Resist composition and resist pattern forming method

Abstract

A negative resist composition containing: a high molecular compound (A1) having a structural unit (a10) containing a phenolic hydroxyl group, an acid generator (B0) represented by the following general formula (b0-1), a crosslinking agent (C), an aromatic compound (Z) having 1 or 2 phenolic hydroxyl groups and not having a carboxyl group in the molecule (in the formula, Rb 1 is an organic group, and Rb 2 is a group represented by the following general formula (b0-r-1) or the following general formula (b0-r-2).[Chemical Formula 1]

Description

Technical Field

[0001] This invention relates to resist compositions and methods for forming resist patterns.

[0002] This application claims priority based on Japanese Patent Application No. 2019-227234 filed in Japan on December 17, 2019, the contents of which are incorporated herein by reference. Background Technology

[0003] In recent years, the miniaturization of patterns has rapidly progressed in the manufacturing of semiconductor devices and liquid crystal display devices due to advancements in photolithography technology. As a method of miniaturization, generally speaking, the wavelength of the exposure light source is shortened (higher energy).

[0004] For resist materials, photolithographic properties such as sensitivity relative to these exposure light sources and resolution capable of reproducing fine-sized patterns are required.

[0005] As a resist material that meets such requirements, conventionally used resist compositions include a chemically amplified resist composition containing a substrate component whose solubility in the developer changes due to the action of acid, and an acid-generating agent component that generates acid through exposure.

[0006] For resist materials, photolithographic properties such as sensitivity relative to these exposure light sources and resolution capable of reproducing fine-sized patterns are required.

[0007] As a resist material that meets such requirements, conventionally used resist compositions include a chemically amplified resist composition containing a substrate component whose solubility in the developer changes due to the action of acid, and an acid-generating agent component that generates acid through exposure.

[0008] For example, when the developer is an alkaline developer (alkaline development process), a positive chemical amplification resist composition is generally used, which contains a resin component (base resin) whose solubility in the alkaline developer increases due to the action of acid, and an acid-generating agent component. If the resist film formed using the aforementioned resist composition is selectively exposed during resist pattern formation, acid is generated in the exposed areas by the acid-generating agent component. The polarity of the base resin increases due to the action of this acid, and the exposed areas of the resist film become soluble relative to the alkaline developer. Therefore, by performing alkaline development, a positive pattern is formed as the pattern residue in the unexposed areas of the resist film.

[0009] Furthermore, conventionally, chemically amplified resist compositions containing a substrate component (alkali-soluble substrate component) soluble in alkaline developer, an acid-generating agent component that generates acid upon exposure, and a crosslinking agent component have been used as resist materials. For example, when acid is generated from the acid-generating agent component upon exposure, this acid acts to crosslink between the alkali-soluble substrate component and the crosslinking agent component, resulting in reduced solubility in alkaline developer. Therefore, in the formation of resist patterns, if the resist film obtained by coating the aforementioned chemically amplified resist composition onto a support is selectively exposed, the exposed portion of the resist film becomes less soluble in alkaline developer, while the unexposed portion of the resist film retains no change in solubility in alkaline developer. Therefore, by developing with alkaline developer, negative resist patterns can be formed.

[0010] For example, Patent Document 1 describes a negative chemical amplification resist composition containing an alkali-soluble polyhydroxystyrene resin, an acid crosslinking substance, a specific photoacid generator, and a dissolution promoter.

[0011] Existing technical documents

[0012] Patent documents

[0013] Patent Document 1: Japanese Patent No. 3655030 Summary of the Invention

[0014] The technical problem that the invention aims to solve

[0015] The inventors found that when using a negative resist composition with an alkali-soluble polyhydroxystyrene resin as a substrate component to form a resist pattern, the etching resistance is sometimes insufficient when forming a micron-scale thick resist film using wet etching resistance, and then forming the resist pattern and etching.

[0016] The present invention was made in view of the above circumstances, and its technical problem is to provide a resist composition capable of forming a resist pattern with good etching resistance and a method for forming a resist pattern using the resist composition.

[0017] Solution to the above technical problems

[0018] To solve the above-mentioned technical problems, the present invention adopts the following structure.

[0019] That is, the first aspect of the present invention is a negative resist composition comprising: a polymeric compound (A1) having a structural unit (a10) represented by the following general formula (a10-1), an acid-generating agent (B0) represented by the following general formula (b0-1), a crosslinking agent (C), and an aromatic compound (Z) having one or two phenolic hydroxyl groups in the molecule and not having a carboxyl group.

[0020] [Chemistry 1]

[0021]

[0022] [In the formula, R is a hydrogen atom, an alkyl group having 1 to 5 carbon atoms, or a haloalkyl group having 1 to 5 carbon atoms. Ya] x1 It is a single bond or a divalent linker. Wa x1 It is an aromatic hydrocarbon group that can have substituents. ax1 Integers greater than or equal to 1.

[0023] [Chemistry 2]

[0024]

[0025] [In the formula, Rb] 1 It is an organic group. Rb 2 It is a group represented by the following general formula (b0-r-1) or the following general formula (b0-r-2).

[0026] [Chemistry 3]

[0027]

[0028] In the formula (b0-r-1), Rb 201 and Rb 202 Each is an independent organic group. * indicates a bond. In formula (b0-r-2), Xb is a group that, together with -(O=)CNC(=O)-, forms a cyclic group with a cyclic imide structure. * indicates a bond.

[0029] The second aspect of the present invention is a method for forming a resist pattern, comprising: a step of forming a resist film on a support using the resist composition of the first aspect; a step of exposing the resist film; and a step of developing the exposed resist film to form a resist pattern.

[0030] Invention Effects

[0031] According to the present invention, a resist composition capable of forming a resist pattern with good etching resistance and a method for forming a resist pattern using the resist composition can be provided. Detailed Implementation

[0032] In this specification and the claims of this invention, "aliphatic" is a relative concept compared to aromatic, and is defined as a group, compound, etc. that does not have aromatic properties.

[0033] Unless otherwise specified, "alkyl" includes straight-chain, branched, and cyclic monovalent saturated hydrocarbon groups. The same applies to alkyl groups in alkoxy groups.

[0034] Unless otherwise specified, "alkylene" includes straight-chain, branched, and cyclic divalent saturated hydrocarbon groups.

[0035] Examples of "halogen atoms" include fluorine atoms, chlorine atoms, bromine atoms, and iodine atoms.

[0036] "Structural unit" refers to the monomer unit (monomeric unit) that makes up a polymer compound (resin, polymer, copolymer).

[0037] When it is stated that "substituents may be present", there are two cases: replacing the hydrogen atom (-H) with a monovalent group and replacing the methylene group (-CH2-) with a divalent group.

[0038] "Exposure" refers to the concept of exposure to all types of radiation.

[0039] "Acid-degradable group" is a group that has acid-degradable properties, meaning that at least some of the bonds in the structure of the acid-degradable group can be broken under the action of an acid.

[0040] As an acid-decomposing group whose polarity increases due to the action of an acid, examples can be given of groups that decompose to produce polar groups through the action of an acid.

[0041] Examples of polar groups include carboxyl, hydroxyl, amino, and sulfonic acid groups (-SO3H).

[0042] More specifically, as an acid-dissociating group, an example can be a group obtained by protecting the polar group with an acid-dissociating group (for example, a group obtained by protecting the hydrogen atom of a polar group containing OH with an acid-dissociating group).

[0043] "Acid-dissociable group" refers to either of the following: (i) an acid-dissociable group whose bonds with the adjacent atom can be broken by the action of an acid; or (ii) a group whose bonds, after being broken by the action of an acid, further undergo a decarboxylation reaction, thereby allowing the bonds with the adjacent atom to be broken.

[0044] The acid-dissociating groups that constitute the acid-dissociating groups must be groups with lower polarity than the polar groups generated through the dissociation of these acid-dissociating groups. Therefore, when these acid-dissociating groups dissociate under the action of acid, groups with higher polarity than the original acid-dissociating groups are generated, thus increasing the overall polarity of the (A1) component. This increased polarity leads to a relative change in the solubility in the developer; solubility increases when the developer is alkaline and decreases when the developer is organic.

[0045] "Substrate component" refers to an organic compound with film-forming ability. Organic compounds used as substrate components are broadly classified into non-polymers and polymers. Non-polymers typically use compounds with a molecular weight of 500 or higher but less than 4000. Hereinafter, "low molecular weight compound" refers to a non-polymer with a molecular weight of 500 or higher but less than 4000. Polymers typically use compounds with a molecular weight of 1000 or higher. Hereinafter, "resin," "high molecular weight compound," or "polymer" refers to a polymer with a molecular weight of 1000 or higher. The molecular weight of polymers is the mass-average molecular weight calculated for polystyrene based on GPC (gel permeation chromatography).

[0046] "Derived structural units" refer to structural units formed by the breaking of multiple bonds between carbon atoms, such as alkene double bonds.

[0047] The hydrogen atom bonded to the carbon atom at the α-position of "acrylate" can be replaced by a substituent. The substituent (R) that replaces the hydrogen atom bonded to the carbon atom at the α-position... αx () refers to atoms or groups other than hydrogen atoms. It also includes substituents (R...). αx Itaconic acid diesters substituted with substituents containing ester bonds, substituents (R) αx α-hydroxy acrylates substituted with hydroxyalkyl groups or groups modifying their hydroxyl groups. Furthermore, unless otherwise specified, the carbon atom at the α-position of the acrylate refers to the carbon atom bonded to the carbonyl group of acrylic acid.

[0048] Hereinafter, acrylates obtained by replacing the hydrogen atom bonded to the carbon atom at the α-position with a substituent are sometimes referred to as α-substituted acrylates.

[0049] "Derivative" refers to compounds in which the hydrogen atom at the α-position of the target compound is replaced by other substituents such as alkyl or haloalkyl groups, and their derivatives. Examples of their derivatives include compounds obtained by replacing the hydrogen atom of the hydroxyl group in the target compound with an organic group; and compounds obtained by bonding a substituent other than a hydroxyl group to the target compound in which the hydrogen atom at the α-position can be replaced by a substituent. Furthermore, unless otherwise specified, the α-position refers to the first carbon atom adjacent to the functional group.

[0050] As a substituent for the hydrogen atom at the α-position of hydroxystyrene, examples can be found with R αx The same group.

[0051] In this specification and the claims of this invention, depending on the structure represented by the chemical formula, there exist asymmetric carbon structures, and there may be enantiomers or diastereomers. In this case, these isomers are represented by a single chemical formula. These isomers can be used alone or as mixtures.

[0052] (Resistant Composition)

[0053] The resist composition of the first aspect of the present invention is a negative resist composition.

[0054] As one embodiment of the above-mentioned resist composition, an example of a resist composition may be provided, which contains a substrate component (A) whose solubility in the developer changes due to the action of acid (hereinafter also referred to as "(A) component"), an acid-generating agent component (B) that generates acid through exposure (hereinafter also referred to as "(B) component"), a crosslinking agent (C) (hereinafter also referred to as "(C) component"), and an aromatic compound (Z) having one or two phenolic hydroxyl groups in the molecule but not a carboxyl group (hereinafter also referred to as "(Z) component").

[0055] In the resist composition of this embodiment, component (A) comprises a polymeric compound (A1) having a structural unit (a10) represented by general formula (a10-1) (hereinafter referred to as "(A1) component"), and component (B) comprises an acid-generating agent (B0) represented by general formula (b0-1) (hereinafter referred to as "(B0) component").

[0056] If a resist film is formed using the resist composition of this embodiment and the resist film is selectively exposed, acid is generated in the exposed portion of the resist film. The solubility of component (A) in the developer changes due to the action of this acid. On the other hand, in the unexposed portion of the resist film, the solubility of component (A) in the developer does not change. Therefore, a difference in solubility in the developer occurs between the exposed and unexposed portions of the resist film. Thus, if the resist film is subjected to alkaline development, the unexposed portion of the resist film is dissolved and removed, forming a negative resist pattern.

[0057] In this specification, a resist composition in which the exposed portion of the resist film is dissolved and removed to form a positive resist pattern is referred to as a positive resist composition, and a resist composition in which the unexposed portion of the resist film is dissolved and removed to form a negative resist pattern is referred to as a negative resist composition. The resist composition of this embodiment is a negative resist composition.

[0058] <(A)Component>

[0059] (A) The composition refers to the substrate components whose solubility in the developer changes due to the action of acid.

[0060] In this invention, "substrate composition" refers to an organic compound with film-forming ability, preferably an organic compound with a molecular weight of 500 or more. By making the molecular weight of the organic compound 500 or more, the film-forming ability is improved, and in addition, it is easier to form nanoscale resist patterns.

[0061] Organic compounds used as base material components are broadly classified into non-polymers and polymers.

[0062] As non-polymers, non-polymers with a molecular weight of 500 or higher and less than 4000 are generally used. Hereinafter, when "low molecular weight compound" is mentioned, it refers to a non-polymer with a molecular weight of 500 or higher and less than 4000. As polymers, polymers with a molecular weight of 1000 or higher are generally used. Hereinafter, when "resin," "high molecular weight compound," or "polymer" is mentioned, it refers to a polymer with a molecular weight of 1000 or higher. The molecular weight of polymers is the weight-average molecular weight calculated for polystyrene based on GPC (gel permeation chromatography).

[0063] In the resist composition of this embodiment, at least a polymeric compound (A1) having a structural unit (a10) represented by the general formula (a0-1) is used in component (A), and polymeric compounds and / or low molecular weight compounds other than component (A1) may also be used.

[0064] If a resist film is formed using a resist composition containing at least component (A1), and this resist film is selectively exposed, acid is generated from component (B) in the exposed portion of the resist film, for example, if the resist composition contains component (B). Through the action of this acid, cross-linking occurs between the cross-linking structural unit (a10) and component (A1). As a result, the solubility of the exposed portion of the resist film in alkaline developer decreases. Therefore, in the formation of a resist pattern, if the resist film obtained by coating the resist composition of this embodiment onto a support is selectively exposed, the exposed portion of the resist film becomes less soluble in alkaline developer. On the other hand, the solubility of the unexposed portion of the resist film in alkaline developer remains unchanged. Therefore, by developing with alkaline developer, a negative resist pattern can be formed.

[0065] Regarding component (A1)

[0066] (A1) component is a polymeric compound having a structural unit (a10) represented by the general formula (a0-1).

[0067] As component (A1), a copolymer having a structural unit (a11) in addition to structural unit (a10) is preferred, wherein the structural unit (a11) is a structural unit that contains an aromatic ring (excluding the aromatic ring bonded to a hydroxyl group) in the side chain.

[0068] In addition, the (A1) component may have other structural units besides structural units (a10) and structural units (a11).

[0069] Regarding structural unit (a10):

[0070] The structural unit (a10) is a structural unit represented by the following general formula (a10-1).

[0071] [Chemistry 4]

[0072]

[0073] [In the formula, R is a hydrogen atom, an alkyl group having 1 to 5 carbon atoms, or a haloalkyl group having 1 to 5 carbon atoms. Ya] x1 It is a single bond or a divalent linker. Wa x1 It is an aromatic hydrocarbon group that can have substituents. ax1 Integers greater than or equal to 1.

[0074] [In the formula, R is a hydrogen atom, an alkyl group having 1 to 5 carbon atoms, or a haloalkyl group having 1 to 5 carbon atoms. Ya] x1 It is a single bond or a divalent linker. Wa x1 It is an aromatic hydrocarbon group that can have substituents. ax1 Integers greater than or equal to 1.

[0075] In the 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.

[0076] The alkyl group having 1 to 5 carbon atoms in R is preferably a straight-chain or branched alkyl group having 1 to 5 carbon atoms. Examples include methyl, ethyl, propyl, isopropyl, n-butyl, isobutyl, tert-butyl, pentyl, isopentyl, neopentyl, etc.

[0077] The alkyl halogroup having 1 to 5 carbon atoms in R is a group obtained by substituting some or all of the hydrogen atoms of the alkyl halogroup having 1 to 5 carbon atoms with halogen atoms. Fluorine atoms are particularly preferred as this halogen atom.

[0078] R is preferably a hydrogen atom, an alkyl group having 1 to 5 carbon atoms, or a fluoroalkyl group having 1 to 5 carbon atoms. From the perspective of industrial availability, it is more preferably a hydrogen atom, a methyl group, or a trifluoromethyl group. It is even more preferably a hydrogen atom or a methyl group, and particularly preferably a methyl group.

[0079] In the aforementioned formula (a10-1), Ya x1 It is a single bond or a divalent linker.

[0080] In the chemical formula, Ya is used as... x1 The divalent linking group is not particularly limited, and examples such as divalent hydrocarbon groups with substituents and divalent linking groups containing heteroatoms can be used as preferred linking groups.

[0081] • Divalent hydrocarbon groups that may have substituents:

[0082] In Ya x1 In the case of a divalent hydrocarbon group that may have substituents, the hydrocarbon group can be an aliphatic hydrocarbon group or an aromatic hydrocarbon group.

[0083] ··Ya x1 aliphatic hydrocarbon groups

[0084] Aliphatic hydrocarbon groups refer to hydrocarbon groups that do not possess aromaticity. These aliphatic hydrocarbon groups can be saturated or unsaturated, but are generally preferred to be saturated. Examples of such aliphatic hydrocarbon groups include straight-chain or branched aliphatic hydrocarbon groups, or aliphatic hydrocarbon groups containing rings in their structure.

[0085] ...straight-chain or branched aliphatic hydrocarbon groups

[0086] The linear aliphatic hydrocarbon group preferably has 1 to 10 carbon atoms, more preferably 1 to 6 carbon atoms, even more preferably 1 to 4 carbon atoms, and most preferably 1 to 3 carbon atoms.

[0087] As a straight-chain aliphatic hydrocarbon group, a straight-chain alkylene group is preferred. Specifically, examples include methylene [-CH2-], ethylene [-(CH2)2-], propylene [-(CH2)3-], butylene [-(CH2)4-], and pentylene [-(CH2)5-].

[0088] The branched aliphatic hydrocarbon group preferably has 2 to 10 carbon atoms, more preferably 3 to 6 carbon atoms, even more preferably 3 or 4 carbon atoms, and most preferably 3 carbon atoms.

[0089] As a branched aliphatic hydrocarbon group, a branched alkylene group is preferred. Specifically, examples include alkylmethylene groups such as -CH(CH3)-, -CH(CH2CH3)-, -C(CH3)2-, -C(CH3)(CH2CH3)-, -C(CH3)(CH2CH2CH3)-, and -C(CH2CH3)2-; alkylethylene groups such as -CH(CH3)CH2-, -CH(CH3)CH(CH3)-, -C(CH3)2CH2-, -CH(CH2CH3)CH2-, and -C(CH2CH3)2-CH2-; alkylpropylene groups such as -CH(CH3)CH2CH2- and -CH2CH(CH3)CH2-; and alkylalkylene groups such as -CH(CH3)CH2CH2CH2- and -CH2CH(CH3)CH2CH2-. The alkyl group in the alkyl alkylene group is preferably a straight-chain alkyl group having 1 to 5 carbon atoms.

[0090] The straight-chain or branched aliphatic hydrocarbon group may or may not have substituents. Examples of such substituents include fluorine atoms, fluoroalkyl groups with 1 to 5 carbon atoms substituted by fluorine atoms, and carbonyl groups.

[0091] ...aliphatic hydrocarbon groups containing rings in their structure

[0092] Examples of aliphatic hydrocarbon groups containing a ring in the structure include cyclic aliphatic hydrocarbon groups containing heteroatoms and substituents (groups obtained by removing two hydrogen atoms from an aliphatic hydrocarbon ring), groups obtained by bonding the cyclic aliphatic hydrocarbon group to the end of a straight-chain or branched aliphatic hydrocarbon group, and groups where the cyclic aliphatic hydrocarbon group is intermediate between a straight-chain or branched aliphatic hydrocarbon group. Examples of straight-chain or branched aliphatic hydrocarbon groups are the same aliphatic hydrocarbon groups as described above.

[0093] The cyclic aliphatic hydrocarbon group preferably has 3 to 20 carbon atoms, more preferably 3 to 12 carbon atoms.

[0094] The cyclic alicyclic hydrocarbon group can be either a polycyclic or a monocyclic group. As a monocyclic alicyclic hydrocarbon group, it is preferably a group obtained by removing two hydrogen atoms from a monocyclic alkane. As the monocyclic alkane, a monocyclic alkane with 3 to 6 carbon atoms is preferred; examples include cyclopentane and cyclohexane. As a polycyclic alicyclic hydrocarbon group, it is preferably a group obtained by removing two hydrogen atoms from a polycyclic alkane. As the polycyclic alkane, a polycyclic alkane with 7 to 12 carbon atoms is preferred; examples include adamantane, norbornane, isobornane, tricyclodecane, and tetracyclododecane.

[0095] Cyclic aliphatic hydrocarbon groups may or may not have substituents. Examples of substituents include alkyl groups, alkoxy groups, halogen atoms, haloalkyl groups, hydroxyl groups, and carbonyl groups.

[0096] The alkyl group used as the substituent is preferably an alkyl group having 1 to 5 carbon atoms, and more preferably methyl, ethyl, propyl, n-butyl, or tert-butyl.

[0097] The alkoxy group used as the substituent is preferably an alkoxy group having 1 to 5 carbon atoms, more preferably methoxy, ethoxy, n-propoxy, isopropoxy, n-butoxy, or tert-butoxy, and even more preferably methoxy or ethoxy.

[0098] The halogen atom used as the substituent is preferably a fluorine atom.

[0099] The alkyl halogroup that serves as the substituent can be exemplified by groups obtained by replacing some or all of the hydrogen atoms of the alkyl group with the halogen atom.

[0100] A portion of the carbon atom constituting the ring structure of a cyclic aliphatic hydrocarbon group can also be replaced by a substituent containing a heteroatom. Preferred substituents containing heteroatom include -O-, -C(=O)-O-, -S-, -S(=O)2-, and -S(=O)2-O-.

[0101] ··Ya x1 aromatic hydrocarbon groups

[0102] The aromatic hydrocarbon group is a hydrocarbon group having at least one aromatic ring.

[0103] The aromatic ring is not particularly limited to a cyclic conjugated system having 4n+2 π electrons; it can be monocyclic or polycyclic. The number of carbon atoms in the aromatic ring is preferably 5 to 30, more preferably 5 to 20, further preferably 6 to 15, and particularly preferably 6 to 12. This number of carbon atoms does not include the carbon atoms in the substituents.

[0104] Examples of aromatic rings include aromatic hydrocarbon rings such as benzene, naphthalene, anthracene, and phenanthrene; and aromatic heterocycles formed by replacing a portion of the carbon atoms in the aforementioned aromatic hydrocarbon rings with heteroatoms. Examples of heteroatoms in aromatic heterocycles include oxygen atoms, sulfur atoms, and nitrogen atoms. Examples of aromatic heterocycles include pyridine rings and thiophene rings.

[0105] Specifically, examples of aromatic hydrocarbon groups include groups (aryl or heteroaryl) obtained by removing two hydrogen atoms from an aromatic hydrocarbon ring or aromatic heterocycle; groups obtained by removing two hydrogen atoms from an aromatic compound containing two or more aromatic rings (e.g., biphenyl, fluorene, etc.); and groups obtained by substituting one hydrogen atom of an aryl or heteroaryl group obtained by removing one hydrogen atom from an aryl alkyl group (e.g., groups obtained by further removing one hydrogen atom from an aryl alkyl group such as benzyl, phenethyl, 1-naphthylmethyl, 2-naphthylmethyl, 1-naphthylethyl, 2-naphthylethyl, etc.). The alkyl group bonded to the aryl or heteroaryl group preferably has 1 to 4 carbon atoms, more preferably 1 to 2, and particularly preferably 1.

[0106] In the aromatic hydrocarbon group, the hydrogen atoms present in the aromatic hydrocarbon group may also be replaced by substituents. For example, the hydrogen atoms bonded to the aromatic ring in the aromatic hydrocarbon group may be replaced by substituents. Examples of such substituents include alkyl groups, alkoxy groups, halogen atoms, haloalkyl groups, hydroxyl groups, etc.

[0107] The alkyl group used as the substituent is preferably an alkyl group having 1 to 5 carbon atoms, and more preferably methyl, ethyl, propyl, n-butyl, or tert-butyl.

[0108] The alkoxy, halogen atom, and haloalkyl groups that are said to be substituents can be exemplified as substituents that replace the hydrogen atoms of the cyclic aliphatic hydrocarbon group.

[0109] • Divalent linking groups containing heteroatoms:

[0110] In Ya x1 In the case of a divalent linking group containing a heteroatom, examples of such linking groups include -O-, -C(=O)-O-, -OC(=O)-, -C(=O)-, -OC(=O)-O-, -C(=O)-NH-, -NH-, -NH-C(=NH)- (H can be substituted by alkyl, acyl, or other substituents), -S-, -S(=O)2-, -S(=O)2-O-, and those with the general formula -Y 21 -OY 22 -、-Y 21 -O-、-Y 21 -C(=O)-O-、-C(=O)-OY 21 -、-[Y21 -C(=O)-O] m” -Y 22 -、-Y 21 -OC(=O)-Y 22 -or-Y 21 -S(=O)2-OY 22 - represents a group [where Y is a group that represents ... 21 and Y 22 Preferred groups include divalent hydrocarbon groups that can be independently substituted, where O is an oxygen atom and m" is an integer from 0 to 3.

[0111] When the divalent linking group containing heteroatoms is -C(=O)-NH-, -C(=O)-NH-C(=O)-, -NH-, or -NH-C(=NH)-, its H can be replaced by substituents such as alkyl or acyl groups. The number of carbon atoms in the substituent (alkyl, acyl, etc.) is preferably 1 to 10, more preferably 1 to 8, and particularly preferably 1 to 5.

[0112] General formula -Y 21 -OY 22 -、-Y 21 -O-、-Y 21 -C(=O)-O-、-C(=O)-OY 21 -、-[Y 21 -C(=O)-O] m” -Y 22 -、-Y 21 -OC(=O)-Y 22 -or-Y 21 -S(=O)2-OY 22 -Medium,Y 21 and Y 22 Each is independently a divalent hydrocarbon group that may have substituents. Examples of such divalent hydrocarbon groups include those related to Ya. x1 The same groups (which may be divalent hydrocarbon groups with substituents) are listed in the description of the divalent linking groups.

[0113] As Y 21 Preferably, it is a straight-chain aliphatic hydrocarbon group, more preferably a straight-chain alkylene group, even more preferably a straight-chain alkylene group with 1 to 5 carbon atoms, and particularly preferably methylene or ethylene.

[0114] As Y 22 Preferably, the alkyl group is a straight-chain or branched aliphatic hydrocarbon group, more preferably methylene, ethylene, or alkylmethylene. The alkyl group in the alkylmethylene group is preferably a straight-chain alkyl group with 1 to 5 carbon atoms, more preferably a straight-chain alkyl group with 1 to 3 carbon atoms, and most preferably methyl.

[0115] With formula - [Y21 -C(=O)-O] m” -Y 22 In the group represented by -, m” is an integer from 0 to 3, preferably an integer from 0 to 2, more preferably 0 or 1, and particularly preferably 1. That is, as a group represented by the formula -[Y 21 -C(=O)-O] m” -Y 22 - represents a group, particularly preferably represented by the formula -Y 21 -C(=O)-OY 22 - represents a group. Preferably, it is represented by the formula -(CH2). a’ -C(=O)-O-(CH2) b’ - represents a group. In this formula, a' is an integer from 1 to 10, preferably an integer from 1 to 8, more preferably an integer from 1 to 5, further preferably 1 or 2, and most preferably 1. b' is an integer from 1 to 10, preferably an integer from 1 to 8, more preferably an integer from 1 to 5, further preferably 1 or 2, and most preferably 1.

[0116] Of the above, as Ya x1 Preferably, it is a single bond, an ester bond [-C(=O)-O-, -OC(=O)-], an ether bond (-O-), a straight-chain or branched alkylene group, or a combination thereof, more preferably a single bond or an ester bond [-C(=O)-O-, -OC(=O)-].

[0117] In the aforementioned formula (a10-1), Wa x1 It is an aromatic hydrocarbon group that can have substituents.

[0118] As Wa x1 The aromatic hydrocarbon group in the figure can be exemplified by the removal of (n) from an aromatic ring that may have substituents. ax1 A group obtained by adding (+1) hydrogen atoms. The aromatic ring here is not particularly limited to a cyclic conjugated system having 4n+2 π electrons; it can be monocyclic or polycyclic. The number of carbon atoms in the aromatic ring is preferably 5 to 30, more preferably 5 to 20, further preferably 6 to 15, and particularly preferably 6 to 12. Examples of such aromatic rings include aromatic hydrocarbon rings such as benzene, naphthalene, anthracene, and phenanthrene; and aromatic heterocycles obtained by replacing a portion of the carbon atoms constituting the aromatic hydrocarbon ring with heteroatoms. Examples of heteroatoms in aromatic heterocycles include oxygen atoms, sulfur atoms, and nitrogen atoms. Examples of aromatic heterocycles include pyridine rings and thiophene rings.

[0119] In addition, as Wa x1 The aromatic hydrocarbon groups in the text can be exemplified by those removed from aromatic compounds containing two or more aromatic rings that may have substituents (e.g., biphenyl, fluorene, etc.). ax1A group obtained by adding 1+ hydrogen atoms.

[0120] Of the above, as Wa x1 Preferably, it is removed from benzene, naphthalene, anthracene, or biphenyl (n ax1 A group obtained by removing (n) hydrogen atoms is more preferably derived from benzene or naphthalene. ax1 The group obtained by removing (n) hydrogen atoms is further preferably derived from benzene. ax1 A group obtained by adding 1+ hydrogen atoms.

[0121] Wa x1 The aromatic hydrocarbon group in the aromatic hydrocarbon group may or may not have substituents. Examples of substituents include alkyl groups, alkoxy groups, halogen atoms, and haloalkyl groups. Examples of alkyl, alkoxy, halogen atoms, and haloalkyl groups that can be used as substituents include those used as Ya. x1 The substituent is the same group as the cyclic aliphatic hydrocarbon group exemplified in the example. The substituent is preferably a straight-chain or branched alkyl group having 1 to 5 carbon atoms, more preferably a straight-chain or branched alkyl group having 1 to 3 carbon atoms, further preferably methyl or ethyl, and particularly preferably methyl. x1 The aromatic hydrocarbon groups in the sample preferably do not have substituents.

[0122] In the formula (a10-1), n ax1 It is an integer of 1 or more, preferably an integer from 1 to 10, more preferably an integer from 1 to 5, further preferably 1, 2 or 3, and particularly preferably 1 or 2.

[0123] The following shows a specific example of the structural unit (a10) represented by the formula (a10-1).

[0124] In the following formulas, R α It represents a hydrogen atom, a methyl group, or a trifluoromethyl group.

[0125] [Chemistry 5]

[0126]

[0127] [Chemistry 6]

[0128]

[0129] [Chemistry 7]

[0130]

[0131] [Chemistry 8]

[0132]

[0133] The structural unit (a10) of component (A1) can be one or more types.

[0134] The proportion of structural unit (a10) in component (A1) relative to the total (100 mol%) of all structural units constituting component (A1) is preferably 70 to 99 mol%, more preferably 75 to 99 mol%, further preferably 80 to 99 mol%, and particularly preferably 85 to 95 mol%.

[0135] By setting the proportion of the structural unit (a10) above the lower limit, the development and photolithography characteristics are further improved. On the other hand, by setting it below the upper limit, it is easier to achieve a balance with other structural units.

[0136] Regarding structural unit (a11):

[0137] The (A1) component is preferably a copolymer that has a structural unit (a11) in addition to the above-mentioned structural unit (a10), wherein the structural unit (a11) is a structural unit derived from a compound that contains an aromatic ring (excluding an aromatic ring bonded to a hydroxyl group) in its side chain.

[0138] As a compound containing an aromatic ring (excluding the aromatic ring bonded to a hydroxyl group) in its side chain, a compound represented by the following general formula (a11-1) may be preferably exemplified, for example.

[0139] [Chemistry 9]

[0140]

[0141] In formula (a11-1), Ra x2 It is a group containing a polymerizable group. Wa x2 It is (n ax2 +1) valence aromatic hydrocarbon group. It can also be composed of Ra x2 With Wa x2 Formation of fused ring structures. Ra x02 It is a substitute for the composition of Wa x2 Substituents for hydrogen atoms in (aromatic hydrocarbon groups). ax2 n is an integer between 0 and 3. ax2 When the value is 2 or higher, multiple Ra x02 They can bond together to form a ring structure.

[0142] In the aforementioned formula (a11-1), Ra x2 It is a group containing a polymerizable group.

[0143] Ra x2The term "polymerizable group" refers to a group in which a compound can be polymerized through free radical polymerization, such as a group containing multiple bonds between carbon atoms, such as alkene double bonds.

[0144] Examples of polymerizable groups include vinyl, allyl, acryloyl, methacryloyl, fluorovinyl, difluorovinyl, trifluorovinyl, difluorotrifluoromethylvinyl, trifluoroallyl, perfluoroallyl, trifluoromethylacryloyl, nonylfluorobutylacryloyl, vinyl ether, fluorinated vinyl ether, allyl ether, fluorinated allyl ether, styryl, vinylnaphthyl, fluorinated styryl, fluorinated vinylnaphthyl, norbornyl, fluorinated norbornyl, silyl, etc.

[0145] A group containing a polymerizable group can be a group consisting solely of a polymerizable group, or a group consisting of a polymerizable group and other groups besides that polymerizable group. Examples of other groups besides that polymerizable group include divalent hydrocarbon groups that may have substituents and divalent linking groups containing heteroatoms.

[0146] As Ra x2 For example, the chemical formula CH2=C(R)-Ya can be preferably exemplified. x0 - indicates a group. In this chemical formula, R is a hydrogen atom, an alkyl group with 1 to 5 carbon atoms, or a haloalkyl group with 1 to 5 carbon atoms, and Ya x0 It is a divalent linker.

[0147] In the aforementioned formula (a11-1), Wa x2 For (n ax2 +1) valence aromatic hydrocarbon groups, such as Wa in (a10-1) can be exemplified. x1 The same group.

[0148] Among them, it can also be Ra x2 With Wa x2 It forms a fused ring structure.

[0149] In Ra x2 With Wa x2 In the case of forming a fused ring structure, the fused ring structure contains components derived from Wa x2 The aromatic ring. Furthermore, it originates from Ra. x2 The multiple bonds between carbon atoms in the polymeric group break to form the main chain of the (A1) component. That is, a portion of the carbon atoms constituting the fused ring constitute the main chain of the (A1) component.

[0150] In the aforementioned formula (a11-1), Ra x02 It is a substitute for the composition of Wa x2 Substituents of hydrogen atoms in (aromatic hydrocarbon groups).

[0151] As Ra x02 Substituents in the group can be, for example, alkyl, alkoxy, acyloxy, etc.

[0152] As Ra x02 The alkyl substituents in the group are preferably alkyl groups with 1 to 5 carbon atoms, and more preferably methyl, ethyl, propyl, n-butyl, or tert-butyl.

[0153] As Ra x02 The alkoxy group of the substituent is preferably an alkoxy group having 1 to 5 carbon atoms, more preferably methoxy, ethoxy, n-propoxy, isopropoxy, n-butoxy, or tert-butoxy, and particularly preferably methoxy or ethoxy.

[0154] As Ra x02 The number of carbon atoms in the acyloxy group of the substituent is preferably 2 to 6, more preferably CH3C(=O)-O-(acetoxy) or C2H5C(=O)-O-, and particularly preferably CH3C(=O)-O-(acetoxy).

[0155] In the aforementioned formula (a11-1), n ax2 It is an integer from 0 to 3, preferably 0, 1 or 2, and more preferably 0 or 1.

[0156] n ax2 When the value is 2 or higher, multiple Ra x02 They can bond together to form ring structures. The ring structures formed can be hydrocarbon rings or heterocycles. For example, Wa... x2 Two Ra molecules bonded to the same aromatic ring in the middle x02 And the two Ra x02 The bonded aromatic ring (Wa) x2 A ring structure formed by the bonding between carbon atoms on one side of the ring.

[0157] As the above-mentioned structural unit (a11), for example, structural units represented by the following general formulas (a11-u1-1) to (a11-u1-6) can be preferably exemplified.

[0158] [Chemistry 10]

[0159]

[0160] [In the formula, R] α It can be a hydrogen atom, a methyl group, or a trifluoromethyl group. R β It can be alkyl, alkoxy, or acyloxy. ax2 n is an integer between 0 and 3. ax2 When the value is 2 or higher, multiple R β They can bond together to form a ring structure. 21 n 22 n24 and n 25 Each can be 0 or 1 independently. 23 and n 26 Each can be independently represented as 1 or 2.

[0161] In the formulas (a11-u1-1) to (a11-u1-6), R β The alkyl, alkoxy, and acyloxy groups in the formula (a11-1) react with Ra, which is Ra in the formula (a11-1). x02 The same applies to the substituents in the example, such as alkyl, alkoxy, and acyloxy.

[0162] The following are specific examples of structural units (structural units (a11)) derived from compounds represented by the general formula (a11-1).

[0163] In the following formulas, R α It represents a hydrogen atom, a methyl group, or a trifluoromethyl group.

[0164] [Chemistry 11]

[0165]

[0166] [Chemistry 12]

[0167]

[0168] [Chemistry 13]

[0169]

[0170] [Chemistry 14]

[0171]

[0172] [Chemistry 15]

[0173]

[0174] In the above examples, the structural unit (a11) is preferably at least one selected from the group consisting of structural units represented by general formulas (a11-u1-1) to (a11-u1-3), and more preferably a structural unit represented by general formula (a11-u1-1).

[0175] Among these structural units, the structural unit (a11) is preferably a structural unit represented by any one of the chemical formulas (a11-u1-11), (a11-u1-21), or (a11-u1-31).

[0176] The structural unit (a11) of component (A1) can be one or more types.

[0177] When the (A1) component has structural unit (a11), the proportion of structural unit (a11) in the (A1) component relative to the total (100 mol%) of all structural units constituting the (A1) component is preferably 1 to 30 mol%, more preferably 1 to 25 mol%, even more preferably 1 to 20 mol%, and particularly preferably 5 to 15 mol%.

[0178] By setting the proportion of the structural unit (a11) above the lower limit, etching resistance and photolithography characteristics are further improved. On the other hand, by setting it below the upper limit, it is easier to achieve a balance with other structural units.

[0179] Other Structural Units

[0180] In addition to structural units (a10) and (a11), component (A1) may also have other structural units.

[0181] Examples of compounds that derive the other structural units mentioned above include monocarboxylic acids such as acrylic acid, methacrylic acid, and crotonic acid; dicarboxylic acids such as maleic acid, fumaric acid, and itaconic acid; methacrylic acid derivatives with carboxyl and ester bonds such as 2-methacryloyloxyethyl succinic acid, 2-methacryloyloxyethyl maleic acid, 2-methacryloyloxyethyl phthalic acid, and 2-methacryloyloxyethyl hexahydrophthalic acid; alkyl methacrylates such as methyl methacrylate, ethyl methacrylate, and butyl methacrylate; and 2-hydroxy methacrylate. Ethyl methacrylate, 2-hydroxypropyl methacrylate, and other hydroxyalkyl methacrylates; phenyl methacrylate, benzyl methacrylate, and other aryl methacrylates; diethyl maleate, dibutyl fumarate, and other dicarboxylic acid diesters; vinyl acetate and other vinyl-containing aliphatic compounds; butadiene, isoprene, and other conjugated dienes; acrylonitrile, methacrylonitrile, and other nitrile-containing polymeric compounds; vinyl chloride, vinylidene chloride, and other chlorine-containing polymeric compounds; acrylamide, methacrylamide, and other amide-containing polymeric compounds; epoxy-containing polymeric compounds, etc.

[0182] In the resist composition of this embodiment, component (A) comprises a polymeric compound (A1) having a structural unit (a10) ((A1) component).

[0183] As a preferred component (A1), examples include polymeric compounds having at least one structural unit (a10). Specifically, examples include: polymeric compounds having a repeating structure of structural unit (a10) (homogeneities composed of structural unit (a10); and polymeric compounds having repeating structures of structural units (a10) and structural units (a11).

[0184] The weight-average molecular weight (Mw) of component (A1) (based on polystyrene conversion standard using gel permeation chromatography (GPC)) is not particularly limited, but is preferably 500 to 50,000, more preferably 1,000 to 30,000, and even more preferably 2,000 to 20,000.

[0185] If the Mw of component (A1) is below the preferred upper limit of the range, it has sufficient solubility in the resist solvent to be used as a resist; if it is above the preferred lower limit of the range, it has better resistance to dry etching and better resist pattern cross-sectional shape.

[0186] The molecular weight distribution coefficient (Mw / Mn) of component (A1) is not particularly limited, but is preferably 1.0 to 4.0, more preferably 1.0 to 3.0, and particularly preferably 1.0 to 2.5. Mn represents the number-average molecular weight.

[0187] The (A1) component can be manufactured by dissolving the monomers from which the structural units are derived in a polymerization solvent, wherein a free radical polymerization initiator such as azobisisobutyronitrile (AIBN) or dimethyl azobisisobutyrate (e.g., V-601) is added to the solvent for polymerization.

[0188] Alternatively, the (A1) component can be manufactured by dissolving the monomer that derives the structural unit (a10) and the monomer that derives the structural unit other than (a10) as needed in a polymerization solvent, wherein a free radical polymerization initiator as described above is added to perform polymerization, followed by a deprotection reaction.

[0189] Additionally, during polymerization, a chain transfer agent such as HS-CH2-CH2-CH2-C(CF3)2-OH can be used, for example, to introduce a -C(CF3)2-OH group at the end. In this way, copolymers of hydroxyalkyl groups, obtained by replacing a portion of the hydrogen atoms of the introduced alkyl group with fluorine atoms, are effective in reducing development defects and LER (line edge roughness: unevenness of the line sidewalls).

[0190] Regarding ingredient (A2)

[0191] The resist composition of this embodiment may use a substrate component (hereinafter referred to as "(A2) component") that is not part of component (A1) and whose solubility in the developer changes due to the action of acid as component (A1) as component (A).

[0192] As for component (A2), there are no particular limitations, and it is permissible to select any of the various components that have been known as base material components for chemically amplified resist compositions.

[0193] (A2) Components can be a single high molecular weight compound or a low molecular weight compound, or a combination of two or more.

[0194] The proportion of (A1) component in (A) component relative to the total mass of component (A) is preferably 25% by mass or more, more preferably 50% by mass or more, even more preferably 75% by mass or more, and may also be 100% by mass. If the proportion is 25% by mass or more, it becomes easier to form resist patterns with various excellent photolithographic properties such as high sensitivity or resolution and improved roughness.

[0195] In the resist composition of this embodiment, the content of component (A) can be adjusted according to the desired resist film thickness, etc.

[0196] <(B) Ingredients>

[0197] Regarding ingredient (B0)

[0198] (B) is an acid-generating agent that generates acid through exposure. In the resist composition of this embodiment, (B) contains at least an acid-generating agent (B0) represented by the following general formula (b0-1) ((B0) component).

[0199] [Chemistry 16]

[0200]

[0201] [In the formula, Rb] 1 It is an organic group. Rb 2 It is a group represented by the following general formula (b0-r-1) or the following general formula (b0-r-2).

[0202] [Chemistry 17]

[0203]

[0204] In the formula (b0-r-1), Rb 201 and Rb 202 Each is an independent organic group. * indicates a bond. In formula (b0-r-2), Xb is a group that, together with -(O=)CNC(=O)-, forms a cyclic group with a cyclic imide structure. * indicates a bond.

[0205] In this embodiment, the (B0) component is not particularly limited as long as it is a compound represented by the formula (b0-1). For example, at least one compound selected from the group consisting of the following general formulas (b0-1-1) to (b0-1-6) can be cited.

[0206] [Chemistry 18]

[0207]

[0208] [In the formula, Rb] 11 and Rb 21 Each is an independent non-aromatic group.

[0209] [Chemistry 19]

[0210]

[0211] [In the formula, Rb] 12 It is an alkyl or haloalkyl group. Rb 22 It is an aromatic group.

[0212] [Chemistry 20]

[0213]

[0214] [In the formula, Rb] 13 It is a hydrocarbon group that can have substituents. nb3 is 2 or 3. Ab is a divalent or trivalent organic group.

[0215] [Chemistry 21]

[0216]

[0217] [In the formula, Rb] 14 It is an aromatic polycyclic hydrocarbon group, a saturated or unsaturated non-aromatic polycyclic hydrocarbon group, or a substituted derivative thereof. Rb 24 It is an inert organic group.

[0218] [Chemistry 22]

[0219]

[0220] [In the formula, Rb] 15 It is a substituted or unsubstituted monovalent saturated hydrocarbon group, an unsaturated hydrocarbon group, or an aromatic group. Xb 5 It is a group that, together with -(O=)CNC(=O)-, forms a cyclic group with a cyclic imide structure.

[0221] [Chemistry 23]

[0222]

[0223] [In the formula, Rb] 16 It can be an alkyl group that may have substituents, or an aromatic hydrocarbon group that may have substituents. Rb 261 ~Rb 263 Each of the following is independently a halogen atom, an alkyl group having 1 to 6 carbon atoms, or an alkoxy group having 1 to 6 carbon atoms. nb6 is an integer from 0 to 5.

[0224] In the above equation (b0-1-1), Rb 11 and Rb 12 Non-aromatic groups in the group can be exemplified by alkyl, haloalkyl, alkenyl, cycloalkyl, cycloalkenyl, alkoxy, cycloalkoxy, and adamantyl.

[0225] As Rb 11 and Rb 12 The alkyl group in the alkyl group is preferably a straight-chain or branched alkyl group having 1 to 12 carbon atoms, such as methyl, ethyl, n-propyl, isopropyl, n-butyl, isobutyl, sec-butyl, tert-butyl, n-pentyl, n-octyl, n-dodecyl, etc.

[0226] For Rb 11 and Rb 12 There is no particular limitation on the number of halogen atoms in the haloalkyl group; one or more can be introduced. Furthermore, the halogen atom can be any of a fluorine atom, a chlorine atom, a bromine atom, or an iodine atom. Preferably, the haloalkyl group has 1 to 4 carbon atoms, such as chloromethyl, trichloromethyl, trifluoromethyl, 2-bromopropyl, etc.

[0227] As Rb 11 and Rb 12 The alkenyl group in the form of the alkenyl group is preferably a straight-chain or branched alkenyl group with 2 to 6 carbon atoms, such as vinyl, 1-propenyl, isopropenyl, 2-butenyl, etc.

[0228] As Rb 11 and Rb 12 The cycloalkyl group in the cycloalkyl group is preferably a cycloalkyl group with 5 to 12 carbon atoms, such as cyclopentyl, cyclohexyl, cyclooctyl, cyclododecyl, etc. In addition, as a cycloalkenyl group, a cycloalkenyl group with 4 to 8 carbon atoms is preferred, such as 1-cyclobutenyl, 1-cyclopentenyl, 1-cyclohexenyl, 1-cycloheptenyl, 1-cyclooctenyl, etc.

[0229] As Rb 11 and Rb 12 The alkoxy group in the alkoxy group is preferably an alkoxy group with 1 to 8 carbon atoms, such as methoxy, ethoxy, propoxy, butoxy, pentoxy, etc.

[0230] As Rb 11 and Rb 12 The cycloalkoxy group in the cycloalkoxy group is preferably a cycloalkoxy group with 5 to 8 carbon atoms, such as cyclopentoxy or cyclohexoxy.

[0231] In the above equation (b0-1-1), Rb 11 Alkyl, haloalkyl, and cycloalkyl groups are preferred, with alkyl groups being particularly preferred. As Rb 21 Alkyl, cycloalkyl, and cycloalkenyl groups are preferred, with cycloalkenyl groups being particularly preferred. Rb is more preferred.11 Rb is an alkyl group having 1 to 4 carbon atoms. 21 It is cyclopentenyl.

[0232] Specific examples of compounds represented by the formula (b0-1-1) include α-(methanesulfonyloxyimino)-1-cyclopentenylacetonitrile, α-(methanesulfonyloxyimino)-1-cyclohexenylacetonitrile, α-(methanesulfonyloxyimino)-1-cycloheptenylacetonitrile, α-(methanesulfonyloxyimino)-1-cyclooctenylacetonitrile, α-(trifluoromethanesulfonyloxyimino)-1-cyclopentenylacetonitrile, α-(trifluoromethanesulfonyloxyimino)-cyclohexylacetonitrile, α-(ethylsulfonyloxyimino)-ethylacetonitrile, α-(propylsulfonyloxyimino)-propylacetonitrile, α... -(cyclohexylsulfonyloxyimino)-cyclopentylacetonitrile, α-(cyclohexylsulfonyloxyimino)-cyclohexylacetonitrile, α-(cyclohexylsulfonyloxyimino)-1-cyclopentenylacetonitrile, α-(ethylsulfonyloxyimino)-1-cyclopentenylacetonitrile, α-(isopropylsulfonyloxyimino)-1-cyclopentenylacetonitrile, α-(n-butylsulfonyloxyimino)-1-cyclopentenylacetonitrile, α-(ethylsulfonyloxyimino)-1-cyclohexenylacetonitrile, α-(isopropylsulfonyloxyimino)-1-cyclohexenylacetonitrile, α-(n-butylsulfonyloxyimino)-1-cyclohexenylacetonitrile, etc.

[0233] In the aforementioned equation (b0-1-2), Rb is used as... 12 Alkyl groups can be exemplified by straight-chain or branched alkyl groups having 1 to 4 carbon atoms, such as methyl, ethyl, n-propyl, isopropyl, n-butyl, isobutyl, sec-butyl, tert-butyl, etc.

[0234] As Rb 12 The haloalkyl groups in the text can be exemplified by haloalkyl groups having 1 to 4 carbon atoms, such as chloromethyl, trichloromethyl, trifluoromethyl, 2-bromopropyl, etc.

[0235] In the formula (b0-1-2), Rb 22 Aromatic groups in the text refer to groups that indicate the unique physical and chemical properties of aromatic compounds; examples include phenyl, naphthyl, furanyl, and thiophene groups. Rb 22 In the aromatic group, a portion of the hydrogen atom of the aromatic ring constituting the aromatic group can also be replaced by a substituent. Examples of such substituents include halogen atoms, alkyl groups, alkoxy groups, and nitro groups.

[0236] Specifically, examples of compounds represented by the formula (b0-1-2) include α-(methanesulfonyloxyimino)-phenylacetonitrile, α-(methanesulfonyloxyimino)-4-methoxyphenylacetonitrile, α-(methanesulfonyloxyimino)-4-methylphenylacetonitrile, α-(trifluoromethanesulfonyloxyimino)-phenylacetonitrile, α-(trifluoromethanesulfonyloxyimino)-4-methoxyphenylacetonitrile, α-(ethylsulfonyloxyimino)-4-methoxyphenylacetonitrile, α-(propylsulfonyloxyimino)-4-methylphenylacetonitrile, and α-(methanesulfonyloxyimino)-4-bromophenylacetonitrile.

[0237] In the above equation (b0-1-3), Rb 13 The hydrocarbon group in the formula can be either an aromatic group or a non-aromatic hydrocarbon group. Here, as an aromatic group, an aromatic group having 6 to 14 carbon atoms is preferred, such as phenyl, tolyl, methoxyphenyl, xylyl, biphenyl, naphthyl, anthracene, etc., or heterocyclic groups such as furanyl, pyridyl, quinolinyl, etc. Furthermore, non-aromatic hydrocarbon groups include hydrocarbon groups that do not have aromatic rings such as benzene rings, naphthyl rings, furan rings, thiophene rings, or pyridyl rings, such as aliphatic hydrocarbon groups and alicyclic hydrocarbon groups, including, for example, alkyl, alkenyl, cycloalkyl, and cycloalkenyl groups. The alkyl and alkenyl groups can be either straight-chain or branched-chain, preferably groups having 1 to 12 carbon atoms, and cycloalkyl and cycloalkenyl groups preferably have 4 to 12 carbon atoms. Examples of alkyl groups include methyl, ethyl, propyl, isopropyl, n-butyl, sec-butyl, tert-butyl, n-pentyl, n-octyl, and n-dodecyl. Examples of alkenyl groups include vinyl, propenyl, butenyl, butadienyl, hexenyl, and octadienyl. Examples of cycloalkyl groups include cyclopentyl, cyclohexyl, cyclooctyl, and cyclododecyl. Examples of cycloalkenyl groups include 1-cyclobutenyl, 1-cyclopentenyl, 1-cyclohexenyl, 1-cycloheptenyl, and 1-cyclooctenyl.

[0238] In the formula (b0-1-3), Rb 13 The hydrocarbon group in the hydrocarbon group can have substituents. Examples of such substituents include halogen atoms, hydroxyl groups, alkoxy groups, and acyl groups.

[0239] In the formula (b0-1-3), examples of divalent or trivalent organic groups in Ab include aliphatic hydrocarbon groups and aromatic hydrocarbon groups.

[0240] Specific examples of compounds represented by the formula (b0-1-3) are shown below.

[0241] [Chemistry 24]

[0242]

[0243] [Chemistry 25]

[0244]

[0245] In the aforementioned equation (b0-1-4), Rb is used as... 14 The aromatic polycyclic hydrocarbon groups in the group can be exemplified by, for example, fused aromatic polycyclic hydrocarbon groups such as 2-indenyl, 1-naphthyl, 2-naphthyl, and 2-anthrayl, and non-fused aromatic polycyclic hydrocarbon groups such as biphenyl and terphenyl. Furthermore, as substituted derivative groups, examples include groups whose aromatic rings are replaced by halogen atoms such as chlorine, bromine, and iodine, or by substituents such as nitro, amino, hydroxyl, alkyl, and alkoxy groups, such as 5-hydroxy-1-naphthyl and 4-amino-1-naphthyl.

[0246] In the aforementioned equation (b0-1-4), Rb is used as... 14 The saturated or unsaturated non-aromatic polycyclic hydrocarbon group in the ring may be, for example, a polycyclic terpene residue or an adamantyl group, with a polycyclic terpene residue being preferred. Furthermore, as substituted derivative groups, examples include groups having suitable substituents such as halogen atoms (e.g., chlorine, bromine, iodine), nitro, amino, hydroxyl, oxo, alkyl, or alkoxy groups on the ring. Examples of such groups include camphor-3-yl, camphor-8-yl, camphor-10-yl, and 3-bromocamphor-10-yl.

[0247] As the Rb 14 Naphthyl and camphor-10-yl are preferred, especially 1-naphthyl, which is preferred due to its excellent resolution.

[0248] In the formula (b0-1-4), Rb 24 The inert organic group in this context refers to an organic group that is inert to coexisting components under operating conditions. There are no particular restrictions, but aromatic groups are preferred from the viewpoint of sensitivity to excimer lasers, electron beams, and X-rays. Examples of such aromatic groups include phenyl, naphthyl, furanyl, and thiophene groups. Furthermore, these aromatic groups may have inert substituents such as halogen atoms (e.g., chlorine, bromine, iodine), alkyl groups, alkoxy groups, and nitro groups.

[0249] Specific examples of compounds represented by the formula (b0-1-4) include α-(1-naphthylsulfonyloxyimino)-4-methoxybenzyl cyanide, α-(2-naphthylsulfonyloxyimino)-4-methoxybenzyl cyanide, α-(1-naphthylsulfonyloxyimino)benzyl cyanide, α-(2-naphthylsulfonyloxyimino)benzyl cyanide, α-(10-camphorsulfonyloxyimino)-4-methoxybenzyl cyanide, α-(10-camphorsulfonyloxyimino)benzyl cyanide, α-(3-camphorsulfonyloxyimino)-4-methoxybenzyl cyanide, α-(3-bromo-10-camphorsulfonyloxyimino)-4-methoxybenzyl cyanide, etc.

[0250] In the above equation (b0-1-5), Rb 15 The substituted or unsubstituted monovalent saturated or unsaturated hydrocarbon groups in the Rb group can be exemplified by, for example, straight-chain or branched saturated or unsaturated hydrocarbon groups having 1 to 8 carbon atoms, and groups obtained by substituting them with halogen atoms, nitro groups, acetamido groups, lower alkoxy groups, monocyclic aryl groups, etc., with groups having halogen atoms, lower alkoxy groups, etc., being particularly preferred. Furthermore, as Rb... 15 The substituted or unsubstituted monovalent aromatic group in the benzene ring, such as monocyclic or bicyclic groups, is particularly preferred, and is a group in which the benzene ring is substituted by vinyl, alkyl, alkoxy, halogen atom, etc.

[0251] In the above formula (b0-1-5), Xb is used as... 5 Cyclic groups that form cyclic imide structures together with -(O=)CNC(=O)- can be exemplified by succinimide rings, maleimide rings, glutarimide rings, phthalimide rings, and 1,8-naphthalenediamide rings. Xb 5 The cyclic group forming a cyclic imide structure with -(O=)CNC(=O)- can have substituents. Examples of such substituents include halogen atoms, nitro groups, acetamido groups, alkoxy groups, and monocyclic aryl groups.

[0252] Specific examples of compounds represented by the formula (b0-1-5) include N-methylsulfonyloxysuccinimide, N-isopropylsulfonyloxysuccinimide, N-chloroethylsulfonyloxysuccinimide, N-(p-methoxyphenyl)sulfonyloxysuccinimide, N-(p-vinylphenyl)sulfonyloxysuccinimide, N-naphthalenesulfonyloxysuccinimide, N-phenylsulfonyloxysuccinimide, N-(2,4,6-trimethylphenyl)sulfonyloxysuccinimide, N-methylsulfonyloxymaleimide, N-isopropylsulfonyloxymaleimide, N-chloroethylsulfonyloxymaleimide, N-(p-methoxyphenyl)sulfonyloxymaleimide, and N-(p-vinylphenyl)sulfonyloxymaleimide. Amines, N-naphthalenesulfonyloxymaleimide, N-phenylsulfonyloxymaleimide, N-(2,4,6-trimethylphenyl)sulfonyloxymaleimide, N-methylsulfonyloxyphthalimide, N-isopropylsulfonyloxyphthalimide, N-chloroethylsulfonyloxyphthalimide, N-(p-methoxyphenyl)sulfonyloxyphthalimide, N-(p-vinylphenyl)sulfonyloxyphthalimide, N-naphthalenesulfonyloxyphthalimide, N-phenylsulfonyloxyphthalimide, N-(2,4,6-trimethylphenyl)sulfonyloxyphthalimide, and compounds described in paragraphs

[0089] -

[0091] of Japanese Patent Application Publication No. 10-097075.

[0253] In the above equation (b0-1-6), Rb 16 The alkyl group in the alkyl group is preferably a straight-chain, branched, or cyclic alkyl group having 1 to 18 carbon atoms. Examples include methyl, ethyl, propyl, isopropyl, n-butyl, sec-butyl, isobutyl, tert-butyl, pentyl, hexyl, heptyl, 2,4,4-trimethylpentyl, 2-ethylhexyl, octyl, nonyl, decyl, undecyl, dodecyl, tetradecyl, pentadecyl, hexadecyl, heptadecanyl, octadecyl, cyclopentyl, cyclohexyl, cyclooctyl, and cyclododecyl.

[0254] Among them, as Rb 16 The alkyl group in the alkyl group is preferably a straight-chain or branched alkyl group having 1 to 10 carbon atoms, and more preferably a straight-chain or branched alkyl group having 1 to 5 carbon atoms.

[0255] Rb 16 The alkyl group can have substituents. Examples of such substituents include halogen atoms, haloalkyl groups, CN, NO2, phenyl, alkoxy, carboxyl, carbonyl, sulfonyl, and amino groups.

[0256] In the aforementioned equation (b0-1-6), Rb is used as... 16 Aromatic hydrocarbon groups in Rb can be exemplified by phenyl, naphthyl, phenanthryl, anthracene, and heteroaryl groups. 16The aromatic hydrocarbon group in the substance may have substituents. Examples of such substituents include halogen atoms, haloalkyl groups, CN, NO2, phenyl, alkoxy, carboxyl, carbonyl, sulfonyl, and amino groups.

[0257] Specific examples of compounds represented by the formula (b0-1-6) include compounds represented by the following chemical formula (b0-1-61), and compounds of Examples 25 to 40 and 53 of Japanese Patent Publication No. 2002-508774.

[0258] [Chemistry 26]

[0259]

[0260] Other specific examples of (B0) components include the compounds described in paragraphs

[0056] ,

[0058] ,

[0060] , and

[0063] of Japanese Patent No. 4110392, and the compounds described in paragraphs

[0053] ,

[0054] ,

[0056] ,

[0058] , and

[0060] -

[0062] of Japanese Patent No. 4000469.

[0261] As component (B1), preferably at least one is selected from the group consisting of the compound represented by formula (b0-1-2), the compound represented by formula (b0-1-3), the compound represented by formula (b0-1-5), and the compound represented by formula (b0-1-6), and more preferably at least one is selected from the group consisting of the compound represented by formula (b0-1-2), the compound represented by formula (b0-1-3), and the compound represented by formula (b0-1-6).

[0262] The following are specific examples of preferred components (B0).

[0263] [Chemistry 27]

[0264]

[0265] The (BO) component contained in the resist composition of this embodiment can be used alone or in combination with two or more components.

[0266] In the resist composition of this embodiment, the content of component (B0) is preferably 50 parts by mass or less relative to 100 parts by mass of component (A), more preferably 0.1 to 40 parts by mass, even more preferably 0.1 to 30 parts by mass, and particularly preferably 0.1 to 20 parts by mass.

[0267] By ensuring that the content of component (B) is within the above range, pattern formation can be sufficiently achieved.

[0268] Regarding ingredient (B1)

[0269] The resist composition of this embodiment may also contain an acid-generating agent (hereinafter referred to as "(B1) component") other than component (B0) as component (B) component.

[0270] There are no particular limitations on component (B1), and any acid-generating agent proposed so far as an acid-generating agent for chemically amplified resist compositions can be used.

[0271] Examples of such acid-producing agents include iodonium salts, sulfonium salts, and other ononium salts; sulfonate oxime esters; dialkyl or diarylsulfonyl diazomethanes, poly(disulfonyl)diazomethanes, and other diazomethanes; nitrobenzyl sulfonates; and disulfones.

[0272] Examples of onium salt acid-producing agents include 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").

[0273] [Chemistry 28]

[0274]

[0275] [In the formula, R] 101 R 104 ~R 108 Each can be independently a cyclic group that may have substituents, a chain alkyl group that may have substituents, or a chain alkenyl group that may have substituents. R 104 R 105 They can bond together to form a ring. R 102 It is a fluorine atom or a fluoroalkyl group having 1 to 5 carbon atoms. 101 It is a single bond or a divalent linker containing an oxygen atom. V 101 ~V 103 Each can be independently a single bond, an alkylene group, or a fluoroalkylene group. L 101 ~L 102 Each can be a single bond or an oxygen atom, independently. L 103 ~L 105 Each can be a single bond, -CO-, or -SO2-, independently. m is an integer greater than or equal to 1, M' m+ It is an m-valent ononium cation.

[0276] {Anion Section}

[0277] • (b-1) Anionic portion of component

[0278] In equation (b-1), R 101It can be a cyclic group that may have substituents, a chain alkyl group that may have substituents, or a chain alkenyl group that may have substituents.

[0279] Cyclic groups that may have substituents:

[0280] The cyclic group is preferably a cyclic hydrocarbon group, which can be an aromatic hydrocarbon group or an aliphatic hydrocarbon group. An aliphatic hydrocarbon group indicates a hydrocarbon group that is not aromatic. Furthermore, the aliphatic hydrocarbon group can be saturated or unsaturated, but is generally preferred to be saturated.

[0281] R 101 The aromatic hydrocarbon group in the form 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, further preferably 5 to 20, particularly preferably 6 to 15, and most preferably 6 to 10. This number of carbon atoms does not include the number of carbon atoms in the substituents.

[0282] As R 101 The aromatic rings contained in aromatic hydrocarbon groups can be specifically exemplified by benzene, fluorene, naphthalene, anthracene, phenanthrene, biphenyl, or aromatic heterocycles obtained by replacing part of the carbon atoms constituting these aromatic rings with heteroatoms. Examples of heteroatoms in aromatic heterocycles include oxygen atoms, sulfur atoms, and nitrogen atoms.

[0283] As R 101 The aromatic hydrocarbon group in the aromatic ring can specifically include groups obtained by removing one hydrogen atom from the aromatic ring (aryl: for example, phenyl, naphthyl, etc.), and groups obtained by substituting one hydrogen atom of the aromatic ring with an alkylene group (for example, benzyl, phenethyl, 1-naphthylmethyl, 2-naphthylmethyl, 1-naphthylethyl, 2-naphthylethyl, etc., arylalkyl groups). The alkylene group (the alkyl chain in the arylalkyl group) preferably has 1 to 4 carbon atoms, more preferably 1 to 2, and particularly preferably 1.

[0284] R 101 Examples of cyclic aliphatic hydrocarbon groups in the structure include aliphatic hydrocarbon groups containing rings.

[0285] Examples of alicyclic hydrocarbon groups containing a ring in the structure include alicyclic hydrocarbon groups (groups obtained by removing one hydrogen atom from an alicyclic hydrocarbon ring), groups obtained by bonding an alicyclic hydrocarbon group to the end of a straight-chain or branched alicyclic hydrocarbon group, and groups in which the alicyclic hydrocarbon group is intermediate between a straight-chain or branched alicyclic hydrocarbon group.

[0286] The alicyclic hydrocarbon group preferably has 3 to 30 carbon atoms, more preferably 3 to 20.

[0287] The alicyclic hydrocarbon group can be either a polycyclic or monocyclic group. As a monocyclic alicyclic hydrocarbon group, it is preferably a group obtained by removing one or more hydrogen atoms from a monocyclic alkane. As the monocyclic alkane, a monocyclic alkane with 3 to 6 carbon atoms is preferred; examples include cyclopentane and cyclohexane. As a polycyclic alicyclic hydrocarbon group, it is preferably a group obtained by removing one or more hydrogen atoms from a polycyclic alkane; as the polycyclic alkane, a polycyclic alkane with 7 to 30 carbon atoms is preferred. More preferably, as the polycyclic alkane, polycyclic alkanes with a cross-linked ring structure such as adamantane, norbornane, isobornane, tricyclodecane, and tetracyclododecane; and polycyclic alkanes with a fused ring structure such as a cyclic group with a steroidal skeleton are preferred.

[0288] Among them, as R 101 The cyclic aliphatic hydrocarbon group in the form is preferably a group obtained by removing one or more hydrogen atoms from a monocyclic alkane or polycyclic alkane, more preferably a group obtained by removing one hydrogen atom from a polycyclic alkane, particularly preferably adamantyl, norbornyl, or a cyclic group having a steroid skeleton, and most preferably adamantyl or a cyclic group having a steroid skeleton.

[0289] The aliphatic hydrocarbon group that can be bonded to the alicyclic hydrocarbon group preferably has 1 to 10 carbon atoms, more preferably 1 to 6 carbon atoms, even more preferably 1 to 4 carbon atoms, and particularly preferably 1 to 3 carbon atoms.

[0290] As a straight-chain aliphatic hydrocarbon group, a straight-chain alkylene group is preferred. Specifically, examples include methylene [-CH2-], ethylene [-(CH2)2-], propylene [-(CH2)3-], butylene [-(CH2)4-], and pentylene [-(CH2)5-].

[0291] As a branched aliphatic hydrocarbon group, a branched alkylene group is preferred. Specifically, examples include alkylmethylene groups such as -CH(CH3)-, -CH(CH2CH3)-, -C(CH3)2-, -C(CH3)(CH2CH3)-, -C(CH3)(CH2CH2CH3)-, and -C(CH2CH3)2-; alkylethylene groups such as -CH(CH3)CH2-, -CH(CH3)CH(CH3)-, -C(CH3)2CH2-, -CH(CH2CH3)CH2-, and -C(CH2CH3)2-CH2-; alkylpropylene groups such as -CH(CH3)CH2CH2- and -CH2CH(CH3)CH2-; and alkylalkylene groups such as -CH(CH3)CH2CH2CH2- and -CH2CH(CH3)CH2CH2-. The alkyl group in the alkyl alkylene group is preferably a straight-chain alkyl group having 1 to 5 carbon atoms.

[0292] In addition, R 101The cyclic hydrocarbon group in the formula can contain heteroatoms, just like heterocycles. Specifically, examples include lactone-containing cyclic groups represented by the general formulas (a2-r-1) to (a2-r-7), -SO2-containing cyclic groups represented by the general formulas (a5-r-1) to (a5-r-4), and other heterocyclic groups represented by the following chemical formulas (r-hr-1) to (r-hr-16).

[0293] [Chemistry 29]

[0294]

[0295] As R 101 Substituents in the cyclic group can include, for example, alkyl, alkoxy, halogen atom, haloalkyl, hydroxy, carbonyl, nitro, etc. The alkyl group used as a substituent is preferably an alkyl group having 1 to 5 carbon atoms, and most preferably methyl, ethyl, propyl, n-butyl, or tert-butyl.

[0296] The alkoxy group used as a substituent is preferably an alkoxy group having 1 to 5 carbon atoms, more preferably methoxy, ethoxy, n-propoxy, isopropoxy, n-butoxy, or tert-butoxy, and most preferably methoxy or ethoxy.

[0297] Examples of halogen atoms that can be used as substituents include fluorine atoms, chlorine atoms, bromine atoms, and iodine atoms, with fluorine atoms being the preferred option.

[0298] Examples of alkyl halogens that can be used as substituents include alkyl groups having 1 to 5 carbon atoms, such as methyl, ethyl, propyl, n-butyl, tert-butyl, etc., in which some or all of the hydrogen atoms are replaced by the halogen atom.

[0299] The carbonyl group, as a substituent, is a group that replaces the methylene (-CH2-) group that constitutes the cyclic hydrocarbon group.

[0300] Chain alkyl groups that may have substituents:

[0301] As R 101 The chain alkyl group can be either straight-chain or branched.

[0302] As a straight-chain alkyl group, it is preferably composed of 1 to 20 carbon atoms, more preferably 1 to 15, and most preferably 1 to 10. Specifically, examples include methyl, ethyl, propyl, butyl, pentyl, hexyl, heptyl, octyl, nonyl, decyl, undecyl, dodecyl, tridecyl, isotriadecyl, tetradecyl, pentadecyl, hexadecyl, isohexadecanyl, heptadecanyl, octadecyl, nonadecanyl, eicosyl, dodecyl, and dodecyl.

[0303] As a branched alkyl group, the number of carbon atoms is preferably 3 to 20, more preferably 3 to 15, and most preferably 3 to 10. Specifically, examples include 1-methylethyl, 1-methylpropyl, 2-methylpropyl, 1-methylbutyl, 2-methylbutyl, 3-methylbutyl, 1-ethylbutyl, 2-ethylbutyl, 1-methylpentyl, 2-methylpentyl, 3-methylpentyl, 4-methylpentyl, etc.

[0304] Chain alkenyl groups that may have substituents:

[0305] As R 101 The chain-like alkenyl group can be either straight-chain or branched, and the number of carbon atoms is preferably 2 to 10, more preferably 2 to 5, further preferably 2 to 4, and particularly preferably 3. Examples of straight-chain alkenyl groups include vinyl, allyl, and butynyl. Examples of branched alkenyl groups include 1-methylvinyl, 2-methylvinyl, 1-methylpropenyl, and 2-methylpropenyl.

[0306] As a chain-like alkenyl group, the linear alkenyl group is preferred, more preferably vinyl or propenyl, and particularly preferably vinyl.

[0307] As R 101 Substituents in the chain alkyl or chain alkenyl groups, for example, alkoxy, halogen atom, haloalkyl, hydroxyl, carbonyl, nitro, amino, and the above R 101 Ring-shaped bases, etc.

[0308] Among them, R 101 Preferably, it is a cyclic group that can have substituents, and more preferably a cyclic hydrocarbon group that can have substituents. More specifically, it is preferably a group obtained by removing one or more hydrogen atoms from phenyl, naphthyl, or polycyclic alkanes; a lactone-containing cyclic group represented by the general formulas (a2-r-1), (a2-r-3) to (a2-r-7), respectively; or a -SO2-containing cyclic group represented by the general formulas (a5-r-1) to (a5-r-4), respectively.

[0309] In equation (b-1), Y 101 It is a single bond or a divalent linker containing an oxygen atom.

[0310] In Y 101 In the case where the Y is a divalent linking group containing an oxygen atom, 101 It can contain atoms other than oxygen atoms. Examples of atoms other than oxygen atoms include carbon atoms, hydrogen atoms, sulfur atoms, and nitrogen atoms.

[0311] Examples of the divalent linking groups containing oxygen atoms include linking groups represented by the above general formulas (y-al-1) to (y-al-8).

[0312] As Y 101 Preferably, the linking group contains a divalent ester bond or a divalent ether bond, and more preferably the linking group represented by the above general formulas (y-al-1) to (y-al-5).

[0313] In equation (b-1), V 101 It is a single bond, an alkylene group, or a fluoroalkylene group. V 101 The alkylene and fluoroalkylene groups preferably have 1 to 4 carbon atoms. As V 101 The fluoroalkylene groups in the text can be exemplified by V. 101 A group obtained by replacing some or all of the hydrogen atoms of the alkylene group with fluorine atoms. Wherein, V 101 Preferably, it is a single bond or a fluoroalkylene group having 1 to 4 carbon atoms.

[0314] In equation (b-1), R 102 It is a fluorine atom or a fluoroalkyl group having 1 to 5 carbon atoms. R 102 Preferably, it is a fluorine atom or a perfluoroalkyl group having 1 to 5 carbon atoms, more preferably a fluorine atom.

[0315] Specific examples of the anionic portion of component (b-1) include, for example, in Y 101 In the case of a single bond, examples include fluoroalkyl sulfonate anions such as trifluoromethane sulfonate anion or perfluorobutane sulfonate anion; in Y 101 In the case of a divalent linking group containing an oxygen atom, anions represented by any one of the following formulas (an-1) to (an-3) can be cited.

[0316] [Chemistry 30]

[0317]

[0318] [In the formula, R”] 101 It can be 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), or a chain alkyl group that may have substituents. R” 102 It can be an aliphatic cyclic group that may have substituents, a lactone-containing cyclic group represented by the general formulas (a2-r-1), (a2-r-3) to (a2-r-7), or a -SO2-containing cyclic group represented by the general formulas (a5-r-1) to (a5-r-4). R” 103 It can be 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 It is a single bond, an alkylene group having 1 to 4 carbon atoms, or a fluoroalkylene group having 1 to 4 carbon atoms. R 102It is a fluorine atom or a fluoroalkyl group having 1 to 5 carbon atoms. v” is an independent integer from 0 to 3, q” is an independent integer from 1 to 20, and n” is 0 or 1.

[0319] R” 101 、R” 102 and R” 103 The aliphatic cyclic group that may have substituents is preferably the R group. 101 The group exemplified is a cyclic aliphatic hydrocarbon group. Examples of substituents include those related to R. 101 The same substituents are used for the substituted cyclic aliphatic hydrocarbon groups.

[0320] R” 103 The aromatic cyclic group that may have substituents is preferably the R group. 101 Examples of substituents include aromatic hydrocarbon groups within cyclic hydrocarbon groups. Examples of substituents include those related to R. 101 The same substituents that can replace the aromatic hydrocarbon group in the same group.

[0321] R” 101 The substituted chain alkyl group in the R is preferably a substituent. 101 The chain-like alkyl group is exemplified by the group "R". 104 The chain alkenyl group that may have substituents is preferably the R group. 101 The chain-like alkenyl group is exemplified by the group.

[0322] V” 101 Preferably, it is a single bond or a fluoroalkylene group, more preferably a single bond or a fluoroalkylene group having 1 to 3 carbon atoms. In V” 101 In the case of a fluoroalkylene group, -V” 101 -C(F)(R” 102 )-SO3 - The V in 101 Preferably, it is -CF2-, -CHF-, -CF2CF2-, -CHFCF2-, -CF(CF3)CF2-, or -CH(CF3)CF2-, and more preferably -CF2- or -CHF-.

[0323] R 102 It is a fluorine atom or a fluoroalkyl group having 1 to 5 carbon atoms. R 102 Preferably, it is a fluorine atom or a perfluoroalkyl group having 1 to 5 carbon atoms, more preferably a fluorine atom.

[0324] v” is an integer from 0 to 3, preferably 0 or 1. q” is an integer from 1 to 20, preferably an integer from 1 to 10, more preferably an integer from 1 to 5, further preferably 1, 2 or 3, and particularly preferably 1 or 2. n” is 0 or 1.

[0325] • (b-2) Anionic portion of component

[0326] In equation (b-2), R 104 R 105 Each can be 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, and examples can be given for R in formula (b-1). 101 The same group. Among them, R... 104 R 105 They can bond together to form a ring.

[0327] R 104 R 105 Preferably, it is a chain alkyl group that may have substituents, more preferably a straight-chain or branched alkyl group, or a straight-chain or branched fluoroalkyl group.

[0328] The chain-like alkyl group preferably has 1 to 10 carbon atoms, more preferably 1 to 7, and even more preferably 1 to 3. For reasons such as good solubility in solvents used for resists, R... 104 R 105 The number of carbon atoms in the chain alkyl group is preferably as small as possible within the aforementioned range. Furthermore, R... 104 R 105 In a chain alkyl group, the more hydrogen atoms replaced by fluorine atoms, the stronger the acid, and therefore this is preferred. The proportion of fluorine atoms in the chain alkyl group, i.e., the fluorination rate, is preferably 70-100%, more preferably 90-100%, and most preferably a perfluoroalkyl group obtained by replacing all hydrogen atoms with fluorine atoms.

[0329] In equation (b-2), V 102 V 103 Each can be independently a single bond, an alkylene group, or a fluoroalkylene group, and examples can be given for V in formula (b-1). 101 The same group.

[0330] In equation (b-2), L 101 L 102 Each can be a single bond or an oxygen atom, independently.

[0331] • (b-3) Anionic portion of component

[0332] In equation (b-3), R 106 ~R 108 Each can be independently a cyclic group that may have substituents, a chain alkyl group that may have substituents, or a chain alkenyl group that may have substituents, and examples can be given for R in formula (b-1). 101 The same group.

[0333] L 103 ~L 105Each can be a single bond, -CO-, or -SO2-, respectively.

[0334] {Cation Section}

[0335] In equations (b-1), (b-2), and (b-3), m is an integer greater than or equal to 1, and M' m+ The m-valent onium cation can preferably be sulfonium cation or iodoonium cation, for example, organic cations represented by the general formulas (ca-1) to (ca-4).

[0336] [Chemistry 31]

[0337]

[0338] [In the formula, R] 201 ~R 207 and R 211 ~R 212 Each can be independently represented as an aryl group, an alkyl group, or an alkenyl group, which may have substituents. R 201 ~R 203 R 206 ~R 207 R 211 ~R 212 They can bond with each other individually to form a ring together with the sulfur atom in the formula. R 208 ~R 209 Each can independently represent a hydrogen atom or an alkyl group having 1 to 5 carbon atoms, or they can be bonded together to form a ring with the sulfur atom in the formula. R 210 It 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 -SO2- cyclic group that may have substituents. L 201 This represents -C(=O)- or -C(=O)-O-. Multiple Y's 201 Each can be independently represented as arylene, alkylene, or alkenyl. x is 1 or 2. W 201 [This represents a linking group with a valence of (x+1).]

[0339] As R 201 ~R 207 and R 211 ~R 212 The aryl group in the formula can be exemplified by aryl groups with 6 to 20 carbon atoms, with phenyl and naphthyl groups being preferred.

[0340] As R 201 ~R 207 and R 211 ~R 212 The alkyl group in the alkyl group is preferably a chain-like or cyclic alkyl group with 1 to 30 carbon atoms.

[0341] As R201 ~R 207 and R 211 ~R 212 The alkenyl group in the alkenyl group preferably has 2 to 10 carbon atoms.

[0342] As R 201 ~R 207 and R 211 ~R 212 The substituents that may be present include, for example, alkyl, halogen atom, haloalkyl, carbonyl, cyano, amino, aryl, and groups represented by the following general formulas (ca-r-1) to (ca-r-7).

[0343] [Chemistry 32]

[0344]

[0345] [In the formula, R'] 201 Each group can be an independent 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.

[0346] R' 201 Examples of substituent cyclic groups, substituent chain alkyl groups, or substituent chain alkenyl groups can be found with R in formula (b-1) described below. 101 In addition to the same group, other examples of the same group as the acid-dissociable group represented by the above formula (a1-r-2) can be cited as cyclic groups that may have substituents or chain alkyl groups that may have substituents.

[0347] In R 201 ~R 203 R 206 ~R 207 R 211 ~R 212 When they bond together and form a ring with the sulfur atom in the formula, they can be linked via heteroatoms such as sulfur, oxygen, and nitrogen atoms, carbonyl groups, -SO-, -SO2-, -SO3-, -COO-, -CONH-, or -N(R) N )-(the R N The ring is bonded to functional groups such as alkyl groups having 1 to 5 carbon atoms. Preferably, the ring structure containing the sulfur atom in the formula is a three- to ten-membered ring, and particularly preferably a five- to seven-membered ring. Specific examples of the formed ring include thiophene rings, thiazole rings, benzothiophene rings, thiathracene rings, benzothiophene rings, dibenzothiophene rings, 9H-thioxanthium rings, thioxanone rings, thiathracene rings, phenoxathiin rings, tetrahydrothiophenonium rings, and tetrahydrothiaranonium rings.

[0348] R 208~R 209 Each of the above independently represents a hydrogen atom or an alkyl group having 1 to 5 carbon atoms, preferably an alkyl group having 1 to 3 carbon atoms, in R 208 ~R 209 When they are alkyl groups, they can bond with each other to form a ring.

[0349] R 210 It can be an aryl group that may have a substituent, an alkyl group that may have a substituent, an alkenyl group that may have a substituent, or a -SO2- cyclic group that may have a substituent.

[0350] As R 210 The aryl group in the aryl group can be exemplified by unsubstituted aryl groups having 6 to 20 carbon atoms, with phenyl and naphthyl groups being preferred.

[0351] As R 210 The alkyl group in the alkyl group is preferably a chain or cyclic alkyl group with 1 to 30 carbon atoms.

[0352] As R 210 The alkenyl group in the R group is preferably an alkenyl group with 2 to 10 carbon atoms. 210 The group may contain a substituent-containing -SO2-cyclic group, preferably a "-SO2-containing polycyclic group", and more preferably a group represented by the general formula (a5-r-1).

[0353] Y 201 Each can be independently represented as arylene, alkylene, or alkenyl.

[0354] Y 201 The aryl group in the equation can be exemplified by R from equation (b-1) as described later. 101 The aromatic hydrocarbon group in the example is a group obtained by removing one hydrogen atom from the aryl group.

[0355] Y 201 The alkylene and alkenylene groups in the formula can be exemplified by R in formula (b-1) described later. 101 The group obtained by removing one hydrogen atom from the chain alkyl or chain alkenyl groups exemplified in the text.

[0356] In the formula (ca-4), x is 1 or 2.

[0357] W 201 It is a (x+1) valence, that is, a divalent or trivalent linking group.

[0358] As W 201 The divalent linking group in the formula (a2-1) is preferably a divalent hydrocarbon group that may have substituents, and can be exemplified by Ya in the formula (a2-1) above. 21 Similarly, divalent hydrocarbon groups that can have substituents. W 201The divalent linking group can be any of the following: linear, branched, or cyclic, preferably cyclic. Preferably, it is a group formed by combining two carbonyl groups at both ends of the arylene group. Examples of arylene groups include phenylene and naphthylene, with phenylene being particularly preferred.

[0359] As W 201 The trivalent linker group in W can be exemplified by the following: 201 Groups obtained by removing one hydrogen atom from a divalent linking group, and groups obtained by bonding another divalent linking group to the divalent linking group, etc. As W 201 The trivalent linking group in the group is preferably a group obtained by bonding two carbonyl groups to an arylene group.

[0360] As preferred cations represented by the formula (ca-1), examples can be given of cations represented by the following chemical formulas (ca-1-1) to (ca-1-78) and (ca-1-101) to (ca-1-149), respectively.

[0361] In the following chemical formulas, g1 represents the number of repetitions, which is an integer from 1 to 5. g2 represents the number of repetitions, which is an integer from 0 to 20. g3 represents the number of repetitions, which is an integer from 0 to 20.

[0362] [Chemistry 33]

[0363]

[0364] [Chemistry 34]

[0365]

[0366] [Chemistry 35]

[0367]

[0368] [Chemistry 36]

[0369]

[0370] [Chemistry 37]

[0371]

[0372] [Chemistry 38]

[0373]

[0374] [Chemistry 39]

[0375]

[0376] [Chemistry 40]

[0377]

[0378] [Chemistry 41]

[0379]

[0380] [Chemistry 42]

[0381]

[0382] [In the formula, R”] 201 It can be a hydrogen atom or a substituent. Examples of such substituents include the aforementioned R. 201 ~R 207 and R 211 ~R 212 Examples of substituents that may be present include alkyl groups, halogen atoms, haloalkyl groups, carbonyl groups, cyano groups, amino groups, aryl groups, and groups represented by general formulas (ca-r-1) to (ca-r-7).

[0383] As preferred cations represented by the formula (ca-2), examples include cations represented by the formulas (ca-2-1) to (ca-2-3), diphenyliodonium cation, and bis(4-tert-butylphenyl)iodonium cation.

[0384] [Chemistry 43]

[0385]

[0386] As preferred cations represented by the formula (ca-3), examples can be given of cations represented by the formulas (ca-3-1) to (ca-3-7) respectively.

[0387] [Chemistry 44]

[0388]

[0389] As preferred cations represented by the formula (ca-4), examples can be given of cations represented by the formulas (ca-4-1) to (ca-4-2) respectively.

[0390] [Chemistry 45]

[0391]

[0392] Of the above, the cation portion ((M) m+ ) 1 / mThe cations are preferably represented by the general formula (ca-1) or (ca-2), and more preferably by the chemical formulas (ca-1-1) to (ca-1-78), (ca-1-101) to (ca-1-149) and (ca-2-1) to (ca-2-3), respectively.

[0393] In the resist composition of this embodiment, component (B1) can be used alone or in combination with two or more components.

[0394] When the resist composition contains component (B1), the content of component (B1) in the resist composition is preferably 50 parts by mass or less relative to 100 parts by mass of component (A), more preferably 0.1 to 40 parts by mass, even more preferably 0.1 to 30 parts by mass, and particularly preferably 0.1 to 20 parts by mass.

[0395] <(C) Ingredients>

[0396] Component (C) is a crosslinking agent. Component (C) is not particularly limited and can be selected from any crosslinking agent known to date as a crosslinking agent in negative resist compositions. Examples of such acid-crosslinking substances include amino resins having hydroxyl or alkoxy groups, such as melamine resin, urea resin, guanidine resin, acetylguanidine resin, benzoguanidine resin, glycourea-formaldehyde resin, succinamide-formaldehyde resin, and ethylene urea-formaldehyde resin. The above-mentioned acid-crosslinking substances can be readily obtained by reacting melamine, urea, guanidine, acetylguanidine, benzoguanidine, glycourea, succinamide, or ethylene urea with formalin in boiling water to achieve hydroxymethylation, or by further reacting them with lower alcohols to achieve alkoxylation. From a practical standpoint, it can be obtained as melamine resins such as Nikalac (ニカラツク, registered trademark) MX-750, Nikalac MW-30, and Nikalac MW100LM, and urea resins such as Nikalac MX-290 (all manufactured by Sanwa Chemical Co., Ltd.). Furthermore, benzoguanamine resins such as CYMEL1123 and CYMEL1128 (manufactured by Mitsui Cyanamid Co., Ltd.) are also available as commercially available products.

[0397] In addition, as component (C), benzene compounds with alkoxy groups such as 1,3,5-tris(methoxymethoxy)benzene, 1,2,4-tris(isopropoxymethoxy)benzene, and 1,4-bis(sec-butoxymethoxy)benzene; and phenolic compounds with hydroxyl or alkoxy groups such as 2,6-dihydroxymethyl-p-tert-butylphenol can also be used.

[0398] Among them, as component (C), it is preferred to be a compound having a -NCH2-OCH3 group, more preferably a compound represented by the following formula (c1-1) or (c1-2), and even more preferably a compound having a melamine skeleton represented by the following formula (c1-1) or (c1-2).

[0399] [Chemistry 46]

[0400]

[0401] [In the formula, nc1 and nc2 are independent integers from 1 to 3.]

[0402] (C) Components can be used alone or in combination of two or more.

[0403] In the resist composition of this embodiment, the content of component (C) relative to 100 parts by mass of component (A) is preferably 1 to 50 parts by mass, more preferably 3 to 40 parts by mass, further preferably 3 to 30 parts by mass, and most preferably 5 to 25 parts by mass.

[0404] If the content of component (C) is above the lower limit, cross-linking formation is fully achieved, resulting in improved resolution performance and photolithography characteristics. Furthermore, a good resist pattern with minimal expansion can be obtained. Conversely, if the content is below the upper limit, the resist composition exhibits good storage stability, and the degradation of sensitivity over time is easily suppressed.

[0405] <(Z) component>

[0406] (Z) There are no special restrictions on the components as long as they are aromatic compounds with one or two phenolic hydroxyl groups in the molecule and no carboxyl groups.

[0407] As component (Z), it preferably contains at least one compound selected from the group consisting of compounds represented by the following general formula (z1-1) and compounds represented by the following general formula (z2-1).

[0408] [Chemistry 47]

[0409]

[0410] In formula (z1-1), V z 1 It is a divalent linker without hydroxyl or carboxyl groups. In formula (z2-1), Rz 2 It is a hydrocarbon group. n1 is 1 or 2. n2 is an integer from 2 to 5. Where n1 + n2 ≤ 6.

[0411] In the aforementioned equation (z1-1), V is used as... z 1The divalent linking group that does not have hydroxyl and carboxyl groups can be exemplified by Ya in the above general formula (a10-1). x1 The divalent linker in it does not contain either a hydroxyl or a carboxyl group. Furthermore, as V... z 1 The divalent linking group can also be exemplified by Ya, which is formed as the general formula (a10-1) above. x1 A group is a group obtained by replacing part of the hydrogen atom of a straight-chain or branched aliphatic hydrocarbon group with an aromatic hydrocarbon group in which a divalent linker group is formed.

[0412] Examples of straight-chain or branched aliphatic hydrocarbon groups in "groups obtained by replacing part of the hydrogen atom constituting a straight-chain or branched aliphatic hydrocarbon group with an aromatic hydrocarbon group" include methylene [-CH2-], ethylene [-(CH2)2-], -CH(CH3)-, -CH(CH2CH3)-, -C(CH3)2-, -C(CH3)(CH2CH3)-, -C(CH3)(CH2CH2CH3)-, -C(CH2CH3)2-, and alkylmethylene groups.

[0413] Aromatic hydrocarbon groups, which are groups obtained by replacing part of the hydrogen atom of the aliphatic hydrocarbon group that constitutes a straight or branched aliphatic hydrocarbon group with an aromatic hydrocarbon group, can be exemplified by groups obtained by removing a hydrogen atom from the aromatic rings of benzene, fluorene, naphthalene, anthracene, phenanthrene, biphenyl, etc.

[0414] The aromatic hydrocarbon group in "a group obtained by replacing part of the hydrogen atom of a straight-chain or branched aliphatic hydrocarbon group with an aromatic hydrocarbon group" may have substituents. Examples of such substituents include alkyl groups, alkoxy groups, halogen atoms, haloalkyl groups, hydroxyl groups, arylalkyl groups, etc.

[0415] The alkyl group used as the substituent is preferably an alkyl group having 1 to 5 carbon atoms, and most preferably methyl, ethyl, propyl, n-butyl, or tert-butyl.

[0416] The alkoxy group, halogen atom, and haloalkyl group that are the substituents can be exemplified by Ya in the above general formula (a10-1). x1 Among the divalent linking groups, the group exemplified is a substituent for the hydrogen atom present in the cyclic aliphatic hydrocarbon group.

[0417] Examples of arylalkyl groups that can be used as substituents include benzyl, phenethyl, phenyl-tert-butyl, 1-naphthylmethyl, 2-naphthylmethyl, 1-naphthylethyl, and 2-naphthylethyl. The arylalkyl group may have substituents such as alkyl, alkoxy, halogen atom, haloalkyl, hydroxyl, or arylalkyl groups.

[0418] As a compound represented by the formula (z1-1), it is preferred to be a compound represented by the general formula (z1-1-1).

[0419] [Chemistry 48]

[0420]

[0421] [In the formula, R] z 11 and R z 12 Each can be a hydrogen atom or a hydrocarbon group that may have substituents. R z 11 and R z 12 They can bond together to form a ring.

[0422] In the aforementioned equation (z1-1-1), R is used as... z 11 and R z 12 Hydrocarbon groups can be exemplified by straight-chain or branched alkyl groups, or aromatic hydrocarbon groups that may have substituents.

[0423] The linear alkyl group preferably has 1 to 5 carbon atoms, more preferably 1 to 4, and even more preferably 1 or 2. Specifically, examples include methyl, ethyl, n-propyl, n-butyl, and n-pentyl. Among these, methyl, ethyl, or n-butyl are preferred, and methyl or ethyl are more preferred.

[0424] The branched alkyl group preferably has 3 to 10 carbon atoms, more preferably 3 to 5. Specifically, examples include isopropyl, isobutyl, tert-butyl, isopentyl, neopentyl, 1,1-diethylpropyl, 2,2-dimethylbutyl, etc., with isopropyl being the most preferred.

[0425] As R z 11 and R z 12 Aromatic hydrocarbon groups can be exemplified by groups obtained by removing one hydrogen atom from the aromatic rings of benzene, fluorene, naphthalene, anthracene, phenanthrene, biphenyl, etc.

[0426] R z 11 and R z 12 The aromatic hydrocarbon group in the form may have substituents. As such substituents, they are the same as those that may be present in the "group obtained by replacing a portion of the hydrogen atom constituting a straight-chain or branched aliphatic hydrocarbon group with an aromatic hydrocarbon group".

[0427] In the aforementioned formula (z1-1-1), R z 11 and Rz 12 They can bond with each other to form rings. Examples of the rings formed include aliphatic rings such as cyclopentane, cyclohexane, and cycloheptane.

[0428] In the aforementioned formula (z1-1-1), R z 11 and R z 12 Preferably, it is a straight-chain alkyl group having 1 to 5 carbon atoms or an aromatic hydrocarbon group that may have substituents, or R z 11 and R z 12 They bond together to form an aliphatic ring, more preferably methyl, phenyl, or 4-(4-hydroxyphenyl-tert-butyl)phenyl, or R z 11 and R z 12 They bond together to form a cyclohexane ring.

[0429] In the above equation (z2-1), Rz 2 The hydrocarbon group in the formula (z1-1-1) can be exemplified as R. z 11 and R z 12 The group exemplified is a hydrocarbon group. Among them, Rz is... 2 The preferred group is an aromatic hydrocarbon group, more preferably phenyl or benzyl, and even more preferably phenyl.

[0430] In the formula (z2-1), n1 is preferably 1. n2 is preferably 2 or 3, more preferably 2.

[0431] As a compound represented by the formula (z2-1), it is preferred to be a compound represented by the general formula (z1-2-1).

[0432] [Chemistry 49]

[0433]

[0434] [In the formula, Rz] 21 and Rz 22 Each is an aromatic hydrocarbon group independently.

[0435] In the aforementioned equation (z1-2-1), Rz 2 The hydrocarbon group can be exemplified as Rz in the formula (z1-1-1). 11 and Rz 12 The group exemplified is a hydrocarbon group. Among them, Rz is... 2 Preferably phenyl or benzyl, more preferably phenyl.

[0436] The following are specific examples of component (Z).

[0437] [Transformation 50]

[0438]

[0439] The mass-average molecular weight (Mw) of component (Z) is preferably 1000 or less, more preferably 100 to 950, and even more preferably 150 to 900.

[0440] If the mass-average molecular weight of component (Z) is below the upper limit of the preferred range, it becomes easier to improve the substrate adhesion performance and wet etching resistance.

[0441] The (Z) component contained in the resist composition of this embodiment can be used alone or in combination with two or more components.

[0442] In the resist composition of this embodiment, the content of component (Z) is preferably 0.5 to 30 parts by mass relative to 100 parts by mass of component (A), more preferably 1 to 25 parts by mass, and even more preferably 3 to 20 parts by mass.

[0443] If the proportion of the (Z) component is within the preferred range, then the etching resistance is good and it is easy to form a pattern with a good shape.

[0444] <Any ingredient>

[0445] (D) Ingredients

[0446] In addition to components (A), (B), (C), and (Z), the resist composition in this embodiment may also contain an acid diffusion control component (hereinafter referred to as "component (D)"). Component (D) acts as a quencher (acid diffusion control agent) that captures acid generated in the resist composition due to exposure.

[0447] Examples of (D) components include nitrogen-containing organic compounds (D1) (hereinafter referred to as "(D1) components") and photodegradable bases (D2) that lose acid diffusion control through exposure decomposition, which do not belong to the (D1) component (hereinafter referred to as "(D2) components").

[0448] By using a resist composition containing component (D), the contrast between the exposed and unexposed areas of the resist film can be further improved when forming a resist pattern.

[0449] Regarding component (D1)

[0450] (D1) is an alkaline component, a nitrogen-containing organic compound that functions as an acid diffusion control agent in the resist composition.

[0451] As a component of (D1), there are no particular limitations as long as it functions as an acid diffusion control agent, such as aliphatic amines and aromatic amines.

[0452] Among aliphatic amines, aliphatic secondary amines and aliphatic tertiary amines are preferred.

[0453] Aliphatic amines are amines having one or more aliphatic groups, preferably with 1 to 12 carbon atoms.

[0454] Examples of aliphatic amines include amines (alkylamines or alkylolamines) or cyclic amines obtained by replacing at least one hydrogen atom of ammonia (NH3) with an alkyl or hydroxyalkyl group having 12 or fewer carbon atoms.

[0455] Specific examples of alkylamines and alkylolamines include monoalkylamines such as n-hexylamine, n-heptylamine, n-octylamine, n-nonylamine, and n-decylamine; dialkylamines such as diethylamine, di-n-propylamine, di-n-heptylamine, di-n-octylamine, and dicyclohexylamine; trialkylamines such as trimethylamine, triethylamine, tri-n-propylamine, tri-n-butylamine, tri-n-pentylamine, tri-n-hexylamine, tri-n-heptylamine, tri-n-octylamine, tri-n-nonylamine, tri-n-decylamine, and tri-n-dodecylamine; and alkylolamines such as diethanolamine, triethanolamine, diisopropanolamine, triisopropanolamine, di-n-octylamine, and tri-octylamine. Among these, trialkylamines having 5 to 10 carbon atoms are further preferred, and tri-n-pentylamine or tri-octylamine are particularly preferred.

[0456] 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).

[0457] Examples of aliphatic monocyclic amines include piperidine and piperazine. Examples of aliphatic polycyclic amines are preferably those with 6 to 10 carbon atoms, such as 1,5-diazabicyclo[4.3.0]-5-nonene, 1,8-diazabicyclo[5.4.0]-7-undecene, hexamethylenetetramine, and 1,4-diazabicyclo[2.2.2]octane.

[0458] Other aliphatic amines include tris(2-methoxymethoxyethyl)amine, tris{2-(2-methoxyethoxy)ethyl}amine, tris{2-(2-methoxyethoxymethoxy)ethyl}amine, tris{2-(1-methoxyethoxy)ethyl}amine, tris{2-(1-ethoxyethoxy)ethyl}amine, tris{2-(1-ethoxypropoxy)ethyl}amine, tris[2-{2-(2-hydroxyethoxy)ethoxy}ethyl]amine, triethanolamine triacetate, etc., with triethanolamine triacetate being preferred.

[0459] Examples of aromatic amines include 4-dimethylaminopyridine, pyrrole, indole, pyrazole, imidazole or their derivatives, tribenzylamine, aniline compounds, n-tert-butoxycarbonylpyrrolidine, etc.

[0460] (D1) Components can be used alone or in combination of two or more.

[0461] Of the above, component (D1) is preferably an aromatic amine, and more preferably an aniline compound. Examples of aniline compounds include 2,6-diisopropylaniline, N,N-dimethylaniline, N,N-dibutylaniline, and N,N-dihexylaniline.

[0462] Regarding component (D2)

[0463] As for component (D2), there is no particular limitation on whether it is a component that loses acid diffusion control through exposure decomposition. Preferably, it is one or more compounds selected from the group consisting of compounds represented by the following general formula (d2-1) (hereinafter referred to as "(d2-1) component"), compounds represented by the following general formula (d2-2) (hereinafter referred to as "(d2-2) component"), and compounds represented by the following general formula (d2-3) (hereinafter referred to as "(d2-3) component").

[0464] The components (d2-1) to (d2-3) decompose in the exposed portion of the resist film and lose their acid diffusion control (alkalinity), thus they cannot function as quenchers. Instead, they function as quenchers in the unexposed portion of the resist film.

[0465] [Chemistry 51]

[0466]

[0467] [In the formula, Rd] 1 ~Rd 4 It can be a cyclic group that may have substituents, a chain alkyl group that may have substituents, or a chain alkenyl group that may have substituents. Wherein, Rd in general formula (d2-2) 2 The carbon atom adjacent to the S atom in Yd has an unbonded fluorine atom. 1 It is a single bond or a divalent linker. m is an integer greater than or equal to 1, M' m+ Each is an m-valent ononium cation.

[0468] {(d2-1) component}

[0469] Anion section

[0470] In equation (d2-1), Rd 1The substitutable group can be a cyclic group, a chain alkyl group, or a chain alkenyl group, respectively, and examples can be made of R in formula (b-1). 101 The same group.

[0471] Among these, as Rd 1 Preferably, the substituent is an aromatic hydrocarbon group, an aliphatic cyclic group, or a chain alkyl group. Examples of substituents that can be present in these groups include hydroxyl, oxo, alkyl, aryl, fluorine, fluoroalkyl, lactone-containing cyclic groups represented by the above general formulas (a2-r-1) to (a2-r-7), ether bonds, ester bonds, or combinations thereof. In cases where an ether bond or ester bond is included as a substituent, an alkylene group can be used as the substituent, preferably a linking group represented by the above formulas (y-al-1) to (y-al-5).

[0472] As the aromatic hydrocarbon group, examples of preferred examples are polycyclic structures comprising a phenyl, naphthyl, or bicyclooctane skeleton (e.g., polycyclic structures consisting of a bicyclooctane skeleton ring structure and other ring structures).

[0473] The aliphatic cyclic group is more preferably a group obtained by removing one or more hydrogen atoms from polycyclic alkanes such as adamantane, norbornene, isoboronane, tricyclodecane, and tetracyclododecane.

[0474] The preferred chain alkyl group has 1 to 10 carbon atoms. Specifically, examples include straight-chain alkyl groups such as methyl, ethyl, propyl, butyl, pentyl, hexyl, heptyl, octyl, nonyl, and decyl; and branched-chain alkyl groups such as 1-methylethyl, 1-methylpropyl, 2-methylpropyl, 1-methylbutyl, 2-methylbutyl, 3-methylbutyl, 1-ethylbutyl, 2-ethylbutyl, 1-methylpentyl, 2-methylpentyl, 3-methylpentyl, and 4-methylpentyl.

[0475] When the chain-like alkyl group is a fluoroalkyl group having a fluorine atom or a fluoroalkyl group as a substituent, the fluoroalkyl group preferably has 1 to 11 carbon atoms, more preferably 1 to 8, and even more preferably 1 to 4. The fluoroalkyl group may contain atoms other than fluorine atoms. Examples of atoms other than fluorine atoms include oxygen atoms, sulfur atoms, and nitrogen atoms.

[0476] As Rd 1 Preferably, it is a fluoroalkyl group in which some or all of the hydrogen atoms constituting the straight-chain alkyl group are replaced by fluorine atoms, and particularly preferably it is a fluoroalkyl group (a straight-chain perfluoroalkyl group) in which all of the hydrogen atoms constituting the straight-chain alkyl group are replaced by fluorine atoms.

[0477] The following shows a preferred example of the anionic portion of component (d2-1).

[0478] [Chemistry 52]

[0479]

[0480] • Cation section

[0481] In equation (d2-1), M' m+ It is an m-valent onium cation.

[0482] As M' m+ The onium cations can preferably be the same as the cations represented by the general formulas (ca-1) to (ca-4), more preferably the cations represented by the general formula (ca-1), and even more preferably the cations represented by the formulas (ca-1-1) to (ca-1-78) and (ca-1-101) to (ca-1-149).

[0483] (d2-1) Components can be used alone or in combination of two or more.

[0484] {(d2-2) composition}

[0485] Anion section

[0486] In equation (d2-2), Rd 2 The cyclic group may have substituents, the chain alkyl group may have substituents, or the chain alkenyl group may have substituents; examples can be made of R in formula (b-1). 101 The same group.

[0487] Among them, Rd 2 The carbon atom adjacent to the S atom in the (d2-2) component has no bonded fluorine atom (no fluorine substitution). As a result, the anion of the (d2-2) component becomes a moderately weak acid anion, thus enhancing its quenching ability as a (D2) component.

[0488] As Rd 2 Preferably, it is a chain alkyl group that may have substituents, or an aliphatic cyclic group that may have substituents. As a chain alkyl group, it is preferably 1 to 10 carbon atoms, more preferably 3 to 10. As an aliphatic cyclic group, it is more preferably a group obtained by removing one or more hydrogen atoms from adamantane, norbornane, isobornane, tricyclodecane, tetracyclododecane, etc. (which may have substituents); or a group obtained by removing one or more hydrogen atoms from camphor, etc.

[0489] Rd 2 The hydrocarbon group may have substituents, and examples of such substituents include Rd of formula (d2-1). 1The hydrocarbon group (aromatic hydrocarbon group, aliphatic cyclic group, chain alkyl group) can have the same substituents as the group.

[0490] The following shows a preferred example of the anionic portion of component (d2-2).

[0491] [Chemistry 53]

[0492]

[0493] • Cation section

[0494] In equation (d2-2), M' m+ A munonium cation with a valence of m, and M' in the formula (d2-1) m+ They are the same onium cations.

[0495] (d2-2) Components can be used alone or in combination of two or more.

[0496] {(d2-3) components}

[0497] • Anion section

[0498] In equation (d2-3), Rd 3 The substituted group can be a cyclic group, a chain alkyl group, or a chain alkenyl group, and examples can be related to R in formula (b-1). 101 The same group is preferably a cyclic group containing a fluorine atom, a chain-like alkyl group, or a chain-like alkenyl group. Among them, fluoroalkyl groups are preferred, and more preferably those similar to the Rd group. 1 The same fluoroalkyl group.

[0499] In equation (d2-3), Rd 4 The cyclic group may have substituents, the chain alkyl group may have substituents, or the chain alkenyl group may have substituents; examples can be made of R in formula (b-1). 101 The same group.

[0500] Preferably, the alkyl, alkoxy, alkenyl, or cyclic groups may have substituents.

[0501] Rd 4 The alkyl group in the formula is preferably a straight-chain or branched alkyl group having 1 to 5 carbon atoms. Examples include methyl, ethyl, propyl, isopropyl, n-butyl, isobutyl, tert-butyl, pentyl, isopentyl, and neopentyl. 4 A portion of the hydrogen atoms in an alkyl group can be replaced by hydroxyl, cyano, or other groups.

[0502] Rd 4The alkoxy group in the alkoxy group is preferably an alkoxy group with 1 to 5 carbon atoms. Examples of alkoxy groups with 1 to 5 carbon atoms include methoxy, ethoxy, n-propoxy, isopropoxy, n-butoxy, and tert-butoxy. Among these, methoxy and ethoxy are preferred.

[0503] Rd 4 The alkenyl group in the formula can be exemplified by R in the formula (b-1). 101 The same group is preferred, such as vinyl, allyl, 1-methylpropenyl, or 2-methylpropenyl. These groups may further have alkyl groups having 1 to 5 carbon atoms or haloalkyl groups having 1 to 5 carbon atoms as substituents.

[0504] Rd 4 The cyclic basis in the equation can be exemplified by R in equation (b-1). 101 The same group is preferred, preferably an alicyclic group obtained by removing one or more hydrogen atoms from cycloalkanes such as cyclopentane, cyclohexane, adamantane, norbornene, isoboronane, tricyclodecane, and tetracyclododecane, or an aromatic group such as phenyl or naphthyl. In Rd 4 In the case of alicyclic groups, the photolithography properties become good by making the resist composition well soluble in organic solvents.

[0505] In equation (d2-3), Yd 1 It is a single bond or a divalent linker.

[0506] As Yd 1 The divalent linking group in the formula (a10-1) is not particularly limited, and examples include divalent hydrocarbon groups (aliphatic hydrocarbon groups, aromatic hydrocarbon groups) that can have substituents, and divalent linking groups containing heteroatoms. Examples of these can be found in relation to Ya in the above formula (a10-1). x1 The description of the divalent linking group is the same as that of the divalent hydrocarbon group that may have substituents and the divalent linking group containing heteroatoms.

[0507] As Yd 1 Preferably, it is a carbonyl group, an ester bond, an amide bond, an alkylene group, or a combination thereof. As an alkylene group, it is more preferably a straight-chain or branched alkylene group, and even more preferably a methylene or ethylene group.

[0508] The following shows a preferred example of the anionic portion of component (d2-3).

[0509] [Chemistry 54]

[0510]

[0511] [Chemistry 55]

[0512]

[0513] • Cation section

[0514] In equation (d2-3), M' m+ A munonium cation with a valence of m, and M' in the formula (d2-1) m+ They are the same onium cations.

[0515] (d2-3) Components can be used alone or in combination of two or more.

[0516] (D2) Component can be any one of the above-mentioned (d2-1) to (d2-3) components, or it can be a combination of two or more components.

[0517] When the resist composition contains component (D2), the content of component (D2) in the resist composition is preferably 0.5 to 35 parts by mass relative to 100 parts by mass of component (A), more preferably 1 to 25 parts by mass, even more preferably 2 to 20 parts by mass, and particularly preferably 3 to 15 parts by mass.

[0518] If the content of component (D2) is above the preferred lower limit, it is easy to obtain particularly good photolithography properties and resist pattern shape. On the other hand, if it is below the upper limit, a balance can be achieved with other components, and various photolithography properties become good.

[0519] (D2) Manufacturing method:

[0520] The manufacturing methods for components (d2-1) and (d2-2) are not particularly limited and can be manufactured by known methods.

[0521] Furthermore, there are no particular limitations on the manufacturing method of component (d2-3), for example, it can be manufactured in the same manner as the method described in US 2012-0149916.

[0522] (E) Ingredients: Compounds selected from at least one of the groups consisting of organic carboxylic acids and oxyacids of phosphorus and their derivatives.

[0523] For purposes such as preventing sensitivity degradation or improving the pattern shape of the resist and stability over time, the resist composition of this embodiment may contain at least one compound (E) selected from the group consisting of organic carboxylic acids and phosphorus oxyacids and their derivatives (hereinafter referred to as "(E) component") as an arbitrary component.

[0524] The preferred organic carboxylic acids are, for example, acetic acid, malonic acid, citric acid, malic acid, succinic acid, benzoic acid, and salicylic acid.

[0525] Examples of oxyacids containing phosphorus include phosphoric acid, phosphonic acid, and hypophosphonic acid, among which phosphonic acid is particularly preferred.

[0526] As derivatives of phosphorus-containing oxyacids, examples include esters obtained by replacing the hydrogen atoms of the aforementioned oxyacids with hydrocarbon groups, and examples of such hydrocarbon groups include alkyl groups having 1 to 5 carbon atoms and aryl groups having 6 to 15 carbon atoms.

[0527] Examples of phosphoric acid derivatives include dibutyl phosphate, diphenyl phosphate, and other phosphate esters.

[0528] Examples of phosphonic acid derivatives include dimethyl phosphonate, di-n-butyl phosphonate, phenylphosphonic acid, diphenyl phosphonate, dibenzyl phosphonate, and other phosphonate esters.

[0529] Examples of derivatives of hypophosphonic acid include hypophosphonate esters and phenylhydatilic acid.

[0530] In the resist composition of this embodiment, component (E) can be used alone or in combination with two or more components.

[0531] When the resist composition contains component (E), it is generally used in a range of 0.01 to 5 parts by mass relative to 100 parts by mass of component (A).

[0532] (F) Ingredients: Fluorine Additives

[0533] In order to impart water resistance to the resist film or to improve photolithography properties, the resist composition of this embodiment may contain a fluorine additive component (hereinafter referred to as "(F) component").

[0534] As component (F), for example, fluorine-containing polymers described in Japanese Patent Application Publication Nos. 2010-002870, 2010-032994, 2010-277043, 2011-13569, and 2011-128226 may be used.

[0535] More specifically, as component (F), examples can be given of polymers having structural units (f1) represented by the following formula (f1-1). Preferably, such polymers are polymers (homopolymers) consisting solely of structural units (f1) represented by the following formula (f1-1); copolymers of the structural unit (f1) with the structural unit (a1); the structural unit (f1), structural units derived from acrylic acid or methacrylic acid, and copolymers with the structural unit (a1). Here, the structural unit (a1) copolymerized with the structural unit (f1) is preferably a structural unit derived from 1-ethyl-1-cyclooctyl (meth)acrylate or a structural unit derived from 1-methyl-1-adamantyl (meth)acrylate.

[0536] [Chemistry 56]

[0537]

[0538] [In the formula, R is the same as described above, Rf] 102 and Rf 103 Each of the following can be independently represented: a hydrogen atom, a halogen atom, an alkyl group having 1 to 5 carbon atoms, or a haloalkyl group having 1 to 5 carbon atoms. Rf 102 and Rf 103 They can be the same or different. nf 1 Rf is an integer from 1 to 5. 101 [This refers to an organic group containing a fluorine atom.]

[0539] In formula (f1-1), R bonded to the carbon atom at the α position is the same as described above. Preferably, R is a hydrogen atom or a methyl group.

[0540] In equation (f1-1), Rf 102 and Rf 103 Halogen atoms can be exemplified by fluorine, chlorine, bromine, and iodine atoms, with fluorine atoms being particularly preferred. As Rf... 102 and Rf 103 The alkyl group having 1 to 5 carbon atoms can be exemplified by groups having the same alkyl group having 1 to 5 carbon atoms as the aforementioned R, preferably methyl or ethyl. As Rf 102 and Rf 103 The alkyl group having 1 to 5 carbon atoms is specifically an alkyl group having 1 to 5 carbon atoms in which some or all of the hydrogen atoms are replaced by halogen atoms. Examples of halogen atoms include fluorine, chlorine, bromine, and iodine atoms, with fluorine atoms being particularly preferred. Among these, Rf... 102 and Rf 103 Preferably, it contains hydrogen atoms, fluorine atoms, or alkyl groups having 1 to 5 carbon atoms, and preferably contains hydrogen atoms, fluorine atoms, methyl or ethyl atoms.

[0541] In equation (f1-1), nf 1 It is an integer from 1 to 5, preferably an integer from 1 to 3, and more preferably 1 or 2.

[0542] In equation (f1-1), Rf 101 It is an organic group containing a fluorine atom, preferably a hydrocarbon group containing a fluorine atom.

[0543] The hydrocarbon group containing fluorine atoms can be linear, branched, or cyclic, preferably with 1 to 20 carbon atoms, more preferably with 1 to 15 carbon atoms, and particularly preferably with 1 to 10 carbon atoms.

[0544] Furthermore, the hydrocarbon group containing fluorine atoms preferably has fluorinated hydrogen atoms of 25% or more, more preferably 50% or more, and from the perspective of improving the hydrophobicity of the resist film during immersion exposure, it is particularly preferred that 60% or more of the hydrogen atoms are fluorinated.

[0545] Among them, as Rf 101 More preferably, fluoroalkyl groups with 1 to 6 carbon atoms, especially trifluoromethyl, -CH2-CF3, -CH2-CF2-CF3, -CH(CF3)2, -CH2-CH2-CF3, -CH2-CH2-CF2-CF2-CF3.

[0546] The mass-average molecular weight (Mw) of component (F) (based on polystyrene conversion standard using gel permeation chromatography) is preferably 1,000 to 50,000, more preferably 5,000 to 40,000, and most preferably 10,000 to 30,000. If it is below the upper limit of this range, it has sufficient solubility in solvents for use as a resist; if it is above the lower limit of this range, the resist film has good water repellency.

[0547] The molecular weight distribution coefficient (Mw / Mn) of component (F) is preferably 1.0 to 5.0, more preferably 1.0 to 3.0, and most preferably 1.2 to 2.5.

[0548] In the resist composition of this embodiment, component (F) can be used alone or in combination with two or more components.

[0549] When the resist composition contains component (F), it is usually used in a ratio of 0.5 to 10 parts by mass of component (F) relative to 100 parts by mass of component (A).

[0550] (S) Ingredients: Organic solvents

[0551] The resist composition of this embodiment can be manufactured by dissolving the resist material in an organic solvent component (hereinafter referred to as "(S) component").

[0552] As component (S), any component that can dissolve the various components used to form a homogeneous solution may be used. Any component may be appropriately selected from substances known in the past as solvents for chemically amplified resist compositions.

[0553] For example, as component (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; polyols such as ethylene glycol, diethylene glycol, propylene glycol, and dipropylene glycol; compounds with ester bonds such as ethylene glycol monoacetate, diethylene glycol monoacetate, propylene glycol monoacetate, or dipropylene glycol monoacetate; polyol derivatives such as monomethyl ether, monoethyl ether, monopropyl ether, monobutyl ether, etc., or compounds with ether bonds such as monoalkyl ether or monophenyl ether of the aforementioned polyols or compounds with ester bonds [among these, Preferred organic solvents include propylene glycol monomethyl ether acetate (PGMEA) and propylene glycol monomethyl ether (PGME); cyclic ethers such as dioxane; methyl lactate, ethyl lactate (EL), methyl acetate, ethyl acetate, butyl acetate, methyl pyruvate, ethyl pyruvate, methyl methoxypropionate, ethyl ethoxypropionate, and other esters; aromatic organic solvents such as anisole, ethyl benzyl ether, methyl toluene, diphenyl ether, dibenzyl ether, phenethyl ether, butyl phenyl ether, ethylbenzene, diethylbenzene, pentylene, cumene, toluene, xylene, isopropyl toluene, and mesitylene; and dimethyl sulfoxide (DMSO).

[0554] In the resist composition of this embodiment, component (S) can be used alone or as a mixed solvent of two or more components.

[0555] Among them, PGMEA, PGME, γ-butyrolactone, EL, and cyclohexanone are preferred.

[0556] Furthermore, a mixed solvent obtained by mixing PGMEA with a polar solvent is preferred. The mixing ratio (mass ratio) can be appropriately determined by taking into account the compatibility between PGMEA and the polar solvent, and is preferably set in the range of 1:9 to 9:1, and more preferably in the range of 2:8 to 8:2.

[0557] More specifically, when EL or cyclohexanone is used as a polar solvent, the mass ratio of PGMEA to EL or cyclohexanone is preferably 1:9 to 9:1, more preferably 2:8 to 8:2. Furthermore, when PGME is used as a polar solvent, the mass ratio of PGMEA to PGME is preferably 1:9 to 9:1, more preferably 2:8 to 8:2, and even more preferably 3:7 to 7:3. Moreover, a mixture of PGMEA and PGME with cyclohexanone is also preferred.

[0558] In addition, as component (S), at least one of the solvents selected from PGMEA and EL, mixed with γ-butyrolactone, is preferably used. In this case, the mass ratio of the former to the latter is preferably set to 70:30 to 95:5.

[0559] The amount of component (S) used is not particularly limited, and is appropriately set according to the coating film thickness at a concentration suitable for coating onto a substrate or the like. Generally, component (S) is used in such a way that the concentration of the solid component in the resist composition is in the range of 0.1 to 50% by mass, preferably 10 to 50% by mass.

[0560] The resist composition of this embodiment may further contain additives with a commensurate nature, such as additional resins for improving the performance of the resist film, dissolution inhibitors, plasticizers, stabilizers, colorants, anti-halo agents, dyes, etc., as desired.

[0561] After dissolving the aforementioned resist material in component (S), the resist composition of this embodiment can also remove impurities using a polyimide porous membrane, a polyamide-imide porous membrane, or the like. For example, the resist composition can be filtered using a filter made of a polyimide porous membrane, a filter made of a polyamide-imide porous membrane, or a filter made of both a polyimide porous membrane and a polyamide-imide porous membrane. Examples of the polyimide porous membrane and the polyamide-imide porous membrane include, for example, the substances described in Japanese Patent Application Publication No. 2016-155121.

[0562] The negative resist composition of this embodiment contains a polymeric compound (A1), an acid-generating agent (B0), a crosslinking agent (C), and an aromatic compound (Z) having one or two phenolic hydroxyl groups in the molecule but no carboxyl groups.

[0563] The inventors' research indicates that when using a negative resist composition employing an alkali-soluble polyhydroxystyrene resin as a substrate component to form a resist pattern, sometimes insufficient etching resistance occurs when forming a micron-scale thick resist film using wet etching resistance, followed by the formation of the resist pattern and subsequent etching. This can be attributed to insufficient adhesion between the resist film formed using the negative resist composition and the substrate interface.

[0564] In the resist composition of this embodiment described above, it is speculated that the (Z) component segregates in the lower layer of the resist film, which contributes to improved substrate adhesion. Therefore, it is speculated that the resist pattern formed using the negative resist composition of this embodiment exhibits good etching resistance.

[0565] (Resist Pattern Formation Method)

[0566] The second aspect of the present invention is a method for forming a resist pattern, comprising: step (i), forming a resist film on a support using the resist composition of the first aspect described above; step (ii), exposing the resist film; and step (iii), developing the exposed resist film to form a resist pattern.

[0567] As one embodiment of the above-described resist pattern forming method, a resist pattern forming method performed as described below can be cited as an example.

[0568] Process (i):

[0569] First, the resist composition of the above embodiment is applied to the support using a spin coater or the like, and for example, a baking (pre-baking (PAB)) treatment is performed at a temperature of 80 to 160°C for 40 to 200 seconds, preferably a baking treatment for 60 to 150 seconds, to form a resist film.

[0570] Process (ii):

[0571] Next, the resist film is selectively exposed by an exposure apparatus such as a KrF exposure apparatus, by exposure through a mask (mask pattern) with a predetermined pattern, and then baked for 40 to 150 seconds at a temperature of, for example, 80 to 150°C (post-exposure bake), preferably for 60 to 120 seconds.

[0572] Process (iii):

[0573] Next, the resist film is subjected to a development treatment. In the case of an alkaline development process, an alkaline developer is used; in the case of a solvent development process, a developer containing an organic solvent (organic developer) is used.

[0574] After development, rinsing is preferably performed. In the case of alkaline development, rinsing with pure water is preferred, while in the case of solvent development, rinsing with a rinsing solution containing organic solvents is preferred.

[0575] In the case of solvent development processes, after the development or rinsing process, a process can be performed to remove the developer or rinsing solution adhering to the pattern using a supercritical fluid.

[0576] Drying is performed after development or rinsing. Alternatively, baking (post-baking) may be performed after development, depending on the circumstances. Here, baking (post-baking) is performed, for example, at a temperature of 80°C or higher, preferably 90–120°C, for 10–120 seconds, and more preferably 30–90 seconds.

[0577] As described above, it is possible to form a resist pattern.

[0578] There are no particular limitations on the support structure; conventionally known supports can be used, such as substrates for electronic components or supports on which a specified wiring pattern is formed. More specifically, examples include silicon wafers, metal substrates made of copper, chromium, iron, aluminum, or glass substrates. For the wiring pattern material, for example, copper, aluminum, nickel, or gold can be used.

[0579] Furthermore, the support can be a support on a substrate as described above, on which an inorganic and / or organic film is provided. Examples of inorganic films include inorganic antireflective films (inorganic BARC). Examples of organic films include organic antireflective films (organic BARC), and organic films such as the lower organic film in a multilayer resist process.

[0580] Here, the multilayer resist method refers to a method in which at least one organic film (lower organic film) and at least one resist film (upper resist film) are formed on a substrate, and the resist pattern formed on the upper resist film is used as a mask to pattern the lower organic film. This method is considered capable of forming patterns with a high aspect ratio. That is, according to the multilayer resist method, the required thickness can be ensured by the lower organic film, thus enabling the resist film to be thinned and high aspect ratio fine patterns to be formed.

[0581] In the multilayer resist method, it is basically divided into a two-layer structure method that uses an upper resist film and a lower organic film (2-layer resist method); and a multilayer structure method that uses three or more layers (3-layer resist method) that sets one or more intermediate layers (such as metal thin film) between the upper resist film and the lower organic film.

[0582] The resist patterning method of the embodiment is a useful method for forming thick resist films. Even if the thickness of the resist film formed in step (i) is, for example, 1 to 10 μm, a resist pattern can be stably formed with a good shape.

[0583] There are no particular limitations on the wavelengths used in the exposure; radiation such as gamma rays, i-rays, ArF excimer lasers, KrF excimer lasers, F2 excimer lasers, EUV (extreme ultraviolet), VUV (vacuum ultraviolet), EB (electron beam), X-rays, and soft X-rays can be used.

[0584] The resist composition of the first embodiment described above is highly useful for use with ultraviolet light such as gamma rays and i-rays, KrF excimer lasers, ArF excimer lasers, EB, or EUV; even more useful for use with ultraviolet light such as gamma rays and i-rays, KrF excimer lasers, and ArF excimer lasers; and particularly useful for use with ultraviolet light such as gamma rays and i-rays, and KrF excimer lasers. The resist patterning method of the second embodiment is particularly preferred when the resist film is irradiated with ultraviolet light such as gamma rays and i-rays, or KrF excimer lasers in step (ii).

[0585] 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.

[0586] Immersion exposure refers to an exposure method in which the space between the resist film and the lens at the bottom of the exposure device is filled with a solvent (immersion medium) with a refractive index greater than that of air, and then the exposure is performed (immersion exposure).

[0587] The preferred immersion medium is a solvent having a refractive index greater than that of air and less than that of the exposed resist film. There are no particular limitations on the refractive index of the solvent if it falls within the specified range.

[0588] Examples of solvents that have a refractive index greater than that of air and less than that of the resist film include water, fluorine-based inert liquids, silicon-based solvents, and hydrocarbon solvents.

[0589] Specific examples of fluorine-based inert liquids include liquids whose main components are fluorine compounds such as C3HCl2F5, C4F9OCH3, C4F9OC2H5, and C5H3F7. Liquids with a boiling point of 70–180°C are preferred, and liquids with a boiling point of 80–160°C are more preferred. If the fluorine-based inert liquid has a boiling point within the above-mentioned range, the medium used for immersion can be removed by a simple method after exposure, which is therefore preferable.

[0590] As an inert fluorine-based liquid, perfluoroalkyl compounds in which all hydrogen atoms of the alkyl group are replaced by fluorine atoms are particularly preferred. Examples of perfluoroalkyl compounds include perfluoroalkyl ethers and perfluoroalkylamines.

[0591] Specifically, examples of perfluoroalkyl ether compounds include perfluoro(2-butyltetrahydrofuran) (boiling point 102°C), and examples of perfluoroalkylamine compounds include perfluorotributylamine (boiling point 174°C).

[0592] From the perspectives of cost, safety, environmental issues, and versatility, water is the preferred immersion medium.

[0593] An example of an alkaline developing solution used in alkaline developing processes is a 0.1 to 10% by mass aqueous solution of tetramethylammonium hydroxide (TMAH).

[0594] The organic solvent contained in the organic developing solution used in solvent-based developing processes can be any organic solvent capable of dissolving component (A) (the component (A) before exposure). It can be appropriately selected from known organic solvents. Specifically, examples include polar solvents such as ketones, esters, alcohols, nitriles, amides, and ethers, as well as hydrocarbon solvents.

[0595] Ketone solvents are organic solvents containing CC(=O)-C in their structure. Ester solvents are organic solvents containing CC(=O)-OC in their structure. Alcohol solvents are organic solvents containing an alcoholic hydroxyl group in their structure. "Alcoholic hydroxyl group" refers to a hydroxyl group bonded to a carbon atom of an aliphatic hydrocarbon group. Nitrile solvents are organic solvents containing a nitrile group in their structure. Amide solvents are organic solvents containing an amide group in their structure. Ether solvents are organic solvents containing COC in their structure.

[0596] Among organic solvents, there are also organic solvents whose structures contain multiple functional groups that possess the characteristics of the solvents described above. In this case, the organic solvent simultaneously belongs to all solvent types containing the aforementioned functional groups. For example, diethylene glycol monomethyl ether simultaneously belongs to either alcohol solvents or ether solvents in the above classifications.

[0597] Hydrocarbon solvents are hydrocarbon solvents composed of halogenable hydrocarbons and without substituents other than halogen atoms. Examples of halogen atoms include fluorine, chlorine, bromine, and iodine atoms, with fluorine atoms being preferred.

[0598] Among the organic solvents contained in organic developing solutions, polar solvents are preferred, and ketone solvents, ester solvents, nitrile solvents, etc. are also preferred.

[0599] Examples of ketone solvents include 1-octanone, 2-octanone, 1-nonanone, 2-nonanone, acetone, 4-heptanone, 1-hexanone, 2-hexanone, diisobutyl ketone, cyclohexanone, methylcyclohexanone, phenylacetone, methyl ethyl ketone, methyl isobutyl ketone, acetylacetone, diacetone, ionone, diacetone alcohol, acetylmethanol, acetophenone, methyl naphthyl ketone, isophorone, propylene carbonate, γ-butyrolactone, and methylpentyl ketone (2-heptanone). Among these, methylpentyl ketone (2-heptanone) is preferred as a ketone solvent.

[0600] Examples of ester solvents include methyl acetate, butyl acetate, ethyl acetate, isopropyl acetate, amyl acetate, isoamyl acetate, ethyl methoxyacetate, ethyl ethoxyacetate, propylene glycol monomethyl ether acetate, ethylene glycol monoethyl ether acetate, ethylene glycol monopropyl ether acetate, ethylene glycol monobutyl ether acetate, ethylene glycol monophenyl ether acetate, diethylene glycol monomethyl ether acetate, diethylene glycol monopropyl ether acetate, diethylene glycol monophenyl ether acetate, diethylene glycol monobutyl ether acetate, diethylene glycol monoethyl ether acetate, 2-methoxybutyl acetate, 3-methoxybutyl acetate, 4-methoxybutyl acetate, 3-methyl-3-methoxybutyl acetate, 3-ethyl-3-methoxybutyl acetate, propylene glycol monomethyl ether acetate, propylene glycol monoethyl ether acetate, propylene glycol monopropyl ether acetate, 2-ethoxybutyl acetate, and 4-ethoxybutyl acetate. 4-Propoxybutylacetic acid ester, 2-Methoxypentylacetic acid ester, 3-Methoxypentylacetic acid ester, 4-Methoxypentylacetic acid ester, 2-Methyl-3-Methoxypentylacetic acid ester, 3-Methyl-3-Methoxypentylacetic acid ester, 3-Methyl-4-Methoxypentylacetic acid ester, 4-Methyl-4-Methoxypentylacetic acid ester, Propylene glycol diacetate, Methyl formate, Ethyl formate, Butyl formate, Propyl formate, Ethyl lactate, Butyl lactate Among these, propyl lactate, ethyl carbonate, propyl carbonate, butyl carbonate, methyl pyruvate, ethyl pyruvate, propyl pyruvate, butyl pyruvate, methyl acetoacetate, ethyl acetoacetate, methyl propionate, ethyl propionate, propyl propionate, isopropyl propionate, methyl 2-hydroxypropionate, ethyl 2-hydroxypropionate, methyl-3-methoxypropionate, ethyl-3-methoxypropionate, ethyl-3-ethoxypropionate, propyl-3-methoxypropionate, etc., butyl acetate is preferred as an ester solvent.

[0601] Examples of nitrile solvents include acetonitrile, propionitrile, valerate, and butyronitrile.

[0602] Organic developers can be mixed with known additives as needed. Examples of such additives include surfactants. There are no particular limitations on the surfactant; for example, ionic and nonionic fluorinated and / or silicone surfactants can be used. Nonionic surfactants are preferred, and nonionic fluorinated surfactants or nonionic silicone surfactants are more preferred.

[0603] When a surfactant is added, the amount added is typically 0.001 to 5% by mass relative to the total amount of the organic developer, preferably 0.005 to 2% by mass, and more preferably 0.01 to 0.5% by mass.

[0604] The developing process can be carried out using known developing methods, such as immersing the support in the developing solution for a certain time (immersion method), bearing the developing solution on the surface of the support by surface tension and letting it remain still for a certain time (puddle method), spraying the developing solution onto the surface of the support (spraying method), and continuously dispensing the developing solution onto the support rotating at a certain speed while scanning the nozzle at a certain speed (dynamic distribution method), etc.

[0605] The organic solvent contained in the rinsing solution used for rinsing after development in a solvent-based developing process can be, for example, an organic solvent that is difficult to dissolve the resist pattern, exemplified as an organic solvent for organic developers. 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 selected from hydrocarbon solvents, ketone solvents, ester solvents, alcohol solvents, and amide solvents is preferred, more preferably selected from at least one selected from alcohol solvents and ester solvents, and particularly preferred is an alcohol solvent.

[0606] The alcohol solvent used in the rinsing solution is preferably a monohydric alcohol with 6 to 8 carbon atoms, which can be straight-chain, branched, or cyclic. Specifically, examples include 1-hexanol, 1-heptanol, 1-octanol, 2-hexanol, 2-heptanol, 2-octanol, 3-hexanol, 3-heptanol, 3-octanol, 4-octanol, and benzyl alcohol. Among these, 1-hexanol, 2-heptanol, and 2-hexanol are preferred, and 1-hexanol and 2-hexanol are more preferred.

[0607] These organic solvents can be used alone or in combination of two or more. Furthermore, they can be mixed with organic solvents other than those mentioned above or with water. However, considering the developing properties, the amount of water mixed in the rinsing solution is preferably 30% by mass or less, more preferably 10% by mass or less, even more preferably 5% by mass or less, and particularly preferably 3% by mass or less, relative to the total amount of the rinsing solution.

[0608] The rinsing solution can be mixed with known additives as needed. Examples of such additives include surfactants. Surfactants can be the same as those described above, preferably nonionic surfactants, more preferably nonionic fluorinated surfactants, or nonionic silicone surfactants.

[0609] When a surfactant is added, the amount added is typically 0.001 to 5% by mass relative to the total amount of rinsing solution, preferably 0.005 to 2% by mass, and more preferably 0.01 to 0.5% by mass.

[0610] Rinsing treatment (cleaning treatment) using rinsing solution can be carried out using known rinsing methods. Examples of such rinsing methods include continuously dispensing rinsing solution onto a support rotating at a certain speed (spin coating), immersing the support in rinsing solution for a certain time (immersion method), and spraying rinsing solution onto the surface of the support (spraying method).

[0611] In the resist pattern forming method of this embodiment described above, it is presumed that since the resist composition of the first scheme described above is used, a resist pattern with good etching resistance can be obtained.

[0612]

Example

[0613] The present invention will be further described in detail below by way of examples, but the present invention is not limited to these examples.

[0614] <Preparation of Anti-corrosion Composition>

[0615] (Examples 1-12, Comparative Examples 1-5)

[0616] The components shown in Tables 1 and 2 were mixed and dissolved to prepare the resist compositions for each example.

[0617] Table 1

[0618]

[0619] Table 2

[0620]

[0621] In Tables 1 and 2, each abbreviation has the following meaning. The value in [] is the amount of blending (parts by mass).

[0622] (A)-1: A polymer compound represented by the following chemical formula (A-1). This polymer compound (A-1) is obtained by free radical polymerization of monomers that derive the structural units constituting this polymer compound in a specified molar ratio. Regarding this polymer compound (A-1), the weight-average molecular weight (Mw) converted to polystyrene standards by GPC measurement is 2500, and the molecular weight distribution coefficient (Mw / Mn) is 1.2. 13 The copolymer composition ratio (the proportion (molar ratio) of each structural unit in the structural formula) obtained by C-NMR is l / m = 90 / 10.

[0623] [Chemistry 57]

[0624]

[0625] (A)-2: A polymeric compound (homopolymer) represented by the following chemical formula (A-2). This polymeric compound (A-2) is obtained by free radical polymerization of a monomer (hydroxystyrene) from which the structural units constituting this polymeric compound are derived. The mass-average molecular weight (Mw) of this polymeric compound (A-2), converted to polystyrene standards by GPC measurements, is 2500, and its molecular weight distribution (Mw / Mn) is 1.2.

[0626] [Chem.58]

[0627]

[0628] (B)-1 to (B)-3: Acid-producing agents composed of compounds represented by the following chemical formulas (B-1) to (B-3).

[0629] [Chemistry 59]

[0630]

[0631] (C)-1: A crosslinking agent consisting of a compound represented by the following chemical formula (C-1).

[0632] (D)-1: A nitrogen-containing organic compound consisting of a compound represented by the following chemical formula (D-1).

[0633] [Transformation 60]

[0634]

[0635] (Z)-1: The compound represented by the following chemical formula (Z-1). The mass-average molecular weight (Mw) is 268.36.

[0636] (Z)-2: A compound represented by the chemical formula (Z-2). Its mass-average molecular weight (Mw) is 352.43.

[0637] (Z)-3: A compound represented by the chemical formula (Z-3). Its mass-average molecular weight (Mw) is 246.31.

[0638] (Z)-11: A compound represented by the following chemical formula (Z-11). The mass-average molecular weight (Mw) is 230.22.

[0639] (Z)-12: A compound represented by the chemical formula (Z-12). Its mass-average molecular weight (Mw) is 278.22.

[0640] (Z)-13: A compound represented by the chemical formula (Z-13). Its mass-average molecular weight (Mw) is 286.33.

[0641] (S)-1: Propylene glycol monomethyl ether acetate

[0642] [Chemistry 61]

[0643]

[0644] <Methods for forming resist patterns>

[0645] Process (i):

[0646] On a silicon substrate treated with hexamethyldisilazane (HMDS), the resist compositions of each example were coated using a spin coater, pre-baked (PAB) at 90°C for 90 seconds on a hot plate, and then dried to form a resist film with a thickness of 3 μm.

[0647] Process (ii):

[0648] Next, the resist film is selectively irradiated with a high-pressure mercury lamp (365nm) through a mask pattern using an i-ray stepper (reduced projection exposure device: NSR-2205i14E (Nikon Corporation; NA (numerical aperture) = 0.57, σ = 0.67)).

[0649] Then, it is subjected to post-exposure heating (PEB) treatment at 110°C for 60 seconds.

[0650] Process (iii):

[0651] Next, alkaline development was performed using a 2.38% by mass tetramethylammonium hydroxide (TMAH) aqueous solution “NMD-3” (trade name, manufactured by Tokyo Ohka Kogyo Co., Ltd.) as the developer at 23°C for 60 seconds.

[0652] Then, bake at 100°C for 60 seconds (post-baking).

[0653] The result is the formation of an isolated line pattern with a spacing width of 600 nm (hereinafter referred to as the "IS pattern").

[0654] <Bottom Cut Review>

[0655] The cross-sectional shape of the IS pattern formed in the <Method for Forming Resist Pattern> was observed using a scanning electron microscope (product name: S4500; manufactured by Hitachi, Ltd.), and the undercut (the cut of the resist itself at the bottom of the resist pattern formed on the substrate) (nm) was evaluated. The results are shown in Tables 3 and 4.

[0656] <Evaluation of resistance to wet etching>

[0657] A portion of the substrate with the IS pattern formed by the above-described resist pattern formation method is cut and immersed in 23% buffered hydrofluoric acid for 12 minutes.

[0658] The cross-sectional shape of the impregnated IS pattern was observed using a scanning electron microscope (product name: S4500; manufactured by Hitachi, Ltd.) to evaluate the side etching (the cut-outs created by etching at the interface between the resist film and the substrate) (μm). The results are shown in Tables 3 and 4.

[0659] Table 3

[0660]

[0661] Table 4

[0662]

[0663] Based on the results shown in Tables 3 and 4, the following was confirmed: the resist patterns formed using the resist compositions of Examples 1 to 12 exhibit good dry etching resistance and wet etching resistance.

[0664] While preferred embodiments of the present invention have been described above, the present invention is not limited to these embodiments. Additions, omissions, substitutions, and other modifications can be made to the structure without departing from the spirit of the invention. The present invention is not limited by the foregoing description, but only by the scope of the appended claims.

Claims

1. A negative resist composition, characterized in that, contain: A polymeric compound (A1) having a structural unit (a10) represented by the following general formula (a10-1); As an acid-producing agent (B0) selected from the group consisting of at least one compound represented by the following chemical formula (B0-1), the following chemical formula (B0-2), and the following chemical formula (B0-3). Crosslinking agent for amino resins containing hydroxyl or alkoxy groups (C); Aromatic compounds (Z) that have one or two phenolic hydroxyl groups in the molecule but no carboxyl group. The aromatic compound (Z) contains at least one compound selected from the group consisting of compounds represented by the following general formula (z1-1-1) and compounds represented by the following general formula (z1-2-1). [Chemistry 1] In the formula, R is a hydrogen atom, an alkyl group having 1 to 5 carbon atoms, or a haloalkyl group having 1 to 5 carbon atoms, and Ya x1 It consists of a straight-chain aliphatic hydrocarbon group or single bond with 1 to 3 carbon atoms. x1 It is a benzene ring, n ax1 Integers greater than or equal to 1 [Chemistry 2] [Chemistry 3] In the formula, R z 11 and R z 12 Each is independently methyl, phenyl, or 4-(4-hydroxyphenyl-tert-butyl)phenyl, or R z 11 and R z 12 They bond together to form a cyclohexane ring. [Chemistry 4] In the formula, Rz 21 and Rz 22 Each is an aromatic hydrocarbon group.

2. The negative resist composition according to claim 1, characterized in that, The structural unit (a10) is at least one selected from the group consisting of structural units represented by the following chemical formulas (a10-1-11) to (a10-1-13), respectively. [Chemistry 5] In the formula, R α It represents a hydrogen atom, a methyl group, or a trifluoromethyl group.

3. The negative resist composition as described in claim 1, characterized in that, The content of the aromatic compound (Z) is 0.5 to 30 parts by mass relative to 100 parts by mass of the polymer compound (A1).

4. A method for forming a resist pattern, characterized in that, The method comprises a step of forming a resist film on a support using the negative resist composition according to any one of claims 1 to 3, a step of exposing the resist film, and a step of developing the exposed resist film to form a resist pattern.

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