Resist composition and resist pattern forming method

Abstract

A resist composition containing: a high molecular compound (A1) having a structural unit (a10) containing a phenolic hydroxyl group; an acid generator (B); at least one crosslinking agent (C) selected from the group consisting of a melamine-based crosslinking agent, a urea-based crosslinking agent, an alkylene urea-based crosslinking agent, a glycol urea-based crosslinking agent, and an epoxy-based crosslinking agent; and a polyether compound (Z) in an amount of less than 50 parts by mass with respect to 100 parts by mass of the high molecular compound (A1).

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. 2020-211619 filed in Japan on December 21, 2020, 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 (energy) of the exposure light source is shortened.

[0004] For resist materials, photolithographic properties such as sensitivity relative to these exposure light sources and resolution capable of reproducing micro-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 micro-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, the unexposed areas of the resist film form a positive pattern with pattern residue.

[0009] Furthermore, as resist materials, conventionally used chemically amplified resist compositions have included 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. In these chemically amplified resist compositions, for example, when acid is generated by the acid-generating agent component upon exposure, the 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 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 remains soluble in alkaline developer without change. 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 have conducted in-depth research and found that when wet etching is performed using a resist composition that employs an alkali-soluble polyhydroxystyrene resin as a substrate component to form a micron-sized thick resist film and a resist pattern, the wet etching resistance is sometimes insufficient.

[0016] On the other hand, when forming a micron-scale thick resist film by using a resist composition with phenolic varnish resin as a base material to form a resist pattern, there is a problem of insufficient resolution.

[0017] 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 resolution and wet etching resistance, and a method for forming a resist pattern using the resist composition.

[0018] Solution to the above technical problems

[0019] To solve the above-mentioned technical problems, the present invention adopts the following structure.

[0020] That is, the first aspect of the present invention is a resist composition comprising: a polymeric compound (A1) having a structural unit (a10) represented by the following general formula (a10-1), an acid-producing agent (B), at least one crosslinking agent (C) selected from the group consisting of melamine crosslinking agents, urea crosslinking agents, alkylene urea crosslinking agents, glycourea crosslinking agents and epoxy crosslinking agents, and a polyether compound (Z), wherein the content of the polyether compound (Z) is less than 50 parts by mass relative to 100 parts by mass of the polymeric compound (A1).

[0021] [Chemistry 1]

[0022]

[0023] [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.

[0024] 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 described above; a step of exposing the resist film; and a step of developing the exposed resist film to form a resist pattern.

[0025] Invention Effects

[0026] According to the present invention, a resist composition capable of forming a resist pattern with good resolution and wet etching resistance, and a method for forming a resist pattern using the resist composition are provided. Detailed Implementation

[0027] In this specification and claims, "aliphatic" is a relative concept compared to aromatic, and is defined as a group, compound, etc. that does not have aromatic properties.

[0028] Unless otherwise specified, "alkyl" includes straight-chain, branched, and cyclic monovalent saturated hydrocarbon groups. The same applies to alkyl groups in alkoxy groups.

[0029] Unless otherwise specified, "alkylene" includes straight-chain, branched, and cyclic divalent saturated hydrocarbon groups.

[0030] Examples of "halogen atoms" include fluorine, chlorine, bromine, and iodine atoms. "Structural unit" refers to the monomer unit (monomer unit) that constitutes a polymer compound (resin, polymer, copolymer).

[0031] 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.

[0032] "Exposure" refers to the concept of exposure to all types of radiation.

[0033] "Acid-decomposable group" is a group whose structure has at least some of the bonds that can be broken under the action of acid.

[0034] 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.

[0035] Examples of polar groups include carboxyl, hydroxyl, amino, and sulfonic acid groups (-SO3H).

[0036] More specifically, examples of acid-dissociable groups include groups obtained by protecting the polar group with an acid-dissociable group (e.g., groups obtained by protecting the hydrogen atom of an OH-containing polar group with an acid-dissociable group).

[0037] "Acid-dissociable group" refers to either of the following: (i) an acid-dissociable group in which the bond between the acid-dissociable group and the atom adjacent to the acid-dissociable group can be broken by the action of an acid; or (ii) a group in which a portion of the bond is broken by the action of an acid, and further decarboxylation occurs, thereby allowing the bond between the acid-dissociable group and the atom adjacent to the acid-dissociable group to be broken.

[0038] The acid-dissociating groups that constitute the acid-dissociating groups must be of lower polarity than the polar groups generated by the dissociation of these acid-dissociating groups. Therefore, when these acid-dissociating groups dissociate under the action of acid, polar groups of higher polarity 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.

[0039] "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).

[0040] "Derived structural units" refer to structural units formed by the breaking of multiple bonds between carbon atoms, such as alkene double bonds.

[0041] 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.

[0042] 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.

[0043] "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.

[0044] As a substituent for the hydrogen atom at the α-position of hydroxystyrene, examples include R αx The same group.

[0045] In this specification and claims, 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 may be used alone or as mixtures.

[0046] (Resistant Composition)

[0047] The resist composition of the first embodiment of the present invention comprises: a polymeric compound (A1) having a structural unit (a10) represented by the general formula (a10-1) (hereinafter also referred to as "(A1) component"), an acid-generating agent (B) (hereinafter also referred to as "(B) component"), at least one crosslinking agent (C) selected from the group consisting of melamine crosslinking agents, urea crosslinking agents, alkylene urea crosslinking agents, glycourea crosslinking agents, and epoxy crosslinking agents (hereinafter also referred to as "(C) component"), and a polyether compound (Z). In the resist composition of this embodiment, the content of component (Z) is less than 50 parts by mass relative to 100 parts by mass of component (A1).

[0048] If the above-described resist composition is used to form a resist film, a thick resist film (e.g., a film thickness of 1 μm or more) can be formed.

[0049] If a resist film is formed using the above-described resist composition and then selectively exposed, acid is generated in the exposed portions of the resist film. The solubility of component (A) relative to the developer changes due to the action of this acid. Conversely, in the unexposed portions of the resist film, the solubility of component (A) relative to the developer does not change. Therefore, a difference in solubility relative to the developer arises between the exposed and unexposed portions of the resist film. Consequently, if the resist film is developed, when the resist composition is positive, the exposed portions of the resist film are dissolved and removed, thereby forming a positive resist pattern. When the resist composition is negative, the unexposed portions of the resist film are dissolved and removed, thereby forming a negative resist pattern.

[0050] 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 can be either a positive or a negative resist composition. Furthermore, the resist composition of this embodiment can be used in an alkaline developing process where an alkaline developer is used in the developing process during resist pattern formation, or in a solvent developing process where a developer containing an organic solvent (organic developer) is used in the developing process.

[0051] <(A)Component>

[0052] (A) The composition refers to the substrate components whose solubility in the developer changes due to the action of acid.

[0053] 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.

[0054] Organic compounds used as base material components are broadly classified into non-polymers and polymers.

[0055] 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).

[0056] 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.

[0057] If a resist film is formed using a resist composition containing at least component (A1), and this resist film is selectively exposed, then in the exposed portion of the resist film, for example, if the resist composition contains component (B), acid is generated by component (B). Through the action of this acid, cross-linking occurs between components (A1) via cross-linking structural units (a10). 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 unexposed portion of the resist film remains soluble in alkaline developer without change. Therefore, by developing with alkaline developer, a negative resist pattern can be formed.

[0058] Regarding component (A1)

[0059] (A1) is a polymeric compound having a structural unit (a10) represented by the general formula (a10-1).

[0060] As component (A1), a copolymer is preferred that, in addition to structural unit (a10), further has structural unit (a11) containing aromatic rings (excluding aromatic rings bonded with hydroxyl groups) in the side chain.

[0061] In addition, the (A1) component may also have other structural units besides structural unit (a10) and structural unit (a11).

[0062] Regarding structural unit (a10):

[0063] The structural unit (a10) is a structural unit represented by the following general formula (a10-1).

[0064] [Chemistry 2]

[0065]

[0066] [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.

[0067] [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.

[0068] 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.

[0069] 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 of such alkyl groups include methyl, ethyl, propyl, isopropyl, n-butyl, isobutyl, tert-butyl, pentyl, isopentyl, neopentyl, etc.

[0070] 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 aforementioned alkyl halogroup having 1 to 5 carbon atoms with halogen atoms. Fluorine atoms are particularly preferred as the halogen atom.

[0071] 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 preferably a hydrogen atom, a methyl group, or a trifluoromethyl group, and even more preferably a hydrogen atom or a methyl group, and particularly preferably a hydrogen atom.

[0072] In the aforementioned formula (a10-1), Ya x1 It is a single bond or a divalent linker.

[0073] In the chemical formula, Ya is used as... x1 The divalent linking group is not particularly limited, but examples of preferred linking groups include divalent hydrocarbon groups with substituents and divalent linking groups containing heteroatoms.

[0074] • Divalent hydrocarbon groups that may have substituents:

[0075] 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.

[0076] ··Ya x1 aliphatic hydrocarbon groups

[0077] 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.

[0078] ...straight-chain or branched aliphatic hydrocarbon groups

[0079] 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.

[0080] As a straight-chain aliphatic hydrocarbon group, a straight-chain alkylene group is preferred, specifically examples of methylene [-CH2-], ethylene [-(CH2)2-], propylene [-(CH2)3-], butylene [-(CH2)4-], pentylene [-(CH2)5-], etc.

[0081] 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.

[0082] As branched aliphatic hydrocarbon groups, branched alkylene groups are 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-. As for the alkyl group in the alkylalkylene group, a straight-chain alkyl group having 1 to 5 carbon atoms is preferred.

[0083] 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.

[0084] ...aliphatic hydrocarbon groups containing rings in their structure

[0085] Examples of aliphatic hydrocarbon groups containing a ring in the structure include cyclic aliphatic hydrocarbon groups (groups obtained by removing two hydrogen atoms from an aliphatic hydrocarbon ring) that contain substituents including heteroatoms in the ring structure, groups obtained by bonding the cyclic aliphatic hydrocarbon group to the end of a straight-chain or branched aliphatic hydrocarbon group, and groups in which the cyclic aliphatic hydrocarbon group is intermediate between a straight-chain or branched aliphatic hydrocarbon groups. Examples of straight-chain or branched aliphatic hydrocarbon groups are the same aliphatic hydrocarbon groups as described above.

[0086] The cyclic aliphatic hydrocarbon group preferably has 3 to 20 carbon atoms, more preferably 3 to 12 carbon atoms.

[0087] The cyclic aliphatic hydrocarbon group can be either a polycyclic or 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.

[0088] 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.

[0089] 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.

[0090] 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.

[0091] The halogen atom used as the substituent is preferably a fluorine atom.

[0092] 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.

[0093] In cyclic aliphatic hydrocarbon groups, some carbon atoms constituting the ring structure can also be replaced by substituents containing heteroatoms. Preferred substituents containing heteroatoms are -O-, -C(=O)-O-, -S-, -S(=O)2-, and -S(=O)2-O-.

[0094] ··Ya x1 aromatic hydrocarbon groups

[0095] The aromatic hydrocarbon group is a hydrocarbon group having at least one aromatic ring.

[0096] The aromatic ring is not particularly limited to a cyclic conjugated system having 4n+2 π electrons; it can be monocyclic or polycyclic. Preferably, the aromatic ring has 5 to 30 carbon atoms, more preferably 5 to 20, even more preferably 6 to 15, and particularly preferably 6 to 12. This number of carbon atoms does not include the carbon atoms in the substituents.

[0097] Examples of aromatic rings include aromatic hydrocarbon rings such as benzene, naphthalene, anthracene, and phenanthrene; and aromatic heterocycles formed by replacing some 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.

[0098] 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 group (e.g., a group obtained by further removing one hydrogen atom from an aryl group among arylalkyl groups such as benzyl, phenethyl, 1-naphthylmethyl, 2-naphthylmethyl, 1-naphthylethyl, 2-naphthylethyl, etc.). The alkylene group bonded to the aryl or heteroaryl group preferably has 1 to 4 carbon atoms, more preferably 1 to 2 carbon atoms, and particularly preferably 1 carbon atom.

[0099] 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.

[0100] 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.

[0101] The alkoxy, halogen atom, and haloalkyl groups that serve as substituents can be exemplified as substituents replacing hydrogen atoms in the cyclic aliphatic hydrocarbon group.

[0102] • Divalent linking groups containing heteroatoms:

[0103] In Ya x1 In the case of a divalent linking group containing a heteroatom, examples of preferred linking groups include -O-, -C(=O)-O-, -OC(=O)-, -C(=O)-, -OC(=O)-O-, -C(=O)-NH-, -NH-, -NH-C(=NH)- (H may 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 -、-[Y 21 -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 Each can be a divalent hydrocarbon group that can have substituents, where O is an oxygen atom and m” is an integer from 0 to 3, etc.

[0104] 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.

[0105] 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 associated with the Ya group. x1 The same groups (which may have substituents) are listed in the description of the divalent linking groups.

[0106] 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.

[0107] 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.

[0108] With formula - [Y 21 -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.

[0109] 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)-].

[0110] In the aforementioned formula (a10-1), Wa x1 It is an aromatic hydrocarbon group that can have substituents.

[0111] 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. Preferably, the aromatic ring has 5 to 30 carbon atoms, more preferably 5 to 20, even more 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 some carbon atoms of 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.

[0112] In addition, as Wa x1 The aromatic hydrocarbon group in the text can also be cited as an example of the removal of (n) from aromatic compounds containing two or more aromatic rings that may have substituents (e.g., biphenyl, fluorene, etc.). ax1 A group obtained by adding 1+ hydrogen atoms.

[0113] 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 preferred, and more preferably, the group is obtained by removing (n) hydrogen atoms 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.

[0114] Wa x1 The aromatic hydrocarbon group in the form 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 serve as substituents include those used as Ya. x1 The substituent is the same group as the cyclic aliphatic hydrocarbon group exemplified. 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 ethyl or methyl, and particularly preferably methyl. x1 The aromatic hydrocarbon groups in the sample preferably do not have substituents.

[0115] 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.

[0116] The following shows a specific example of the structural unit (a10) represented by the formula (a10-1).

[0117] In the following formulas, R α It represents a hydrogen atom, a methyl group, or a trifluoromethyl group.

[0118] [Chemistry 3]

[0119]

[0120] [Chemistry 4]

[0121]

[0122] [Chemistry 5]

[0123]

[0124] [Chemistry 6]

[0125]

[0126] The structural unit (a10) of component (A1) can be one or more types.

[0127] 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%.

[0128] 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 becomes easier to achieve a balance with other structural units.

[0129] Regarding structural unit (a11):

[0130] The (A1) component is preferably a copolymer that, in addition to the above-mentioned structural unit (a10), further comprises a structural unit (a11) derived from a compound containing an aromatic ring (excluding an aromatic ring bonded with a hydroxyl group) in its side chain.

[0131] As a compound containing an aromatic ring (excluding aromatic rings bonded with hydroxyl groups) in its side chain, a compound represented by the following general formula (a11-1) may be preferably exemplified, for example.

[0132] [Chemistry 7]

[0133]

[0134] In formula (a11-1), Ra x2 It is a group containing a polymerizable group. Wa x2 For (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 To constitute Wa x2 Substituents that replace hydrogen atoms in (aromatic hydrocarbon groups). ax2 Integers between 0 and 3. In n ax2 When the value is 2 or higher, multiple Ra x02 They can bond together to form a ring structure.

[0135] In the aforementioned formula (a11-1), Ra x2 It is a group containing a polymerizable group.

[0136] Ra x2 The 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.

[0137] 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.

[0138] The group containing the polymerizable group can be a group consisting solely of the polymerizable group, or a group consisting of the polymerizable group and other groups besides the polymerizable group. Examples of other groups besides the polymerizable group include divalent hydrocarbon groups that may have substituents and divalent linking groups containing heteroatoms.

[0139] 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, Ya x0 It is a divalent linker.

[0140] In the above formula (a11-1), Wa x2 For (n ax2 +1) aromatic hydrocarbon groups, such as Wa in (a10-1) above, can be cited as examples. x1 Same group.

[0141] Among them, it can also be Ra x2 With Wa x2 It forms a fused ring structure.

[0142] 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, forming the (A1) component backbone. That is, a portion of the carbon atoms constituting the fused ring form the (A1) component backbone.

[0143] In the above equation (a11-1), Ra x02 To constitute Wa x2 Substituents that replace hydrogen atoms in (aromatic hydrocarbon groups).

[0144] As Ra x02 Substituents in the group can be, for example, alkyl, alkoxy, acyloxy, etc.

[0145] 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.

[0146] 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.

[0147] As Ra x02 The acyloxy group of the substituent is preferably 2 to 6 carbons, more preferably CH3C(=O)-O-(acetoxy) or C2H5C(=O)-O-, and particularly preferably CH3C(=O)-O-(acetoxy).

[0148] In the above formula (a11-1), n ax2 It is an integer from 0 to 3, preferably 0, 1 or 2, and more preferably 0 or 1.

[0149] In n ax2 When the value is 2 or higher, multiple Ra x02 They can bond with each other to form ring structures. The ring structures formed can be hydrocarbon rings or heterocycles. For example, a ring structure formed by bonding with Wa... x2 Two Ra molecules bonded to the same aromatic ring in 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.

[0150] 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.

[0151] [Chemistry 8]

[0152]

[0153] [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 Integers between 0 and 3. In n ax2 When the value is 2 or higher, multiple R β They can bond together to form a ring structure. 21 n 22 n 24 and n 25 Each can be 0 or 1 independently. 23 and n 26 Each can be independently represented as 1 or 2.

[0154] In the above formulas (a11-u1-1) to (a11-u1-6), R β The alkyl, alkoxy, and acyloxy groups in the above formula (a11-1) are Ra. x02 The alkyl, alkoxy, and acyloxy groups exemplified are the same as the substituents in the example.

[0155] The following are specific examples of structural units (structural units (a11)) derived from compounds represented by the general formula (a11-1).

[0156] In the following formulas, R α It represents a hydrogen atom, a methyl group, or a trifluoromethyl group.

[0157] [Chemistry 9]

[0158]

[0159] [Chemistry 10]

[0160]

[0161] [Chemistry 11]

[0162]

[0163] [Chemistry 12]

[0164]

[0165] [Chemistry 13]

[0166]

[0167] In the above examples, the structural unit (a11) is preferably selected from at least one type 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).

[0168] Among these, 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).

[0169] The structural unit (a11) of component (A1) can be one or more types.

[0170] 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%.

[0171] By setting the proportion of the structural unit (a11) above the lower limit, the etch resistance and photolithography properties are further improved. On the other hand, by setting it below the upper limit, it becomes easier to achieve a balance with other structural units.

[0172] Other Structural Units

[0173] The (A1) component may also have other structural units besides structural units (a10) and structural units (a11).

[0174] 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-hydroxyethyl methacrylate. Esters, such as 2-hydroxypropyl methacrylate and other hydroxyalkyl methacrylates; phenyl methacrylate, such as 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.

[0175] In the resist composition of this embodiment, component (A) comprises a polymeric compound (A1) having a structural unit (a10) ((A1) component).

[0176] 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 a repeating structure of structural unit (a10) and structural unit (a11).

[0177] 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.

[0178] 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.

[0179] 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.

[0180] The (A1) component can be manufactured by dissolving the monomers from which the structural units are derived in a polymerization solvent, and then adding a free radical polymerization initiator such as azobisisobutyronitrile (AIBN) or dimethyl azobisisobutyrate (e.g., V-601) to the solvent for polymerization.

[0181] 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, adding the free radical polymerization initiator as described above to perform polymerization, followed by a deprotection reaction.

[0182] 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 with hydroxyalkyl groups in which some hydrogen atoms of the alkyl group are replaced by fluorine atoms are effective in reducing development defects and LER (line edge roughness: unevenness of the line sidewalls).

[0183] In addition, component (A1) can also be manufactured by anionic polymerization using organoalkali metals such as n-butyllithium, sec-butyllithium, tert-butyllithium, ethyllithium, sodium ethyl, 1,1-diphenylhexyllithium, and 1,1-diphenyl-3-methylpentyllithium as polymerization initiators.

[0184] Regarding ingredient (A2)

[0185] 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).

[0186] As for component (A2), there are no particular limitations, and any component that has been known as a base material component for chemically amplified resist compositions may be selected and used.

[0187] (A2) Components can be a single high molecular weight compound or a low molecular weight compound, or a combination of two or more.

[0188] The proportion of component (A1) in component (A) relative to the total mass of component (A) is preferably 25% by mass or more, more preferably 50% by mass or more, even more preferably 75% by mass or more, and may also be 100% by mass. If this proportion is 25% by mass or more, it is easy to form resist patterns with excellent photolithographic properties such as high sensitivity, resolution, and improved roughness.

[0189] In the resist composition of this embodiment, the content of component (A) can be adjusted according to the desired resist film thickness, etc.

[0190] Acid-generating component (B)

[0191] As component (B), there are no particular limitations, and any acid-generating agent proposed so far as to be used in chemically amplified resist compositions can be used.

[0192] In this embodiment, as component (B), it is preferable to include an acid-producing agent (B0) represented by the following general formula (b0-1) (hereinafter referred to as "(B0) component").

[0193] Regarding ingredient (B0)

[0194] (B0) is an acid-producing agent represented by the following general formula (b0-1).

[0195] [Chemistry 14]

[0196]

[0197] [In the formula, Rb] 1 It is an organic group. Rb 2 This refers to a group represented by the following general formula (b0-r-1) or the following general formula (b0-r-2).

[0198] [Chemistry 15]

[0199]

[0200] In the formula (b0-r-1), Rb 201 and Rb 202 Each is an independent organic group. * indicates a chemical 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 chemical bond.

[0201] In this embodiment, the (B0) component is not particularly limited as long as it is a compound represented by the above 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.

[0202] [Chemistry 16]

[0203]

[0204] [In the formula, Rb] 11 and Rb 21 Each is an independent non-aromatic group.

[0205] [Chemistry 17]

[0206]

[0207] [In the formula, Rb] 12 It is an alkyl or haloalkyl group. Rb 22 It is an aromatic functional group.

[0208] [Chemistry 18]

[0209]

[0210] [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.

[0211] [Chemistry 19]

[0212]

[0213] [In the formula, Rb] 14 Rb is an aromatic polycyclic hydrocarbon group, a saturated or unsaturated non-aromatic polycyclic hydrocarbon group, or a substituted derivative thereof. 24 It is an inert organic group.

[0214] [Chemistry 20]

[0215]

[0216] [In the formula, Rb] 15 Xb is a monovalent saturated hydrocarbon group, unsaturated hydrocarbon group, or aromatic group, whether substituted or unsubstituted. 5 [A group that, together with -(O=)CNC(=O)-, forms a cyclic group having a cyclic imide structure.]

[0217] [Chemistry 21]

[0218]

[0219] [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 263Each 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.

[0220] 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.

[0221] 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.

[0222] As Rb 11 and Rb 12 The number of halogen atoms in the alkyl halide is not particularly limited; one or more halogen atoms can be introduced. Furthermore, the halogen atom can be any of fluorine, chlorine, bromine, or iodine. Preferably, the alkyl halide has 1 to 4 carbon atoms, such as chloromethyl, trichloromethyl, trifluoromethyl, or 2-bromopropyl.

[0223] 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.

[0224] 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.

[0225] 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.

[0226] 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.

[0227] In the above equation (b0-1-1), Rb 11Alkyl, 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.

[0228] Specific examples of compounds represented by the above 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.

[0229] In the above equation (b0-1-2), Rb 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.

[0230] As Rb 12 The haloalkyl group in the text can be exemplified by haloalkyl groups having 1 to 4 carbon atoms, such as chloromethyl, trichloromethyl, trifluoromethyl, 2-bromopropyl, etc.

[0231] In the above formula (b0-1-2), Rb 22 In Rb, aromatic groups refer to groups that indicate the physical and chemical properties characteristic of aromatic compounds; examples include phenyl, naphthyl, furanyl, and thiophene groups. 22 In the aromatic group, some of the hydrogen atoms in the aromatic ring constituting the aromatic group can also be replaced by substituents. Examples of such substituents include halogen atoms, alkyl groups, alkoxy groups, and nitro groups.

[0232] Specifically, examples of compounds represented by the above 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.

[0233] In the above equation (b0-1-3), Rb 13 The hydrocarbon group in the formula can be either aromatic or non-aromatic. Here, as an aromatic group, an aromatic group with 6 to 14 carbon atoms is preferred, such as phenyl, tolyl, methoxyphenyl, xylyl, biphenyl, naphthyl, anthracene, and other aromatic hydrocarbon groups, as well as heterocyclic groups such as furanyl, pyridyl, and quinolinyl. Furthermore, among the non-aromatic hydrocarbon groups, there are hydrocarbon groups that do not have aromatic rings such as benzene, naphthyl, furanyl, thiophene, or pyridyl rings, such as aliphatic hydrocarbon groups and alicyclic hydrocarbon groups such as alkyl, alkenyl, cycloalkyl, and cycloalkenyl. The alkyl and alkenyl groups can be either straight-chain or branched, and alkyl and alkenyl groups with 1 to 12 carbon atoms are preferred. Furthermore, cycloalkyl and cycloalkenyl groups with 4 to 12 carbon atoms are preferred. 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.

[0234] In the above equation (b0-1-3), Rb 13 The hydrocarbon group in the hydrocarbon can have substituents. Examples of such substituents include halogen atoms, hydroxyl groups, alkoxy groups, and acyl groups.

[0235] In the above formula (b0-1-3), examples of divalent or trivalent organic groups in Ab include aliphatic hydrocarbon groups and aromatic hydrocarbon groups.

[0236] Specific examples of compounds represented by the above formula (b0-1-3) are shown below.

[0237] [Chemistry 22]

[0238]

[0239] [Chemistry 23]

[0240]

[0241] In the above equation (b0-1-4), Rb 14 Aromatic polycyclic hydrocarbon groups, such as fused aromatic polycyclic hydrocarbon groups like 2-indenyl, 1-naphthyl, 2-naphthyl, and 2-anthrayl, and non-fused aromatic polycyclic hydrocarbon groups like biphenyl and terphenyl. Furthermore, as substituted derivative groups, examples include groups obtained by substituting the aromatic ring of these groups with halogen atoms such as chlorine, bromine, and iodine, or with substituents such as nitro, amino, hydroxyl, alkyl, and alkoxy groups, such as 5-hydroxy-1-naphthyl and 4-amino-1-naphthyl.

[0242] In the above equation (b0-1-4), Rb 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.

[0243] As the Rb 14 Naphthyl and camphor-10-yl are preferred, with 1-naphthyl being particularly preferred due to its excellent resolution.

[0244] In the above formula (b0-1-4), Rb 24 The inert organic group refers to an organic group that is inert to the coexisting components under the conditions of use. There are no particular restrictions, but from the viewpoint of sensitivity to excimer lasers, electron beams, and X-rays, aromatic groups are preferred. Examples of such aromatic groups include phenyl, naphthyl, furanyl, and thiophene. In addition, these aromatic groups may have inert substituents such as halogen atoms (such as chlorine, bromine, and iodine atoms), alkyl, alkoxy, and nitro groups.

[0245] Specific examples of compounds represented by the above 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, and α-(3-bromo-10-camphorsulfonyloxyimino)-4-methoxybenzyl cyanide.

[0246] In the above equation (b0-1-5), Rb 15 The substituted or unsubstituted monovalent saturated or unsaturated hydrocarbon groups in the Rb group include, 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 to be a group obtained by substituting vinyl, alkyl, alkoxy, halogen atom, etc., into the benzene ring.

[0247] In the above equation (b0-1-5), Xb 5 Cyclic groups that form cyclic imide structures together with -(O=)CNC(=O)- include, for example, 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.

[0248] Specific examples of compounds represented by the above 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. The compounds described in paragraphs

[0089] -

[0091] of Japanese Patent Application Publication No. 10-097075 include: 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 the compounds described in paragraphs

[0089] -

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

[0249] 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, and 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, cyclododecyl, etc.

[0250] 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.

[0251] 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.

[0252] In the above equation (b0-1-6), Rb 16 Aromatic hydrocarbon groups in Rb can be exemplified by phenyl, naphthyl, phenanthryl, anthracene, and heteroaryl groups. 16The aromatic hydrocarbon group in the atom can have substituents. Examples of such substituents include halogen atoms, haloalkyl groups, CN, NO2, phenyl, alkoxy, carboxyl, carbonyl, sulfonyl, and amino groups.

[0253] Specific examples of compounds represented by the above 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.

[0254] [Chemistry 24]

[0255]

[0256] 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] ,

[0060] -

[0062] of Japanese Patent No. 4000469.

[0257] As component (B0), 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), 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).

[0258] Furthermore, from the viewpoint of balancing sensitivity and resolution, compounds represented by the above formula (b0-1-2) and / or compounds represented by the above formula (b0-1-3) and compounds represented by the above formula (b0-1-6) are preferred.

[0259] The following are preferred examples of component (B0).

[0260] [Chemistry 25]

[0261]

[0262] The (BO) component contained in the resist composition of this embodiment can be used alone or in combination with two or more components.

[0263] 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.

[0264] By setting the content of the (B0) component within the above range, pattern formation can be fully achieved.

[0265] Regarding ingredient (B1)

[0266] The resist composition of this embodiment may also contain an acid-generating agent (hereinafter also referred to as "(B1) component") other than component (B0) as component (B) component.

[0267] As component (B1), there are no particular limitations, and any acid-generating agent proposed so far as an acid-generating agent for chemically amplified resist compositions can be used.

[0268] 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.

[0269] 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").

[0270] [Chemistry 26]

[0271]

[0272] [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 and R 103 Each of the following is independently a hydrogen atom, an alkyl group having 1 to 5 carbon atoms, a fluorine atom, or a fluoroalkyl group having 1 to 5 carbon atoms. nb is 0 or 1. Y 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 ~L102 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.

[0273] In the above equation (b-1), R 101 Preferably, the cyclic group can have substituents, and more preferably, the cyclic hydrocarbon group can have substituents. More specifically, phenyl, naphthyl, groups obtained by removing one or more hydrogen atoms from polycyclic alkanes; groups obtained by removing one or more hydrogen atoms from camphor; lactone-containing cyclic groups represented by the above general formulas (a2-r-1), (a2-r-3) to (a2-r-7), respectively; and -SO2-containing cyclic groups represented by the above general formulas (a5-r-1) to (a5-r-4), respectively (any group can have substituents).

[0274] In the above equation (b-1), Y is... 101 Preferably, it is a single bond, a divalent linker containing an ester bond, or a divalent linker containing an ether bond.

[0275] In the above equation (b-1), V 101 Preferably, it is a single bond or a fluoroalkylene group having 1 to 4 carbon atoms.

[0276] In the above equation (b-1), R 102 It is a perfluoroalkyl group consisting of hydrogen atoms, fluorine atoms, or carbon atoms from 1 to 5.

[0277] In the above equation (b-2), R 104 R 105 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) above. 101 Same group. Wherein, R 104 R 105 They can bond together to form a ring.

[0278] 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.

[0279] 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 Same group.

[0280] In equation (b-2), L101 L 102 Each can be a single bond or an oxygen atom, independently.

[0281] 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 Same group.

[0282] L 103 ~L 105 Each can be a single bond, -CO-, or -SO2-, respectively.

[0283] In the above equations (b-1), (b-2), and (b-3), m is an integer greater than or equal to 1, and M' m+ The onion cation is m-valent, preferably sulfonium cation or iodoonium cation.

[0284] In the resist composition of this embodiment, component (B1) can be used alone or in combination with two or more components.

[0285] 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.

[0286] In the resist composition of this embodiment, component (B) can be used alone or in combination with two or more components.

[0287] In the resist composition of this embodiment, the content of component (B) relative to 100 parts by mass of component (A) is preferably less than 50 parts by mass, more preferably 0.1 to 40 parts by mass, and even more preferably 0.3 to 25 parts by mass.

[0288] By setting the content of component (B) within the aforementioned preferred range, pattern formation can be sufficiently achieved. Furthermore, when the components of the resist composition are dissolved in an organic solvent, a homogeneous solution is readily obtained, resulting in good storage stability of the resist composition, which is therefore preferred.

[0289] <(C) Ingredients>

[0290] (C) is at least one crosslinking agent selected from the group consisting of melamine crosslinking agents, urea crosslinking agents, alkylene urea crosslinking agents, glycourea crosslinking agents and epoxy crosslinking agents.

[0291] Examples of melamine-based crosslinking agents include compounds obtained by reacting melamine with formaldehyde and replacing the hydrogen atom of the amino group with a hydroxymethyl group; and compounds obtained by reacting melamine, formaldehyde, and a lower alcohol and replacing the hydrogen atom of the amino group with a lower alkoxymethyl group. Specifically, examples include hexamethoxymethyl melamine, hexaethoxymethyl melamine, hexapropoxymethyl melamine, and hexabutoxybutyl melamine, with hexamethoxymethyl melamine being preferred.

[0292] Examples of urea crosslinking agents include compounds obtained by reacting urea with formaldehyde and replacing the hydrogen atom of the amino group with a hydroxymethyl group; and compounds obtained by reacting urea, formaldehyde, and a lower alcohol and replacing the hydrogen atom of the amino group with a lower alkoxymethyl group. Specifically, examples include dimethoxymethyl urea, diethoxymethyl urea, dipropoxymethyl urea, and dibutoxymethyl urea, with dimethoxymethyl urea being preferred.

[0293] Examples of alkylene urea crosslinking agents include compounds represented by the following general formula (CA-1).

[0294] [Chemistry 27]

[0295]

[0296] In formula (CA-1), Rc 1 With Rc 2 Rc is independently a hydroxyl or lower alkoxy group. 3 With Rc 4 Each of these can be independently a hydrogen atom, a hydroxyl group, or a lower alkoxy group, and vc is an integer from 0 to 2.

[0297] In Rc 1 With Rc 2 When the alkoxy group is a lower alkoxy group, it is preferably an alkoxy group with 1 to 4 carbon atoms, and it can be either straight-chain or branched. Rc 1 With Rc 2 They can be the same or different from each other. It is preferred that they are the same.

[0298] In Rc 3 With Rc 4 When the alkoxy group is a lower alkoxy group, it is preferably an alkoxy group with 1 to 4 carbon atoms, and it can be either straight-chain or branched. Rc 3 With Rc 4 They can be the same or different from each other. It is preferred that they are the same.

[0299] vc is an integer from 0 to 2, preferably 0 or 1.

[0300] As alkylene urea crosslinking agents, compounds with a VC of 0 (ethylene urea crosslinking agents) and / or compounds with a VC of 1 (propylene urea crosslinking agents) are particularly preferred.

[0301] The compound represented by the above general formula (CA-1) can be obtained by condensing alkylene urea with formalin and reacting the product with a lower alcohol.

[0302] Specific examples of alkylene urea crosslinking agents include, for instance, ethylene urea crosslinking agents such as mono- and / or dihydroxymethylated ethylene urea, mono- and / or dimethoxymethylated ethylene urea, mono- and / or diethoxymethylated ethylene urea, mono- and / or dipropoxymethylated ethylene urea, and mono- and / or dibutoxymethylated ethylene urea; propylene urea crosslinking agents such as mono- and / or dihydroxymethylated propylene urea, mono- and / or dimethoxymethylated propylene urea, mono- and / or diethoxymethylated propylene urea, mono- and / or dipropoxymethylated propylene urea, and mono- and / or dibutoxymethylated propylene urea; and 1,3-di(methoxymethyl)4,5-dihydroxy-2-imidazolinone, 1,3-di(methoxymethyl)-4,5-dimethoxy-2-imidazolinone, etc.

[0303] Examples of glycourea crosslinking agents include glycourea derivatives obtained by substituting one or both of a hydroxyl alkyl group and an alkoxy alkyl group having 1 to 4 carbon atoms at the N-position. Such glycourea derivatives can be obtained by condensing glycourea with formalin and then reacting the product with a lower alcohol.

[0304] Specific examples of glycourea crosslinking agents include mono-, di-, tri-, and / or tetra-hydroxymethylated glycourea; mono-, di-, tri-, and / or tetra-methoxymethylated glycourea; mono-, di-, tri-, and / or tetra-ethoxymethylated glycourea; mono-, di-, tri-, and / or tetra-propoxymethylated glycourea; and mono-, di-, tri-, and / or tetra-butoxymethylated glycourea.

[0305] As an epoxy crosslinking agent, any crosslinking agent containing epoxy groups is acceptable; there are no particular limitations, and any choice can be made. However, it is preferable to have two or more epoxy groups. Having two or more epoxy groups improves the crosslinking reactivity.

[0306] The number of epoxy groups is preferably two or more, more preferably two to four, and most preferably two.

[0307] The following are preferred substances as epoxy crosslinking agents.

[0308] [Chemistry 28]

[0309]

[0310] As component (C), a crosslinking agent having a -NCH2-OCH3 group is preferred, more preferably a crosslinking agent selected from the group consisting of compounds represented by formula (c1-1) or (c1-2) and mono-, di-, tri- and / or tetra-methoxymethylated glycoureas, and even more preferably a crosslinking agent selected from the group consisting of compounds represented by formula (c1-1) or (c1-2) and having a melamine backbone, and mono-, di-, tri- and / or tetra-methoxymethylated glycoureas.

[0311] [Chemistry 29]

[0312]

[0313] [In the formula, nc1 and nc2 are independent integers from 1 to 3.]

[0314] (C) Component can be used alone or in combination of two or more. 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.

[0315] If the content of component (C) is above the lower limit, cross-linking formation proceeds sufficiently, further improving resolution performance and photolithography characteristics. Furthermore, a good resist pattern with less swelling can be obtained. Conversely, if the content is below the upper limit, the resist composition exhibits good storage stability and becomes easier to suppress the deterioration of sensitivity over time.

[0316] <(Z) component>

[0317] (Z) The component is not particularly limited as long as it is a polyether compound, and examples include compounds with local structures represented by the following general formula (z-1).

[0318] [Chemistry 30]

[0319]

[0320] [In the formula, Rz] 11 It is an alkylene group that may have substituents. nz is an integer greater than or equal to 1.

[0321] In the above general formula (z-1), Rz 11 This refers to an alkylene group that may have substituents. The number of carbon atoms in the alkylene group is not particularly limited, but is preferably 1 to 15, more preferably 2 to 8, and even more preferably 2 to 4. The substituents are not particularly limited, but are preferably alkyl groups (preferably with 1 to 10 carbon atoms).

[0322] In the above general formula (z-1), * represents a chemical bond.

[0323] The mass-average molecular weight (Mw) of the compound represented by general formula (z-1) (based on polystyrene conversion standard by gel permeation chromatography (GPC)) is preferably 200 to 25,000, more preferably 250 to 24,000, and even more preferably 300 to 23,000.

[0324] As component (Z), it is preferably a compound represented by the following general formula (z-1-1).

[0325] [Chemistry 31]

[0326]

[0327] [In the formula, Rz] 11 It is an alkylene group that can have substituents. Rz 12 and Rz 13 Each can be an independent hydrogen atom or an alkyl group. nz is an integer greater than or equal to 1.

[0328] Rz in the above general formula (z-1-1) 11 The definition, specific examples, and preferred solutions are related to Rz in the above general formula (1). 11 same.

[0329] In the above general formula (z-1-1), Rz 12 and Rz 13 Each can be represented independently by a hydrogen atom or an alkyl group. The number of carbon atoms in the alkyl group is not particularly limited, but is preferably 1 to 15. Wherein, as Rz... 12 and Rz 13 Preferably, it contains hydrogen atoms.

[0330] The mass-average molecular weight (Mw) of the compound represented by the general formula (z-1-1) (based on polystyrene conversion standard by gel permeation chromatography (GPC)) is preferably 200 to 25,000, more preferably 250 to 24,000, and even more preferably 300 to 23,000.

[0331] As component (Z), more preferably, it is selected from at least one of the following groups: compounds represented by the following general formula (z-1-11), compounds represented by the following general formula (z-1-12), and compounds represented by the following general formula (z-1-13).

[0332] [Chemistry 32]

[0333]

[0334] [Chemistry 33]

[0335]

[0336] [Chemistry 34]

[0337]

[0338] The mass-average molecular weight (Mw) of (Z) (based on polystyrene conversion from gel permeation chromatography (GPC)) is preferably 200 to 25,000, more preferably 250 to 24,000, and even more preferably 300 to 23,000. If the mass-average molecular weight (Mw) of (Z) is above the lower limit of the above-mentioned preferred range, it is easy to form a pattern with good wet etching resistance. On the other hand, if the mass-average molecular weight (Mw) of (Z) is below the upper limit of the above-mentioned preferred range, the solubility of the resist film relative to the developer becomes good, and it is easy to form a pattern with good resolution.

[0339] The (Z) component contained in the resist composition of this embodiment can be used alone or in combination with two or more components.

[0340] In the resist composition of this embodiment, the content of component (Z) is less than 50 parts by mass relative to 100 parts by mass of component (A1), preferably 40 parts by mass or less, more preferably 35 parts by mass or less, even more preferably 30 parts by mass or less, and even more preferably less than 20 parts by mass.

[0341] There is no particular limitation on the lower limit of the content of component (Z), but it is preferably 0.1 parts by mass or more, more preferably 0.2 parts by mass or more, and even more preferably 0.5 parts by mass or more, relative to 100 parts by mass of component (A1).

[0342] By keeping the content of the (Z) component less than 50 parts by mass, it is possible to form patterns with good resolution and wet etching resistance.

[0343] If the content of component (Z) is below the upper limit of the above preferred range, it is easier to form a pattern with better resolution.

[0344] If the content of component (Z) is above the lower limit of the above preferred range, it is easier to form a pattern with better wet etching resistance.

[0345] <Any ingredient>

[0346] (D) Ingredients

[0347] In addition to components (A), (B), (C), and (Z), the resist composition in this embodiment may further contain an acid diffusion control component (hereinafter referred to as "component (D)"). Component (D) is the component in the resist composition that functions as a quencher (acid diffusion control agent) to capture acid generated by exposure.

[0348] 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 (hereinafter referred to as "(D2) components") that do not belong to the (D1) component.

[0349] By preparing 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.

[0350] Regarding component (D1)

[0351] (D1) is an alkaline component, a nitrogen-containing organic compound that acts as an acid diffusion control agent in the resist composition.

[0352] As a component (D1), there are no particular limitations as long as it functions as an acid diffusion control agent, such as aliphatic amines and aromatic amines.

[0353] Among them, aliphatic amines are preferably secondary aliphatic amines or tertiary aliphatic amines.

[0354] Aliphatic amines are amines having one or more aliphatic groups, preferably having 1 to 12 carbon atoms.

[0355] Examples of aliphatic amines include amines (alkylamines or alkylolamines) obtained by replacing at least one hydrogen atom of ammonia NH3 with an alkyl or hydroxyalkyl group having 12 or fewer carbon atoms, or cyclic amines.

[0356] 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-nonylamine, tri-n-decylamine, and tri-n-dodecylamine; and alkylolamines such as diethanolamine, triethanolamine, diisopropanolamine, triisopropanolamine, di-n-octanolamine, and tri-n-octanolamine. Among these, trialkylamines with 5 to 10 carbon atoms are further preferred, and tri-n-pentylamine or tri-n-octylamine are particularly preferred.

[0357] 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).

[0358] Examples of aliphatic monocyclic amines include piperidine and piperazine. For aliphatic polycyclic amines, those with 6 to 10 carbon atoms are preferred; examples include 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.

[0359] 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.

[0360] Examples of aromatic amines include 4-dimethylaminopyridine, pyrrole, indole, pyrazole, imidazole or their derivatives, tribenzylamine, aniline compounds, n-tert-butoxycarbonylpyrrolidine, etc.

[0361] Component (D1) can be used alone or in combination of two or more. Among the above-mentioned components, aromatic amines are preferred as component (D1), and aniline compounds are more preferred. Examples of aniline compounds include 2,6-diisopropylaniline, N,N-dimethylaniline, N,N-dibutylaniline, and N,N-dihexylaniline.

[0362] Regarding component (D2)

[0363] As the (D2) component, there is no particular limitation as long as the component loses its acid diffusion control through exposure decomposition, but it is preferred to be 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") and compounds represented by the following general formula (d2-2) (hereinafter referred to as "(d2-2) component").

[0364] The components (d2-1) to (d2-2) 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.

[0365] [Chemistry 35]

[0366]

[0367] [In the formula, Rd] 1 、Rd 3 and Rd 4Each 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. 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.

[0368] In equation (d2-1), Rd 1 Preferably, it is an aromatic hydrocarbon group that may have substituents, an aliphatic cyclic group that may have substituents, or a chain alkyl group that may have substituents.

[0369] In equation (d2-2), Rd 3 Preferably, it is a cyclic group containing fluorine atoms, a chain alkyl group, or a chain alkenyl group.

[0370] In equation (d2-2), Rd 4 Preferably, the alkyl, alkoxy, alkenyl, or cyclic groups may have substituents.

[0371] In equation (d2-2), Yd 1 Preferably, it is a carbonyl group, ester bond, amide bond, alkylene group, or a combination thereof.

[0372] In equations (d2-1) to (d2-2), m is an integer greater than or equal to 1, and M' m+ The onion cation is m-valent, preferably sulfonium cation or iodoonium cation.

[0373] Component (D2) can be any one of the components (d2-1) to (d2-2) mentioned above, or it can be a combination of two or more.

[0374] 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.

[0375] 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 with other components can be achieved, and various photolithography properties become good.

[0376] (D2) Manufacturing method:

[0377] The manufacturing method of the above-mentioned (d2-1) component is not particularly limited and can be manufactured by known methods.

[0378] Furthermore, the method of manufacturing component (d2-2) is not particularly limited, for example, it can be manufactured in the same manner as the method described in US 2012-0149916.

[0379] (E) Ingredients: at least one compound selected from the group consisting of organic carboxylic acids and oxyacids of phosphorus and their derivatives.

[0380] 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 oxyacids of phosphorus and their derivatives as an arbitrary component.

[0381] The preferred organic carboxylic acids are, for example, acetic acid, malonic acid, citric acid, malic acid, succinic acid, benzoic acid, and salicylic acid.

[0382] Examples of oxyacids containing phosphorus include phosphoric acid, phosphonic acid, and hypophosphonic acid, among which phosphonic acid is particularly preferred.

[0383] 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.

[0384] Examples of phosphoric acid derivatives include dibutyl phosphate, diphenyl phosphate, and other phosphate esters.

[0385] Examples of phosphonic acid derivatives include dimethyl phosphonate, di-n-butyl phosphonate, phenylphosphonic acid, diphenyl phosphonate, dibenzyl phosphonate, and other phosphonate esters.

[0386] Examples of derivatives of hypophosphonic acid include hypophosphonate esters and phenylhydatilic acid.

[0387] In the resist composition of this embodiment, component (E) can be used alone or in combination with two or more components.

[0388] When the resist composition contains component (E), the content of component (E) is usually used in the range of 0.01 to 5 parts by mass relative to 100 parts by mass of component (A).

[0389] (S) Ingredients: Organic solvents

[0390] 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").

[0391] As component (S), any component that can dissolve the various components used to form a homogeneous solution is acceptable. Any component can be appropriately selected from substances known in the past as solvents for chemically amplified resist compositions.

[0392] 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).

[0393] In the resist composition of this embodiment, component (S) can be used alone or as a mixed solvent of two or more components.

[0394] Among them, PGMEA, PGME, γ-butyrolactone, EL, and cyclohexanone are preferred.

[0395] 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.

[0396] 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.

[0397] 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.

[0398] The amount of component (S) used is not particularly limited, and is appropriately set according to the coating film thickness based on the concentration required to coat the substrate, etc. 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.

[0399] In the resist composition of this embodiment, additives with versatility can be further added as desired, such as additional resins for improving the performance of the resist film, ionic or nonionic fluorinated and / or silicone surfactants, dissolution inhibitors, plasticizers, stabilizers, colorants, anti-halo agents, dyes, etc.

[0400] The resist composition of this embodiment can also remove impurities by dissolving the above-mentioned resist material in component (S) and then 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 porous membrane described in Japanese Patent Application Publication No. 2016-155121.

[0401] The resist composition of the present invention comprises: a polymeric compound (A1) having a structural unit (a10) represented by the general formula (a10-1), an acid-producing agent (B), at least one crosslinking agent (C) selected from the group consisting of melamine crosslinking agents, urea crosslinking agents, alkylene urea crosslinking agents, glycourea crosslinking agents and epoxy crosslinking agents, and a polyether compound (Z).

[0402] The inventors' in-depth research has revealed that when using a resist composition employing an alkali-soluble polyhydroxystyrene resin as a substrate to form a micron-sized thick resist film, and then etching to create a resist pattern, wet etching resistance is sometimes insufficient. This can be attributed to insufficient adhesion between the resist film formed using this resist composition and the substrate interface.

[0403] It is speculated that in the resist composition of this embodiment, component (Z) acts as a plasticizer within the resist film, increasing the contact area between the resist film and the substrate. Therefore, it is speculated that component (A1) readily bonds with polar groups present on the substrate surface, which helps improve substrate adhesion, maintains good resolution, and improves wet etching resistance.

[0404] (Resist Pattern Formation Method)

[0405] The second aspect of the present invention is a method for forming a resist pattern, comprising: a step (i) of forming a resist film on a support using the resist composition of the first aspect described above; a step (ii) of exposing the resist film; and a step (iii) of developing the exposed resist film to form a resist pattern.

[0406] 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.

[0407] Process (i):

[0408] First, the resist composition of the above embodiment is applied to the support using a spin coater or the like. 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.

[0409] Process (ii):

[0410] 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 (post-exposure baking (PEB)) at a temperature of 80 to 150°C, preferably for 60 to 120 seconds.

[0411] Process (iii):

[0412] 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.

[0413] After development, rinsing is preferred. 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.

[0414] In the case of solvent development process, after the above-mentioned development or rinsing treatment, a process can be performed to remove the developer or rinsing solution adhering to the pattern by supercritical fluid.

[0415] Drying is performed after development or rinsing. Alternatively, baking (post-baking) may be performed after the above-mentioned development process, depending on the circumstances. The baking (post-baking) here is performed, for example, at a temperature of 80°C or higher, preferably 90 to 120°C, for 10 to 120 seconds, preferably 300 to 90 seconds.

[0416] In this way, a resist pattern can be formed.

[0417] 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. Materials used for the wiring pattern include, for example, copper, aluminum, nickel, and gold.

[0418] Furthermore, the support can be a substrate on which an inorganic and / or organic film is applied. 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.

[0419] 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 can be formed.

[0420] In the multilayer resist method, it is basically divided into two-layer structure with an upper resist film and a lower organic film (2-layer resist method); and three-layer or more multilayer structure with one or more intermediate layers (such as metal thin film) between the upper resist film and the lower organic film (3-layer resist method).

[0421] The resist patterning method described in this embodiment is useful when forming a thick resist film. Even if the thickness of the resist film formed in the above step (i) is, for example, 1 to 10 μm, a resist pattern can be stably formed with a good shape.

[0422] There are no particular limitations on the wavelengths used in the exposure; radiation such as g-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.

[0423] The resist composition of the first embodiment described above is highly useful for use with g-line, i-line, and other ultraviolet light, KrF excimer lasers, ArF excimer lasers, EB, or EUV; even more useful for use with g-line, i-line, and other ultraviolet light, KrF excimer lasers, and ArF excimer lasers; and particularly useful for use with g-line, i-line, and other ultraviolet light, KrF excimer lasers. The resist patterning method of the second embodiment is a particularly preferred method when the resist film is irradiated with g-line, i-line, and other ultraviolet light, or KrF excimer lasers in step (ii) described above.

[0424] 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.

[0425] Immersion exposure is 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).

[0426] As the immersion medium, a solvent having a refractive index greater than that of air and less than that of the exposed resist film is preferred. There are no particular limitations on the refractive index of the solvent if it falls within the aforementioned range.

[0427] Examples of solvents having 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.

[0428] Water is the preferred immersion medium from the perspectives of cost, safety, environmental issues, and versatility.

[0429] 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).

[0430] The organic solvent contained in the organic developing solution used in solvent-based developing processes can be any organic solvent that can dissolve component (A) (the component (A) before exposure), and can be appropriately selected from known organic solvents. Specifically, examples include polar solvents such as ketone solvents, ester solvents, alcohol solvents, nitrile solvents, amide solvents, ether solvents, and hydrocarbon solvents.

[0431] 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.

[0432] Among organic solvents, there are also organic solvents whose structures contain multiple functional groups that are characteristic of the aforementioned solvents. In this case, the organic solvent simultaneously belongs to any solvent class containing the aforementioned functional groups. For example, diethylene glycol monomethyl ether simultaneously belongs to both alcohol solvents and ether solvents in the above classification.

[0433] 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.

[0434] Among the organic solvents contained in organic developing solutions, polar solvents are preferred, and ketone solvents, ester solvents, and nitrile solvents are also preferred.

[0435] 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, acetone-based acetone, 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.

[0436] Examples of ester solvents include methyl acetate, butyl acetate, ethyl acetate, isopropyl acetate, amyl acetate, isoamyl acetate, ethyl methoxy, ethyl ethoxy, 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.

[0437] Examples of nitrile solvents include acetonitrile, propionitrile, valerate, and butyronitrile.

[0438] 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.

[0439] 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.

[0440] 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 holding it still for a certain time (water pit 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.

[0441] 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 used in the organic developer. 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, at least one selected from alcohol solvents and ester solvents is more preferred, and alcohol solvents are particularly preferred.

[0442] 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.

[0443] 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.

[0444] The rinsing solution can be mixed with known additives as needed. Examples of such additives include surfactants. Examples of surfactants include those described above, preferably nonionic surfactants, more preferably nonionic fluorinated surfactants, or nonionic silicone surfactants.

[0445] When a surfactant is added, the amount added is typically 0.001 to 5% by mass relative to the total amount of the rinsing solution, preferably 0.005 to 2% by mass, and more preferably 0.01 to 0.5% by mass.

[0446] 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 (rotation 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).

[0447] It is speculated that in the resist pattern forming method of this embodiment described above, since the resist composition of the first scheme described above is used, a resist pattern with good resolution and wet etching resistance can be obtained.

[0448] Example

[0449] The present invention will be further described in detail below by way of examples, but the present invention is not limited to these examples.

[0450] <Preparation of Anti-corrosion Composition>

[0451] (Examples 1-21, Comparative Examples 1-3)

[0452] The components shown in Tables 1 to 3 were mixed and dissolved to prepare the resist compositions for each example.

[0453] [Table 1]

[0454]

[0455] [Table 2]

[0456]

[0457] [Table 3]

[0458]

[0459] In Tables 1-3, each abbreviation has the following meaning. The value in [] is the amount of blending (parts by mass).

[0460] (A)-1: A polymeric compound represented by the following chemical formula (A-1). This polymeric compound (A-1) is obtained by anionic polymerization of monomers that derive the structural units constituting the polymeric compound at a specified molar ratio. For this polymeric compound (A-1), the weight-average molecular weight (Mw) converted from standard polystyrene 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.

[0461] [Chemistry 36]

[0462]

[0463] (A)-2: A polymeric compound (homopolymer) represented by the following chemical formula (A-2). This polymeric compound (A-2) is obtained by anionic polymerization of a monomer (hydroxystyrene) from which the structural units constituting this polymeric compound are derived. For this polymeric compound (A-2), the weight-average molecular weight (Mw) converted from standard polystyrene by GPC measurement is 2500, and the molecular weight distribution coefficient (Mw / Mn) is 1.2.

[0464] [Chemistry 37]

[0465]

[0466] (B)-1 to (B)-3: Acid-producing agents composed of compounds represented by the following chemical formulas (B-1) to (B-3).

[0467] [Chemistry 38]

[0468]

[0469] (C)-1: A crosslinking agent consisting of a compound represented by the following chemical formula (C-1).

[0470] (C)-11: A crosslinking agent consisting of a compound represented by the following chemical formula (C-11).

[0471] (D)-1: A nitrogen-containing organic compound consisting of a compound represented by the following chemical formula (D-1).

[0472] [Chemistry 39]

[0473]

[0474] (Z)-1: Polypropylene glycol represented by the following chemical formula (Z-1) with a mass-average molecular weight (Mw) of 400.

[0475] (Z)-2: Polypropylene glycol represented by the following chemical formula (Z-1) with a mass-average molecular weight (Mw) of 1000.

[0476] (Z)-3: Polypropylene glycol represented by the following chemical formula (Z-1) with a mass-average molecular weight (Mw) of 3000.

[0477] (Z)-4: Polypropylene glycol represented by the following chemical formula (Z-1) with a mass-average molecular weight (Mw) of 4000.

[0478] [Chemistry 40]

[0479]

[0480] (Z)-5: Polyethylene glycol represented by the following chemical formula (Z-2) with a mass-average molecular weight (Mw) of 1000.

[0481] (Z)-6: Polyethylene glycol represented by the following chemical formula (Z-2) with a mass-average molecular weight (Mw) of 4000.

[0482] (Z)-7: Polyethylene glycol represented by the following chemical formula (Z-2) with a mass-average molecular weight (Mw) of 8000.

[0483] (Z)-8: Polyethylene glycol represented by the following chemical formula (Z-2) with a mass-average molecular weight (Mw) of 20,000.

[0484] [Chemistry 41]

[0485]

[0486] (Z)-9: Polytetrahydrofuran with a mass-average molecular weight (Mw) of 1000, represented by the following chemical formula (Z-3).

[0487] (Z)-10: Polytetrahydrofuran with a mass-average molecular weight (Mw) of 2000, represented by the following chemical formula (Z-3).

[0488] [Chemistry 42]

[0489]

[0490] (S)-1: Propylene glycol monomethyl ether acetate.

[0491] <Methods for forming resist patterns>

[0492] Process (i):

[0493] The resist compositions of each example were applied to a silicon substrate treated with hexamethyldisilazane (HMDS) using a spin coater and dried by pre-baking (PAB) at 90°C for 90 seconds on a hot plate to form a resist film with a thickness of 3 μm.

[0494] Process (ii):

[0495] Next, the resist film was selectively irradiated with a high-pressure mercury lamp (365nm) through a mask using an i-line stepper (reduced projection exposure device: NSR-2205i 14E (Nikon; NA (numerical aperture) = 0.57, σ = 0.67)).

[0496] Next, a post-exposure heating (PEB) treatment was performed at 110°C for 60 seconds.

[0497] Process (iii):

[0498] 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.

[0499] Then, bake at 100°C for 60 seconds (post-baking).

[0500] The result is the formation of isolated line patterns with a spacing width of 700 nm and a pitch of 3500 nm (hereinafter referred to as "IS patterns").

[0501] Furthermore, in Comparative Examples 2 and 3, the aforementioned IS pattern could not be distinguished.

[0502] [Sensitivity Evaluation]

[0503] Determine the optimal exposure value Eop (mJ / cm) for forming an IS pattern with a spacing width of 700 nm and a pitch of 3500 nm in the above <Resist Pattern Formation>. 2 ). This is taken as "Eop(mJ / cm 2 The symbols are shown in Tables 4-6.

[0504] [Resolution Evaluation]

[0505] Using a scanning electron microscope S-9380 (manufactured by Hitachi High Technology Co., Ltd.), the minimum size of the pattern that can be resolved without collapse was determined by gradually increasing the exposure from the optimal exposure Eop for forming an IS pattern of the target size through the above-described <Resist Pattern Formation>. This is shown as "resolution (nm)" in Tables 4-6.

[0506] <Evaluation of resistance to wet etching>

[0507] A portion of the substrate with the IS pattern formed by the above-described method for forming the resist pattern is cut off and immersed in 23% buffered hydrofluoric acid for 12 minutes.

[0508] The cross-sectional shape of the IS pattern after impregnation was observed using a scanning electron microscope (product name: S4500; manufactured by Hitachi, Ltd.), and the side etching (the cut marks caused by etching at the interface between the resist film and the substrate) (μm) was evaluated. The results are shown in Tables 4-6.

[0509] [Table 4]

[0510]

[0511] [Table 5]

[0512]

[0513] [Table 6]

[0514]

[0515] The results shown in Tables 4-6 confirm that the resist patterns formed using the resist compositions of Examples 1-21 exhibit good resolution and wet etching resistance. In particular, the resist patterns formed using the resist compositions of Examples 1-20 demonstrate excellent properties in balancing resolution and wet etching resistance.

[0516] 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 to the structure can be made 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 corrosion resist composition, characterized in that, contain: A polymeric compound (A1) having a structural unit (a10) represented by the following general formula (a10-1). Acid-producing agent (B) At least one crosslinking agent (C) selected from the group consisting of melamine crosslinking agents, urea crosslinking agents, alkylene urea crosslinking agents, glycourea crosslinking agents, and epoxy crosslinking agents. Polyether compounds (Z) represented by the following general formula (z-1-1) The mass-average molecular weight (Mw) of the polyether compound (Z) is 300–25000. The content of the polyether compound (Z) is 0.5 parts by mass and less than 50 parts by mass relative to 100 parts by mass of the polymer compound (A1). [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 Wa is a single bond or a divalent linker. x1 For aromatic hydrocarbon groups with or without substituents, n ax1 Integers greater than or equal to 1 [Chemistry 2] In the formula, Rz 11 Rz is an alkylene group with or without substituents. 12 and Rz 13 For hydrogen atoms, nz is an integer greater than or equal to 1.

2. The resist composition according to claim 1, characterized in that, The content of the polyether compound (Z) is more than 0.5 parts by mass and less than 20 parts by mass relative to 100 parts by mass of the polymer compound (A1).

3. The resist composition according to claim 1, characterized in that, The content of the polyether compound (Z) is 5 parts by mass or more and less than 50 parts by mass relative to 100 parts by mass of the polymer compound (A1).

4. The resist composition according to any one of claims 1 to 3, characterized in that, The acid-producing agent (B) contains an acid-producing agent (B0) represented by the following general formula (b0-1). [Chemistry 3] In the formula, Rb 1 Rb is an organic group. 2 For groups represented by the following general formula (b0-r-1) or the following general formula (b0-r-2), [Chemistry 4] In equation (b0-r-1), Rb 201 and Rb 202 Each is an independent organic group, * indicates a chemical bond. In formula (b0-r-2), Xb is a group that forms a cyclic group with -(O=)CNC(=O)- to form a cyclic imide structure, * indicates a chemical bond.

5. A method for forming a resist pattern, characterized in that, The device comprises: a step of forming a resist film on a support using the resist composition according to any one of claims 1 to 4; 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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