than iodine atoms.]

[0335] The compound represented by general formula (a0-1) in this embodiment is the same as the compound represented by general formula (a0-1) in the inhibitor composition of the first embodiment of the present invention.

[0336] The compound of this embodiment is preferably a compound represented by the following general formula (a0-1-1).

[0337] [In the formula, R01 is a hydrogen atom, an alkyl group having 1 to 10 carbon atoms, or a haloalkyl group having 1 to 10 carbon atoms. L001 is an ester bond, an aromatic hydrocarbon group, a cyclic group containing a lactone, or a divalent linked group having a group composed of such combinations. Ra01 and Ra02 are each independently a hydrocarbon group that can have substituents. Ar01 is an aryl group in which one or all of the hydrogen atoms are replaced by iodine atoms, or a heteroaryl group in which one or all of the hydrogen atoms are replaced by iodine atoms. The aforementioned aryl and heteroaryl groups may also have substituents other than iodine atoms.]

[0338] The compound represented by general formula (a0-1-1) in this embodiment is the same as the compound represented by general formula (a0-1-1) in the inhibitor composition of the first embodiment of the present invention.

[0339] (Methods for manufacturing compounds) The compound of this embodiment can be manufactured, for example, by esterification of the compound shown in the following general formula (C0-1) with the compound shown in the following general formula (AL0-1).

[0340] [In the formula, R01 is a hydrogen atom, an alkyl group having 1 to 10 carbon atoms, or a haloalkyl group having 1 to 10 carbon atoms. L01 is a divalent linkage. Ra01 and Ra02 are each independently a hydrocarbon group that can have substituents. Ar01 is an aryl group in which one or all of the hydrogen atoms are replaced by iodine atoms, or a heteroaryl group in which one or all of the hydrogen atoms are replaced by iodine atoms. The aforementioned aryl and heteroaryl groups may also have substituents other than iodine atoms.]

[0341] There are no particular limitations on the temperature conditions for the above esterification reaction, such as -10 to 120°C. There is no particular limitation on the reaction time of the above esterification reaction, for example, 1 to 72 hours.

[0342] Examples of reaction solvents used in the above esterification reaction include dichloromethane, dichloroethane, chloroform, tetrahydrofuran, N,N-dimethylformamide, acetonitrile, propionitrile, N,N'-dimethylacetamide, and dimethyl sulfoxide.

[0343] Furthermore, condensing agents and alkaline catalysts can also be used in the above esterification reaction. Specific examples of condensing agents include N,N'-dicyclohexylcarbodiimide, N,N'-diisopropylcarbodiimide, 1-ethyl-3-(3-dimethylaminopropyl)carbodiimide hydrochloride, and carbonyl diimidazole (CDI). Examples of alkaline catalysts include tertiary amines such as trimethylamine, triethylamine, and tributylamine; aromatic amines such as pyridine, dimethylaminopyridine (DMAP), and pyrrolopyridine; and diacryldicyclononene (DBN) and diacryldicycloundecene (DBU).

[0344] To enhance electrophilicity and reactivity, the compound represented by the above general formula (C0-1) can also be a chloride of a carboxylic acid. That is, the hydroxyl group in the compound represented by the above general formula (C0-1) can also be replaced by a chlorine atom.

[0345] After the reaction is complete, the compound represented by the general formula (a0-1) in the reaction solution can also be separated and purified. Separation and purification can be performed using previously known methods, such as concentration, solvent extraction, distillation, crystallization, recrystallization, chromatography, or a combination of two or more of these methods. The structure of the compound obtained by the above operations can be confirmed by general organic analysis 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.

[0346] <Synthesis of compounds represented by general formula (AL0-1)> The compound shown in formula (AL0-1) above can be a commercially available product or can be synthesized. For example, as shown below, the compound shown in formula (AL0-1) can also be synthesized by a Grinner reaction, in which a ketone represented by the following general formula (AL0-1pre) is reacted with an organomagnesium halide represented by Ra 02MgBr.

[0347] [In the formula, Ra 01 and Ra 02 are each an independent hydrocarbon group that can have substituents. Ar 01 is an aryl group in which one or all of the hydrogen atoms are replaced by iodine atoms, or a heteroaryl group in which one or all of the hydrogen atoms are replaced by iodine atoms. The aforementioned aryl and heteroaryl groups may also have substituents other than iodine atoms.]

[0348] Examples of reaction solvents used in the aforementioned Grinner reaction that are the same as those used in the aforementioned esterification reaction can be cited.

[0349] The temperature conditions for the above-mentioned Grenner reaction are not particularly limited, for example, within the range of -10 to 120°C. There is no particular limitation on the reaction time of the above-mentioned Grenner reaction, for example, it can be in the range of 1 to 72 hours.

[0350] Furthermore, the compound shown in formula (AL0-1) can be used in strong bases (potassium hexamethyldisilicide (KHMDS)). In the presence of hexamethyldisilazide, etc., it is synthesized by nucleophilic addition reaction of aromatic compounds with iodine atoms to ketones.

[0351] Alternatively, the compound shown in formula (AL0-1) can be reacted with other compounds to synthesize a compound shown in formula (AL0-1) that is different from the original compound. For example, the compound shown in formula (AL0-1) above can also be reacted with 5-norcamphene-2,3-dicarboxylic anhydride to synthesize the compound shown in general formula (AL0-1').

[0352] [In the formula, Ra 01 and Ra 02 are each an independent hydrocarbon group that can have substituents. Ar 01 is an aryl group in which one or all of the hydrogen atoms are replaced by iodine atoms, or a heteroaryl group in which one or all of the hydrogen atoms are replaced by iodine atoms. The aforementioned aryl and heteroaryl groups may also have substituents other than iodine atoms.]

[0353] The compound described above is used to manufacture the resin of the fourth embodiment described later.

[0354] The fourth aspect of the present invention is a resin having constituent units derived from the compound shown in the above general formula (a0-1).

[0355] The resin system of the fourth state of the present invention is the same as the composition of (A1) above. The fourth type of grease in this invention is a resin that is useful in the inhibitor composition. [Example]

[0356] The present invention will be described in more detail below by way of examples, but the present invention is not limited to these examples.

[0357] <Examples of Compound Synthesis> [Example of intermediate synthesis] Synthesis of intermediate AL-1 20 g of 4-iodoacetophenone (AC-1) was dissolved in 80 g of THF, and the solution was added dropwise to 200 mL of methylmagnesium bromide (THF solution, 1.0 mol / L) at below 0 °C, with stirring for 2 hours. Subsequently, 100 g of saturated ammonium chloride was added to stop the reaction, and extraction was performed using 200 g of ethyl acetate. The solvent in the obtained organic layer was distilled off, and the intermediate AL-1 was obtained by silica gel chromatography.

[0358]

[0359] Synthesis of intermediate AL-2 Except for replacing the methyl magnesium bromide solution with an equal mole of ethynyl magnesium bromide solution, intermediate AL-2 was obtained using the same manufacturing method as intermediate AL-1.

[0360]

[0361] Synthesis of intermediate AL-3 25 g of 2-iodothiophene (AC-2) was added to a flask, dissolved in 150 g of THF, and then 240.7 g of 0.6 M KHMDS toluene solution was added dropwise at -30 °C, with stirring at 0 °C for 30 minutes. Subsequently, 10.0 g of acetone was added dropwise at 0 °C, with stirring for 3 hours. The reaction was then stopped by adding 100 g of saturated ammonium chloride aqueous solution, and extracted with 200 g of ethyl acetate. The solvent was then removed by distillation, and the intermediate AL-3 was obtained by silica gel chromatography.

[0362]

[0363] Synthesis of intermediate AL-4 20 g of 2,4,6-triiodoacetophenone (AC-3) was dissolved in 120 g of THF, and the solution was added dropwise to 80 mL of methylmagnesium bromide (THF solution, 1.0 mol / L) at below 0 °C, with stirring for 2 hours. Subsequently, 100 g of saturated ammonium chloride was added to stop the reaction, and extraction was performed using 200 g of ethyl acetate. The solvent in the obtained organic layer was removed by distillation, and the intermediate AL-4 was purified by silica gel chromatography.

[0364]

[0365] Synthesis of intermediate AL-5 Except for replacing the methyl magnesium bromide solution with an equal molar amount of vinyl magnesium bromide solution, AL-5 is obtained using the same manufacturing method as AL-4.

[0366]

[0367] Synthesis of intermediate AL-6 20 g of 5-norcamphene-2,3-dicarboxylic anhydride was placed in a three-necked flask and dissolved in 200 g of THF. Next, 35 g of AL-1 and 3.5 g of NaH were added, and the mixture was stirred at room temperature for 4 hours. Then, 200 g of saturated ammonium chloride aqueous solution was added to stop the reaction. The mixture was then extracted with 400 g of ethyl acetate, and the organic solvent was distilled off. The concentrate was dissolved in 300 g of ethyl acetate, and 35 g of acetone, 19 g of sodium bicarbonate, and 90 g of potassium persulfate (oxone) were added, and the mixture was stirred for 8 hours. The reaction was stopped by adding 300 g of pure water, and 120 g of ethyl acetate was added for extraction, and the solvent was distilled off. The concentrate was purified by silicone column chromatography to obtain intermediate AL-6.

[0368]

[0369] Synthesis of intermediate AL-7 Except for replacing 5-norcamphen-2,3-dicarboxylic anhydride with an equal molar amount of exo-3,6-epoxy-1,2,3,6-tetrahydrophthalic anhydride, AL-7 is obtained using the same manufacturing method as AL-6.

[0370]

[0371] [Synthesis example of compound (a0-01-1)] Intermediate AL-1 (25 g) was placed in a flask and dissolved in dichloromethane (250 g). Then, methacrylate glycolate (19 g), triethylamine (18 g), and DMAP (650 mg) were added, followed by the dropwise addition of diisopropylcarbodiimide (21 g) and stirring for 4 hours. The reaction mixture was filtered, and the filtrate was washed with 1% hydrochloric acid and pure water. The organic solvent was distilled off, and the compound (a0-01-1) was purified by silica gel chromatography.

[0372]

[0373] The obtained compound (a0-01-1) was subjected to NMR measurements (CDCl3), and its structure was identified based on the following results. δ(ppm)=7.66(m, C=CH, C=CH, 2H), 7.11(m, C=CH, C=CH, 2H), 6.40-6.50(m, C=CH 2, 2H), 5.09(s, CH2, 2H), 2.01(s, CH 3, 3H), 1.58(s, CH 3, CH 3, 6H).

[0374] [Synthesis example of compound (a0-01-2)] Except for replacing glycolic acid methacrylate with an equal number of moles of 4-vinylbenzoic acid, compound (a0-01-2) was obtained using the same manufacturing method as compound (a0-01-1).

[0375]

[0376] The obtained compound (a0-01-2) was subjected to NMR measurements (CDCl3), and its structure was identified based on the following results. δ(ppm)=7.70(m, C=CH, C=CH, 2H), 7.59(m, C=CH, C=CH, 2H), 7.45(m, C=CH, C=CH, 2H), 7.08(m, C=CH, C=CH, 2H), 6.72(dd, C=CH, 1H), 5.50-5.75(m, C=CH 2, 2H), 1.58(s, CH 3, CH 3, 6H).

[0377] [Synthesis example of compound (a0-01-3)] Intermediate AL-6 (25 g) was dissolved in 250 g of THF, cooled to 0 °C, and triethylamine (9 g) and chloro methacrylate (8 g) were added dropwise. After returning to room temperature and stirring for 5 hours, 50 g of 5% sodium bicarbonate aqueous solution was added to stop the reaction, and extraction was performed using 150 g of t-butyl methyl ether. The solvent in the obtained organic layer was distilled off, and the compound (a0-01-3) was purified by silica gel chromatography.

[0378]

[0379] The obtained compound (a0-01-3) was subjected to NMR measurements (CDCl3), and its structure was identified based on the following results. δ(ppm)=7.70(m, C=CH, C=CH, 2H), 7.10(m, C=CH, C=CH, 2H), 6.20-6.40(m, C=CH 2, 2H), 5.05-5.10(m, C-CH, C-CH, 2H), 2.70-3.00(m, C-CH, C-CH, 2H)2.50-2.70(m, CH, CH, 2H), 2.00-2.30(m, CH 2, 2H), 1.95(s, CH 3, 3H), 1.58(s, CH 3, CH 3, 6H).

[0380] [Synthesis example of compound (a0-01-4)] Except for changing intermediate AL-1 to an equal molar intermediate AL-2, compound (a0-01-4) was obtained using the same manufacturing method as compound (a0-01-2).

[0381]

[0382] The obtained compound (a0-01-4) was subjected to NMR measurements (CDCl3), and its structure was identified based on the following results. δ(ppm)=7.70(m, C=CH, C=CH, 2H), 7.59(m, C=CH, C=CH, 2H), 7.45(m, C=CH, C=CH, 2H), 7.08(m, C=CH, C=CH, 2H), 6.72(dd, C=CH, 1H), 5.50-5.75(m, C=CH 2, 2H), 3.65(s, C≡CH, 1H), 1.60(s, CH 3, 3H).

[0383] [Synthesis example of compound (a0-01-5)] Except for changing intermediate AL-1 to an equal molar intermediate AL-3, compound (a0-01-5) was obtained using the same manufacturing method as compound (a0-01-2).

[0384]

[0385] The obtained compound (a0-01-5) was subjected to NMR measurements (CDCl3), and its structure was identified based on the following results. δ(ppm)=7.70(m, C=CH, C=CH, 2H), 7.47(m, C=CH, C=CH, 2H), 7.45(m, C=CH, C=CH, 2H), 7.08(d, C=CH, 1H), 6.60-6.75(m, C=CH, C=CH, 2H), 5.75(dd, C=CH, 1H), 5.23(dd, C=CH, 1H)1.60(s, CH 3, CH 3, 6H).

[0386] [Synthesis example of compound (a0-01-6)] AL-1 (25 g) was added to a flask and dissolved in dichloromethane (250 g). Then, 5-vinylsalicylic acid (15 g), CDI (17 g), and DBU (13 g) were added, and the mixture was stirred for 6 hours. Next, 1% citric acid (200 g) was added to the reaction solution to stop the reaction. The organic layer was extracted and washed with pure water. After distilling off the organic solvent, the compound (a0-01-6) was purified by silicone column chromatography.

[0387]

[0388] The obtained compound (a0-01-6) was subjected to NMR measurements (CDCl3), and its structure was identified based on the following results. δ(ppm)=8.80(s, -OH, 1H), 7.65-7.55(m, C=CH, C=CH, C=CH, 3H), 7.20-6.60(m, C=CH, C=CH, C=CH, C=CH, C=CH, 5H), 5.30-5.85(m, C=CH 2, 2H), 1.61(s, CH 3, CH 3, 6H).

[0389] [Synthesis example of compound (a0-01-7)] Except for changing intermediate AL-6 to an equal molar intermediate AL-7, compound (a0-01-7) was obtained using the same manufacturing method as compound (a0-01-3).

[0390]

[0391] The obtained compound (a0-01-7) was subjected to NMR measurements (CDCl3), and its structure was identified based on the following results. δ(ppm)=7.70(m, C=CH, C=CH, 2H), 7.10(m, C=CH, C=CH, 2H), 6.20-6.50(m, C=CH 2, 2H), 5.15-5.40(m, C-CH, C-CH, 2H), 4.40-4.70(m, C-CH, C-CH, 2H)3.00-3.20(m, CH, CH, 2H), 2.05(s, CH 3, 3H), 1.66(s, CH 3, CH 3, 6H).

[0392] [Synthesis example of compound (a0-01-8)] Except for changing intermediate AL-1 to an equal molar intermediate AL-4, compound (a0-01-8) was obtained using the same manufacturing method as compound (a0-01-6).

[0393]

[0394] The obtained compound (a0-01-8) was subjected to NMR measurements (CDCl3), and its structure was identified based on the following results. δ(ppm)=8.20(s, -OH, 1H), 7.75-7.50(m, C=CH, C=CH, C=CH, 3H), 7.20(s, C=CH, 1H), 6.60-6.90(m, C=CH, C=CH, 2H), 5.30-5.85(m, C=CH 2, 2H), 1.68(s, CH 3, CH 3, 6H).

[0395] [Synthesis example of compound (a0-01-9)] Except for changing intermediate AL-1 to an equal molar intermediate AL-5, compound (a0-01-9) was obtained using the same manufacturing method as compound (a0-01-6).

[0396]

[0397] The obtained compound (a0-01-9) was subjected to NMR measurements (CDCl3), and its structure was identified based on the following results. δ(ppm)=8.20(s, -OH, 1H), 7.75-7.50(m, C=CH, C=CH, C=CH, 3H), 7.20(s, C=CH, 1H), 6.60-6.90(m, C=CH, C=CH, 2H), 5.30-5.85(m, C=CH 2, 2H), 5.10-5.30(m, C=CH 2, 2H), 4.80-4.95(m, C=CH, 1H)1.68(s, CH 3, 3H).

[0398] <Example 1 of Polymer Synthesis> [Synthesis example of polymer compound (A1-1)] A dropwise solution was prepared by dissolving 32.4 g of compound (a0-01-1), 10.0 g of compound (m-a10-1pre), and 2.38 g of dimethyl azobis(isobutyrate) (V-601) as a polymerization initiator in 20.3 g of MEK (methyl ethyl ketone). 33.7 g of MEK was added to a three-necked flask connected to a thermometer, reflux tube, and nitrogen inlet tube. The mixture was heated to 85°C under nitrogen and the aforementioned dropwise solution was added dropwise over 4 hours. After the dropwise addition was complete, the reaction mixture was stirred at 85°C for 1 hour. The reaction mixture was then cooled to room temperature. After the reaction was complete, the precipitate was collected in 2600 g of heptane and washed. The obtained white solid was filtered and dried under reduced pressure overnight to obtain the target polymer compound (A1-1).

[0399]

[0400] <Examples 2-15 of Polymer Synthesis> Using the same method as in Example 1 of the synthesis of polymeric compounds, polymeric compounds (A1-2) to (A1-15) were synthesized using the compounds (a0-01-1) to (a0-01-9) shown above, the compounds (m-a10-1pre) to (m-a10-3pre) shown below, and (m-a2-1) to (m-a2-3).

[0401]

[0402] For each obtained polymer compound, the weight average molecular weight (Mw) and molecular weight dispersion (Mw / Mn) were determined by GPC measurement (converted from standard polystyrene). Furthermore, for each obtained polymer compound, the copolymer composition ratio (the proportion of each constituent unit in the structural formula (molar ratio)) was determined by carbon-13 nuclear magnetic resonance spectroscopy (600MHz 13C-NMR).

[0403]

[0404] Polymer compound (A1-1): weight average molecular weight (Mw) 7500, molecular weight dispersion (Mw / Mn) 1.65, l / m=50 / 50. Polymer compound (A1-2): weight average molecular weight (Mw) 7400, molecular weight dispersion (Mw / Mn) 1.67, l / m=50 / 50. Polymer compound (A1-3): weight average molecular weight (Mw) 7500, molecular weight dispersion (Mw / Mn) 1.64, l / m=50 / 50. Polymer compound (A1-4): weight average molecular weight (Mw) 7600, molecular weight dispersion (Mw / Mn) 1.65, l / m=50 / 50. Polymer compound (A1-5): weight average molecular weight (Mw) 7400, molecular weight dispersion (Mw / Mn) 1.63, l / m=50 / 50. Polymer compound (A1-6): weight average molecular weight (Mw) 7500, molecular weight dispersion (Mw / Mn) 1.65, l / m=50 / 50.

[0405]

[0406] Polymer compound (A1-7): weight average molecular weight (Mw) 7500, molecular weight dispersion (Mw / Mn) 1.64, l / m=50 / 50. Polymer compound (A1-8): weight average molecular weight (Mw) 7600, molecular weight dispersion (Mw / Mn) 1.67, l / m=50 / 50. Polymer compound (A1-9): weight average molecular weight (Mw) 7400, molecular weight dispersion (Mw / Mn) 1.66, l / m=50 / 50. Polymer compound (A1-10): weight average molecular weight (Mw) 7400, molecular weight dispersion (Mw / Mn) 1.67, l / m=50 / 50. Polymer compound (A1-11): weight average molecular weight (Mw) 7600, molecular weight dispersion (Mw / Mn) 1.63, l / m / n=50 / 40 / 10.

[0407]

[0408] Polymer compound (A1-12): weight average molecular weight (Mw) 7500, molecular weight dispersion (Mw / Mn) 1.66, l / m / n=50 / 40 / 10. Polymer compound (A1-13): weight average molecular weight (Mw) 7500, molecular weight dispersion (Mw / Mn) 1.66, l / m / n=50 / 40 / 10. Polymer compound (A1-14): weight average molecular weight (Mw) 7500, molecular weight dispersion (Mw / Mn) 1.67, l / m / n=50 / 40 / 10. Polymer compound (A1-15): weight average molecular weight (Mw) 7400, molecular weight dispersion (Mw / Mn) 1.66, l / m / n=50 / 40 / 10.

[0409] <Preparation of Inhibitor Components> (Implementation Examples 1-17, Comparative Examples 1-4) The components shown in Tables 1-3 were mixed and dissolved to prepare the respective inhibitor compositions.

[0410]

[0411]

[0412]

[0413] In Tables 1-3, each abbreviation has the following meaning. The value in [ ] is the amount of admixture (parts by mass).

[0414] (A1)-1~(A1)-15: The above-mentioned polymer compounds (A1-1)~(A1-15).

[0415] (A2)-1: The polymer compound represented by the chemical formula (A2-1) below. For this polymer compound (A2)-1, the weight-average molecular weight (Mw) converted from standard polystyrene by GPC measurement is 7500, and the molecular weight dispersion (Mw / Mn) is 1.64. 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.

[0416] (A2)-2: The polymer compound represented by the chemical formula (A2-2) below. For this polymer compound (A2)-2, the weight-average molecular weight (Mw) converted from standard polystyrene by GPC measurement is 7400, and the molecular weight dispersion (Mw / Mn) is 1.65. 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.

[0417] (A2)-3: The polymer compound represented by the chemical formula (A2-3) below. For this polymer compound (A2)-3, the weight-average molecular weight (Mw) converted from standard polystyrene by GPC measurement is 7600, 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)) determined by 13C-NMR is 1 / m / n / o = 38 / 46 / 11 / 5.

[0418] (A2)-4: The polymer compound represented by the chemical formula (A2-4) below. For this polymer compound (A2)-4, the weight-average molecular weight (Mw) converted from standard polystyrene by GPC measurement is 7400, and the molecular weight dispersion (Mw / Mn) is 1.67. 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.

[0419]

[0420] (B)-1: An acid-generating agent composed of the following compound (B-1). (B)-2: An acid-generating agent consisting of the following compound (B-2). (D)-1: An acid diffusion control agent composed of the following compound (D-1). (S)-1: A mixed solvent of propylene glycol monomethyl ether acetate / propylene glycol monomethyl ether = 60 / 40 (mass ratio).

[0421]

[0422] <Formation of Inhibitor Patterns> On an 8-inch silicon substrate that has been treated with hexamethyldisilazane (HMDS), the resist composition of each example is coated using a spin coater. The resist film with a thickness of 70 nm is formed by pre-baking (PAB) on a hot plate at a temperature of 110°C for 60 seconds and then drying. Secondly, for the aforementioned resist film, using an electronic line drawing device JEOL-JBX-9300FS (manufactured by Japan Electronics Corporation), after drawing (exposure) a 1:1 linewidth and spacing pattern (hereinafter referred to as LS pattern) with a target size of 50nm, at an accelerating voltage of 100kV, the film was subjected to post-exposure heating (PEB) treatment at 100°C for 60 seconds. Next, alkaline development was performed for 60 seconds at 23°C using a 2.38% by mass tetramethylammonium hydroxide (TMAH) aqueous solution "NMD-3" (trade name, manufactured by Tokyo Ohka Kogyo Co., Ltd.). Afterward, rinse with pure water for 15 seconds. The result is a 1:1 LS pattern with a linewidth of 50 nm.

[0423] [Evaluation of Optimal Exposure (Eop)] The optimal exposure value Eop (μC / cm 2) that will form the target size pattern through the above <Resistant Pattern Formation> will be determined. It will be represented as "Eop (μC / cm 2)" in Tables 4 and 5.

[0424] [LWR's Evaluation] For the LS pattern formed by the above <formation of the resist pattern>, the 3σ of the scale showing LWR is determined. This is presented as "LWR (nm)" in Tables 4 and 5. "3σ" refers to the measurement taken at position 400 along the length of the line using a scanning electron microscope (accelerating voltage 800V, trade name: S-9380, manufactured by Hitachi High Technology Co., Ltd.), and the value of three times the standard deviation (σ) obtained from this measurement (3σ) is denoted as "LWR". The smaller the value of 3σ, the smaller the roughness of the line sidewall, resulting in a more uniform width LS pattern.

[0425]

[0426]

[0427] As shown in Tables 4 and 5, it can be confirmed that the resist composition of the Examples has higher sensitivity in resist pattern formation and good LWR compared with the resist composition of the Comparative Examples.

[0428] The preferred embodiments of the present invention have been described above, but the present invention is not limited to these embodiments. Additions, omissions, substitutions, and other modifications to the structure can be implemented without departing from the spirit and scope of the present invention. The present invention is not limited to the foregoing description, but only to the scope of the accompanying patent claims.

Claims

1. A resist composition that generates acid upon exposure and alters the solubility of a developer due to the action of the acid, comprising a resin component (A1) having a constituent unit (a01) derived from a compound of the following general formula (a0-1-1); wherein, R01 is a hydrogen atom, an alkyl group having 1 to 10 carbon atoms, or a haloalkyl group having 1 to 10 carbon atoms; L001 is an ester bond, an aromatic hydrocarbon group, a cyclic group containing a lactone, or a divalent linking group having a group composed of such combinations; Ra01 and Ra02 are each independently a hydrocarbon group that may have substituents; Ar01 is an aryl group in which one or all of the hydrogen atoms are replaced by iodine atoms, or a heteroaryl group in which one or all of the hydrogen atoms are replaced by iodine atoms; the aforementioned aryl and heteroaryl groups may also have substituents other than iodine atoms.

2. The inhibitor composition of claim 1, wherein the proportion of the aforementioned constituent unit (a01) in the aforementioned resin component (A1) is 20 to 80 mol relative to the total (100 mol%) of all constituent units constituting the aforementioned resin component (A1).

3. A method for forming a resist pattern, comprising: a step of forming a resist film on a support using a resist composition such as claimed in claim 1 or 2; a step of exposing the resist film; and a step of developing the exposed resist film to form a resist pattern.

4. The resist pattern forming method as claimed in claim 3, wherein in the aforementioned step of exposing the resist film, the resist film is exposed to extreme ultraviolet (EUV) or electron beam (EB).

5. A compound represented by the following general formula (a0-1-1), wherein R01 is a hydrogen atom, an alkyl group having 1 to 10 carbon atoms, or a haloalkyl group having 1 to 10 carbon atoms; L001 is an ester bond, an aromatic hydrocarbon group, a cyclic group containing a lactone, or a divalent linked group having a group composed of such combinations; Ra01 and Ra02 are each independently a hydrocarbon group that may have substituents; Ar01 is an aryl group in which one or all of the hydrogen atoms are replaced by iodine atoms, or a heteroaryl group in which one or all of the hydrogen atoms are replaced by iodine atoms; the aforementioned aryl and heteroaryl groups may also have substituents other than iodine atoms.