Resist composition and resist pattern forming method

Abstract

The present invention provides a resist composition and a resist pattern forming method which can form a resist pattern having good sensitivity, resolution and CDU capable of reproducing a fine pattern. The present invention relates to a resist composition which generates an acid by exposure and whose solubility in a developer changes due to the action of the acid, the resist composition containing a base material component (A1) whose solubility in a developer changes due to the action of the acid, and an acid generator component (B) which generates an acid by exposure, the aforementioned acid generator component (B) comprising a compound represented by general formula (b-1) described in the specification.

Description

Technical Field

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

[0002] In photolithography, for example, the following steps are performed: forming a resist film made of a resist material on a substrate, selectively exposing the resist film, and performing a development process, thereby forming a resist pattern of a predetermined shape on the resist film. A resist material whose exposed portion is soluble in the developer is called a positive type, and a resist material whose exposed portion is insoluble in the developer is called a negative type.

[0003] In recent years, the miniaturization of patterns has rapidly developed in the manufacturing of semiconductor components and liquid crystal display components due to the advancement of photolithography technology.

[0004] As a method of miniaturization, the exposure light source is generally shortened in wavelength (and increased in energy). Specifically, ultraviolet light, represented by g-lines and i-lines, was previously used, but now mass production of semiconductor devices using KrF excimer lasers and ArF excimer lasers has begun. In addition, research is also being conducted on EUV (extreme ultraviolet), EB (electron beam), and X-rays, which have shorter wavelengths (and higher energies) than these excimer lasers.

[0005] Under these conditions, photolithography properties such as sensitivity to these exposure light sources or energy sources and resolution capable of reproducing fine-sized patterns are required for resist materials.

[0006] As a resist material that meets such requirements, conventionally used resist compositions are chemically reinforced, which contain an acid-generating agent component that generates acid through exposure and a substrate component whose solubility in the developer changes due to the action of acid.

[0007] For example, Patent Document 1 describes a resist composition and a method for forming resist patterns that can form resist patterns with good resolution, DOF (Depth of Focus), and pattern shape. Furthermore, Patent Document 1 also describes resist compositions using an acid-generating agent component with a specific molar absorptivity and employing a polymer compound with multiple structural units having specific structures.

[0008] Existing technical documents Patent documents Patent Document 1: International Publication No. 2023 / 127692 Summary of the Invention

[0009] The problem that the invention aims to solve With the further advancement of photolithography technology and the continuous miniaturization of resist patterns, photoresist compositions are required to have high sensitivity, resolution capable of reproducing fine-sized patterns, and excellent CDU (Critical Dimention Uniformity) and other photolithographic properties.

[0010] The present invention was made in view of the above circumstances, and its object is to provide a resist composition and a method for forming a resist pattern that can form a resist pattern with good sensitivity, resolution and CDU.

[0011] Methods for solving problems The inventors of this application conducted repeated and in-depth research to solve the above-mentioned problems, and as a result, they discovered that by the following configuration, a resist composition and a resist pattern forming method that can form resist patterns with good sensitivity, resolution and CDU can be obtained, thereby completing the present invention.

[0012] That is, the present invention is as follows.

[0013] The photoresist composition according to the first embodiment of the present invention is a photoresist composition that generates acid by exposure and whose solubility in the developer changes due to the action of the acid. The photoresist composition contains a substrate component (A1) whose solubility in the developer changes due to the action of the acid, and an acid-generating component (B) that generates acid by exposure. The aforementioned acid-generating component (B) contains a compound represented by the following general formula (b-1).

[0014] [Chemical Formula 1] In general formula (b-1), Ra represents an optional organic group. m+ This represents an organic cation with a valence of m. m represents an integer greater than or equal to 1. The resist composition according to the second embodiment of the present invention comprises: a substrate component (A2) including an alkali-soluble resin (A2); an acid-generating agent component (B) that generates acid by exposure; and a crosslinking agent (C), wherein the alkali-soluble resin (A2) has a structural unit (a10) represented by the following general formula (a10-1), the aforementioned acid-generating agent component (B) comprises a compound represented by the following general formula (b-1), and the aforementioned crosslinking agent (C) comprises at least one crosslinking agent selected from the group consisting of melamine-based crosslinking agents, urea-based crosslinking agents, alkylene urea-based crosslinking agents, glycourea-based crosslinking agents, and epoxy-based crosslinking agents.

[0015] [Chemical Formula 2] In general 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. x1 It is a single bond or a divalent linker. Wa x1 For (n) ax1 +1) Aromatic hydrocarbon group. ax1 Integers greater than or equal to 1. [Chemical Formula 3] In general formula (b-1), Ra represents an optional organic group. m+ This represents an organic cation with a valence of m. m represents an integer greater than or equal to 1. The resist pattern forming method according to the third embodiment of the present invention is a resist pattern forming method including the following steps: a step of forming a resist film on a support using a resist composition according to the first or second embodiment of the present invention; a step of exposing the aforementioned resist film; and a step of developing the aforementioned resist film to form a resist pattern.

[0016] Invention Effects According to the present invention, a resist composition and a method for forming a resist pattern with good sensitivity, resolution and CDU can be provided. Detailed Implementation

[0017] The following provides a detailed description of the methods for implementing the present invention. It should be noted that the present invention is not limited to the embodiments described below.

[0018] In this publication, "aliphatic" is a relative concept compared to aromatic, and is defined as a group, compound, etc. that does not have aromaticity.

[0019] Unless otherwise specified, "alkyl" includes straight-chain, branched, and cyclic monovalent saturated hydrocarbon groups. The same applies to alkyl groups in alkoxy groups.

[0020] Unless otherwise specified, "alkylene" includes straight-chain, branched, and cyclic divalent saturated hydrocarbon groups.

[0021] "Halogenated alkyl" is a group obtained by replacing some or all of the hydrogen atoms of an alkyl group with halogen atoms. Examples of halogen atoms include fluorine, chlorine, bromine, and iodine.

[0022] "Fluoroalkyl" or "fluoroalkylene" refers to a group in which some or all of the hydrogen atoms of an alkyl or alkylene group are replaced by fluorine atoms.

[0023] "Structural unit" refers to the monomer unit (monomeric unit) that constitutes a polymer compound (resin, polymer, copolymer).

[0024] When it is stated that "substituents may be present", it includes both cases where a hydrogen atom (-H) is replaced with a monovalent group and cases where a methylene group (-CH2-) is replaced with a divalent group.

[0025] "Exposure" refers to the concept of exposure to all types of radiation.

[0026] "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 those 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 those 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 calculated using the mass-average molecular weight of polystyrene based on GPC (gel permeation chromatography).

[0027] "Derived structural units" refer to structural units formed by the breaking of multiple bonds between carbon atoms, such as alkene double bonds.

[0028] "Structural units derived from acrylates" refers to structural units formed by the breaking of olefinic double bonds in acrylates.

[0029] "Acrylates" are compounds obtained by replacing the hydrogen atom at the carboxyl terminus of acrylic acid (CH2=CH-COOH) with an organic group.

[0030] The hydrogen atom bonded to the carbon atom at the α-position in acrylates can also be replaced by a substituent. The substituent (R) that replaces the hydrogen atom bonded to the carbon atom at the α-position... α0 The substituent (R) is an atom or group other than a hydrogen atom, such as alkyl groups having 1 to 5 carbon atoms, haloalkyl groups having 1 to 5 carbon atoms, etc. Additionally, acrylates also include those with substituents (R). α0 Itaconic acid diester obtained by substituting a substituent containing an ester bond, and the substituent (R) α0 α-Hydroxyacrylates are obtained by substituting hydroxyalkyl groups or hydroxyl groups modified with hydroxyl groups. It should be noted that, unless otherwise specified, the carbon atom at the α-position of the acrylate refers to the carbon atom bonded to the carbonyl group of the acrylate.

[0031] 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. In addition, acrylates and α-substituted acrylates are sometimes collectively referred to as "(α-substituted) acrylates".

[0032] "Structural units derived from hydroxystyrene" refers to structural units formed by the cleavage of olefinic double bonds in hydroxystyrene. "Structural units derived from hydroxystyrene derivatives" refers to structural units formed by the cleavage of olefinic double bonds in hydroxystyrene derivatives.

[0033] "Hydroxystyrene derivatives" refers to compounds obtained by substituting the hydrogen atom at the α-position of hydroxystyrene with other substituents such as alkyl or haloalkyl groups, as well as their derivatives. Examples of their derivatives include compounds obtained by substituting the hydrogen atom at the α-position of hydroxystyrene with an organic group; and compounds obtained by bonding a substituent other than a hydroxyl group to the benzene ring of hydroxystyrene in which the hydrogen atom at the α-position can be replaced by a substituent. It should be noted that unless otherwise specified, the α-position (the carbon atom at the α-position) refers to the carbon atom bonded to the benzene ring.

[0034] As a substituent for replacing the hydrogen atom at the α-position of p-hydroxystyrene, examples can be made of the same groups as those mentioned as substituents at the α-position in the above-described α-substituted acrylates.

[0035] Regarding the alkyl group used as the α-position substituent, it is preferred to be a straight-chain or branched alkyl group. Specifically, examples include alkyl groups with 1 to 5 carbon atoms (methyl, ethyl, propyl, isopropyl, n-butyl, isobutyl, tert-butyl, pentyl, isopentyl, neopentyl, etc.).

[0036] Furthermore, regarding the alkyl halogroup as the substituent at the α-position, specifically, examples include groups obtained by replacing some or all of the hydrogen atoms of the aforementioned "alkyl halogroup as the substituent at the α-position" with halogen atoms. Examples of such halogen atoms include fluorine atoms, chlorine atoms, bromine atoms, iodine atoms, etc., with fluorine atoms being particularly preferred.

[0037] Furthermore, regarding the hydroxyalkyl group that serves as a substituent at the α-position, specifically, examples include groups obtained by replacing some or all of the hydrogen atoms of the aforementioned "alkyl group that serves as a substituent at the α-position" with hydroxyl groups. The number of hydroxyl groups in this hydroxyalkyl group is preferably 1 to 5, and most preferably 1.

[0038] In this document, the range of values ​​indicated by “~” refers to the range encompassed by the values ​​recorded before and after “~” as the lower and upper limits.

[0039] Furthermore, in this disclosure, the amount of each component in the composition refers to the total amount of the corresponding substances present in the composition, unless otherwise specified.

[0040] In addition, the chemical structural formulas in this disclosure are sometimes written as simplified structural formulas that omit the hydrogen atoms.

[0041] In this disclosure, depending on the structure represented by the chemical formula, there exist asymmetric carbon structures, and enantiomers and diastereomers may exist. In this case, a single chemical formula is used to representatively represent these isomers. These isomers may be used individually or as mixtures.

[0042] In this public text, “mass%” and “weight%” are synonymous, and “parts of mass” and “parts of weight” are synonymous.

[0043] [Resistant Composition] In this disclosure, 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.

[0044] The resist composition in this embodiment can be a positive resist composition or a negative resist composition.

[0045] Alternatively, the resist composition of this embodiment can be a resist composition for alkaline developing processes that uses an alkaline developer in the developing process during resist pattern formation, or a resist composition for solvent developing processes that uses a developer containing an organic solvent (organic developer) in the developing process.

[0046] That is, the resist composition of this embodiment is a "positive resist composition for alkaline development process" that forms a positive resist pattern in an alkaline development process, and a "negative resist composition for solvent development process" that forms a negative resist pattern in a solvent development process.

[0047] The photoresist composition according to the first embodiment of the present invention is a photoresist composition that generates acid by exposure and whose solubility in the developer changes due to the action of the acid. It contains a substrate component (A1) (hereinafter also referred to as "(A1) component") whose solubility in the developer changes due to the action of the acid, and an acid-generating agent component (B) (hereinafter also referred to as "(B) component") that generates acid by exposure. The aforementioned acid-generating agent component (B) contains a compound represented by the following general formula (b-1).

[0048] The resist composition according to the second embodiment of the present invention contains a substrate component (A2) comprising an alkali-soluble resin (A2) (hereinafter also referred to as "(A2) component"), an acid-generating agent component (B) that generates acid by exposure, and a crosslinking agent (C) (hereinafter also referred to as "(C) component"). The alkali-soluble resin (A2) has a structural unit (a10) represented by the following general formula (a10-1). The aforementioned component (B) comprises a compound represented by the following general formula (b-1). The aforementioned crosslinking agent (C) comprises at least one crosslinking agent selected from the group consisting of melamine-based crosslinking agents, urea-based crosslinking agents, alkylene urea-based crosslinking agents, glycourea-based crosslinking agents, and epoxy-based crosslinking agents.

[0049] When a resist film is formed using the resist composition according to the first embodiment of the present invention and the resist film is selectively exposed, acid is generated in the exposed portion of the resist film. Due to the action of the acid, the solubility of component (Al) in the developer changes. On the other hand, in the unexposed portion of the resist film, the solubility of component (Al) in the developer does not change. Therefore, a difference in solubility in the developer occurs between the exposed and unexposed portions of the resist film.

[0050] Therefore, when the resist film is developed, the exposed portion of the resist film is dissolved and removed, and a positive resist pattern can be formed.

[0051] Regarding the resist film formed using the resist composition according to the second embodiment of the present invention, when acid is generated from component (B) through exposure, the acid acts on component (C), reducing its solubility in the developer solution through a crosslinking reaction. Therefore, during the formation of the resist pattern, when the resist film obtained by coating the resist composition according to the second embodiment onto a support is selectively exposed, the solubility of the exposed portion of the resist film in the developer solution decreases, while the solubility of the unexposed portion of the resist film in the developer solution remains unchanged. Thus, a difference in solubility in the developer solution arises between the exposed and unexposed portions of the resist film. Therefore, when the resist film is developed using alkaline or solvent methods, the unexposed portion of the resist film is dissolved and removed, enabling the formation of a negative resist pattern. Consequently, by selectively exposing through a desired mask pattern, a target resist pattern can be formed with high precision.

[0052] The resist composition according to the second embodiment of the present invention can be a resist composition for alkaline developing processes that uses an alkaline developer in the developing process during resist pattern formation, or a resist composition for solvent developing processes that uses a developer containing an organic solvent (organic developer) in the developing process during resist pattern formation. The resist composition according to the second embodiment of the present invention is a resist composition that is particularly useful for alkaline developing processes.

[0053] [The corrosion resist composition according to the first embodiment] Component (A1) can also generate acid through exposure. In this case, component (A1) becomes "a substrate component that generates acid through exposure and whose solubility in the developer changes due to the action of the acid." When component (A1) is a substrate component that generates acid through exposure and whose solubility in the developer changes due to the action of the acid, it is preferable that component (A1) described later is a polymer compound that generates acid through exposure and whose solubility in the developer changes due to the action of the acid. As such a polymer compound, a copolymer having structural units that generate acid through exposure can be used. Known structural units can be cited as examples of structural units that generate acid through exposure.

[0054] The resist composition according to the first embodiment of the present invention comprises a compound represented by the following general formula (b-1) as an acid-generating component (B).

[0055] Regarding the compound represented by general formula (b-1) according to the first embodiment of the present invention, the anion is stabilized due to the electron-withdrawing effect of pentafluorobenzene, resulting in a lower pKa and enabling high sensitivity. Furthermore, since the compound represented by general formula (b-1) has a large structure, it is presumed that the diffusion length through the acid is shortened, enabling the formation of a well-shaped resist pattern.

[0056] "(A1) Ingredient" In the resist composition of the first embodiment of the present invention, as described above, the (A1) component is a substrate component whose solubility in the developer changes due to the action of acid. The (A1) component is preferably a resin component (A1) whose solubility in the developer changes due to the action of acid (hereinafter also referred to as "resin (A1)"). The resin (A1) can be a resin whose solubility in the developer increases due to the action of acid, or a resin whose solubility in the developer decreases due to the action of acid. By using the resin (A1), the polarity of the substrate component (A1) changes before and after exposure, thus enabling good development contrast not only in alkaline development processes but also in solvent development processes.

[0057] As a component (A1), at least resin (A1) is used, and it may also be used together with other high molecular weight compounds and / or low molecular weight compounds.

[0058] As the resin (A1), the preferred component is a structural unit (a10) represented by the general formula (a10-1). Alternatively, it may contain a polymeric compound having a structural unit (a1) that includes an acid-decomposing group whose polarity increases due to the action of an acid.

[0059] As a resin (A1), in addition to the structural unit (a10), it may also contain a polymeric compound having a structural unit (a1) containing an acid-decomposing group whose polarity increases due to the action of an acid, or a polymeric compound having a structural unit (st) derived from styrene or a styrene derivative.

[0060] In the resist composition according to the first embodiment of the present invention, the resin (A1) may be used alone or in combination with two or more types.

[0061] <Structural Unit (a10)> The resin (A1) is preferably a structural unit (a10) represented by the general formula (a10-1).

[0062] [Chemical Formula 4] [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 For (n) ax1 +1) Aromatic hydrocarbon group. ax1 Integers greater than or equal to 1. In the aforementioned formula (a10-1), R is the same as R in the following formula (a1-1). 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, a hydrogen atom or a methyl group is particularly preferred.

[0063] In the aforementioned formula (a10-1), Ya x1 It is a single bond or a divalent linker.

[0064] In the aforementioned chemical formula, as Ya x1 Examples of divalent linking groups include divalent hydrocarbon groups (aliphatic hydrocarbon groups, aromatic hydrocarbon groups) that may have substituents, and divalent linking groups containing heteroatoms.

[0065] • Divalent hydrocarbon groups that may have substituents: In Ya x1In 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.

[0066] ··Ya x1 aliphatic hydrocarbon groups Aliphatic hydrocarbon groups represent hydrocarbon groups that are not aromatic. These aliphatic hydrocarbon groups can be saturated or unsaturated, but are generally preferred to be saturated.

[0067] Examples of aliphatic hydrocarbon groups include straight-chain or branched aliphatic hydrocarbon groups, or aliphatic hydrocarbon groups containing rings in their structure.

[0068] ...straight-chain or branched aliphatic hydrocarbon groups 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.

[0069] As a straight-chain aliphatic hydrocarbon group, a straight-chain alkylene group is preferred. Specifically, examples include methylene [-CH2-], ethylene [-(CH2)2-], trimethylene [-(CH2)3-], tetramethylene [-(CH2)4-], pentamethylene [-(CH2)5-], etc.

[0070] 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.

[0071] As a branched aliphatic hydrocarbon group, a branched alkylene group is preferred. Specifically, examples include alkylmethylene groups such as -CH(CH3)-, -CH(CH2CH3)-, -C(CH3)2-, -C(CH3)(CH2CH3)-, -C(CH3)(CH2CH2CH3)-, and -C(CH2CH3)2-; alkylethylene groups such as -CH(CH3)CH2-, -CH(CH3)CH(CH3)-, -C(CH3)2CH2-, -CH(CH2CH3)CH2-, and -C(CH2CH3)2-CH2-; alkyltrimethylene groups such as -CH(CH3)CH2CH2- and -CH2CH(CH3)CH2-; and alkylalkylene groups such as -CH(CH3)CH2CH2CH2- and -CH2CH(CH3)CH2CH2-. The alkyl group in the alkyl alkylene group is preferably a straight-chain alkyl group having 1 to 5 carbon atoms.

[0072] The aforementioned straight-chain or branched aliphatic hydrocarbon groups 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.

[0073] ...aliphatic hydrocarbon groups containing rings in their structure 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 may include substituents containing heteroatoms in the ring structure, groups obtained by bonding the aforementioned cyclic aliphatic hydrocarbon group to the end of a straight-chain or branched aliphatic hydrocarbon group, and groups that are intermediate in the middle of the aforementioned cyclic aliphatic hydrocarbon group. Examples of the aforementioned straight-chain or branched aliphatic hydrocarbon groups are the same groups as described above.

[0074] The cyclic aliphatic hydrocarbon group preferably has 3 to 20 carbon atoms, more preferably 3 to 12 carbon atoms.

[0075] The cyclic aliphatic hydrocarbon group can be a polycyclic group or a monocyclic group. As a monocyclic alicyclic hydrocarbon group, it is preferably a group obtained by removing two hydrogen atoms from a monocyclic alkane. As this monocyclic alkane, it is preferably a monocyclic alkane with 3 to 6 carbon atoms, specifically cyclopentane, cyclohexane, etc. As a polycyclic alicyclic hydrocarbon group, it is preferably a group obtained by removing two hydrogen atoms from a polycyclic alkane. As this polycyclic alkane, it is preferably a polycyclic alkane with 7 to 12 carbon atoms, specifically adamantane, norbornane, isobornane, tricyclic [5.2.1.0] 2,6 Decane, tetracyclododecane, etc.

[0076] 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.

[0077] Regarding the alkyl group used as the aforementioned substituent, an alkyl group having 1 to 5 carbon atoms is preferred, and methyl, ethyl, propyl, n-butyl, or tert-butyl are more preferred.

[0078] Regarding the alkoxy group used as the aforementioned substituent, an alkoxy group having 1 to 5 carbon atoms is preferred, more preferably methoxy, ethoxy, n-propoxy, isopropoxy, n-butoxy, or tert-butoxy, and even more preferably methoxy or ethoxy.

[0079] Regarding the halogen atom that can be used as a substituent, examples include fluorine, chlorine, bromine, and iodine atoms, with fluorine atoms being the preferred option.

[0080] Regarding the alkyl halogroups that are the aforementioned substituents, examples can be given of groups obtained by replacing some or all of the hydrogen atoms of the aforementioned alkyl group with the aforementioned halogen atoms.

[0081] In cyclic aliphatic hydrocarbon groups, a portion of the 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-.

[0082] ··Ya x1 aromatic hydrocarbon groups The aromatic hydrocarbon group is a hydrocarbon group having at least one aromatic ring.

[0083] 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.

[0084] 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, sulfur, and nitrogen atoms. Examples of aromatic heterocycles specifically include pyridine rings and thiophene rings.

[0085] Specifically, examples of aromatic hydrocarbon groups include groups (aryl or heteroaryl) obtained by removing two hydrogen atoms from the aforementioned aromatic hydrocarbon ring or aromatic heterocycle; groups obtained by removing two hydrogen atoms from an aromatic compound containing two or more aromatic rings (e.g., biphenyl, fluorene, etc.); and groups obtained by substituting one hydrogen atom of an aryl or heteroaryl group obtained by removing one hydrogen atom from the aforementioned aromatic hydrocarbon ring or aromatic heterocycle with an alkylene group (e.g., groups obtained by further removing one hydrogen atom from an aryl group in arylalkyl groups such as benzyl, phenethyl, 1-naphthylmethyl, 2-naphthylmethyl, 1-naphthylethyl, 2-naphthylethyl, etc.). The alkylene group bonded to the aforementioned aryl or heteroaryl group preferably has 1 to 4 carbon atoms, more preferably 1 to 2 carbon atoms, and particularly preferably 1 carbon atom.

[0086] In the aforementioned aromatic hydrocarbon group, the hydrogen atoms present in the aromatic hydrocarbon group can also be replaced by substituents. For example, the hydrogen atoms bonded to the aromatic ring in the aromatic hydrocarbon group can be replaced by substituents. Examples of such substituents include alkyl groups, alkoxy groups, halogen atoms, haloalkyl groups, and hydroxyl groups.

[0087] Regarding the alkyl group used as the aforementioned substituent, an alkyl group having 1 to 5 carbon atoms is preferred, and methyl, ethyl, propyl, n-butyl, or tert-butyl are more preferred.

[0088] Regarding the alkoxy, halogen atom, and haloalkyl groups that are the aforementioned substituents, examples can be given of groups that replace the hydrogen atoms of the aforementioned cyclic aliphatic hydrocarbon groups.

[0089] • Divalent linking groups containing heteroatoms: In Ya x1 In the case of a divalent linking group containing heteroatoms, preferred links 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 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 is an independent divalent hydrocarbon group that can have substituents, where O is an oxygen atom and m” is an integer from 1 to 3.

[0090] When the aforementioned divalent linking group containing heteroatoms is -C(=O)-NH-, -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.

[0091] 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 -and-Y 21 -S(=O)2-OY 22 -Medium,Y21 and Y 22 Each is independently a divalent hydrocarbon group that may have substituents. Examples of such divalent hydrocarbon groups include those mentioned above, which are related to the aforementioned Ya. x1 The same groups (which may have substituents) are listed in the description of the divalent linking groups.

[0092] As Ya x1 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.

[0093] As Ya x1 The divalent linking group in the above-mentioned group is preferably a carbonyl group, an ester bond, an amide bond, an alkylene group, or a combination thereof. As an alkylene group, a straight-chain or branched alkylene group is more preferred, and a methylene or ethylene group is even more preferred.

[0094] 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, an ester bond [-C(=O)-O-, -OC(=O)-], and even more preferably a single bond.

[0095] In the aforementioned formula (a10-1), Wa x1 For (n) ax1 +1) valence aromatic hydrocarbon group.

[0096] As Wa x1 Aromatic hydrocarbon groups in the aromatic ring can be exemplified by those removed from the aromatic ring (n... 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 number of carbon atoms in the aromatic ring is 5 to 30, more preferably 5 to 20, even more preferably 6 to 15, and particularly preferably 6 to 12. Specifically, examples of this aromatic ring include aromatic hydrocarbon rings such as benzene, naphthalene, anthracene, and phenanthrene; and aromatic heterocycles obtained 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. Specifically, examples of aromatic heterocycles include pyridine rings and thiophene rings.

[0097] Additionally, as Wa x1 The aromatic hydrocarbon groups in the text can also be cited as examples of aromatic compounds containing two or more aromatic rings (such as biphenyl, fluorene, etc.) by removing (n) aromatic hydrocarbon groups. ax1 A group obtained by adding 1 hydrogen atom.

[0098] Of the above, as Wa x1 Preferably, it is removed from benzene, naphthalene, anthracene, or biphenyl (n ax1 A group obtained by removing (n) hydrogen atoms is more preferably a group obtained by removing (n) hydrogen atoms from benzene or naphthalene. ax1 The group obtained by removing (n) hydrogen atoms is more preferably a group obtained by removing (n) hydrogen atoms from benzene. ax1 A group obtained by adding 1 hydrogen atom.

[0099] Wa x1 The aromatic hydrocarbon group in the form may or may not have substituents, but is preferably unsubstituents. Examples of substituents include alkyl groups, alkoxy groups, halogen atoms, and haloalkyl groups. Examples of alkyl, alkoxy, halogen atoms, and haloalkyl groups as substituents include those used as Ya. x1 The same group is mentioned as the substituent of the cyclic aliphatic hydrocarbon group. In Wa x1 To remove (n) from the aromatic ring ax1 In the case of a group obtained by adding (+1) hydrogen atoms, the aforementioned substituent substitution removes (n) hydrogen atoms from the aforementioned aromatic ring. ax1 The hydrogen atom in the group obtained by adding (+1) hydrogen atoms. The aforementioned 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.

[0100] In the aforementioned equation (a10-1), n ax1 The integer is 1 or higher, 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. Wherein, n ax1 The preferred value is 1.

[0101] The following shows a specific example of the structural unit (a10) represented by the aforementioned formula (a10-1).

[0102] In the following formulas, R α It represents a hydrogen atom, a methyl group, or a trifluoromethyl group.

[0103] [Chemical Formula 5] [Chemical Formula 6] [Chemical Formula 7] [Chemical Formula 8] The resin (A1) may have one or more structural units (a10).

[0104] When the resin (A1) has structural units (a10), the proportion of structural units (a10) in the resin (A1) relative to the total (100 mol%) of all structural units constituting the resin (A1) is preferably 20 to 90 mol%, more preferably 30 to 80 mol%, and even more preferably 40 to 80 mol%.

[0105] By setting the proportion of the structural unit (a10) above the lower limit, the sensitivity can be easily improved. On the other hand, by setting it below the upper limit, it is easy to achieve a balance with other structural units.

[0106] <Structural Unit (a1)> The structural unit (a1) is a structural unit containing an acid-decomposing group whose polarity increases due to the action of an acid.

[0107] "Acid-decomposable group" is a group that has the following acid-decomposability property: at least some of the bonds in the structure of the acid-decomposable group can be broken due to the action of acid.

[0108] Examples of acid-decomposing groups that increase in polarity due to the action of acids include groups that decompose due to the action of acids to produce polar groups.

[0109] Examples of polar groups include carboxyl, hydroxyl, amino, and sulfonyl (-SO3H). Among these, polar groups containing -OH in their structure (hereinafter sometimes referred to as "OH-containing polar groups") are preferred, carboxyl or hydroxyl groups are more preferred, and carboxyl groups are particularly preferred.

[0110] More specifically, examples of acid-dissociable groups include those polar groups that are protected by acid-dissociable groups (e.g., groups in which the hydrogen atoms of an OH-containing polar group are protected by acid-dissociable groups).

[0111] Here, "acid-dissociable group" refers to either of the following: (i) an acid-dissociable group whose bonds with the adjacent atoms can be broken by the action of an acid; or (ii) a group whose bonds are partially broken by the action of an acid, and then undergo further decarboxylation, thereby allowing the bonds with the adjacent atoms to be broken.

[0112] The acid-dissociating groups that constitute the acid-dissociating groups must be groups with lower polarity than the polar groups generated through the dissociation of these acid-dissociating groups. Therefore, when these acid-dissociating groups dissociate due to the action of acid, groups with higher polarity than the original acid-dissociating groups are generated, thus increasing the overall polarity of the resin (Al). This increased polarity leads to a change in solubility in the developer; solubility increases in alkaline developers and decreases in organic developers.

[0113] The structural unit (a1) is preferably a structural unit containing an acid-degradable group having an alicyclic hydrocarbon group, and more preferably a structural unit containing an acid-degradable group having a monocyclic alicyclic hydrocarbon group.

[0114] When the acid-dissociating group (acid-dissociating group) in the structural unit (a1) has an alicyclic hydrocarbon group, the diffusion control of the acid and its solubility in the developer can be moderately adjusted due to the appropriate size, thereby reducing the roughness when forming the resist pattern.

[0115] As an acid-dissociating group in structural unit (a1), examples of acid-dissociating groups proposed to date as basic resins used as chemically reinforced resists can be found.

[0116] As for the acid-dissociating groups proposed so far as the base resins used in chemically reinforced resist compositions, examples include "acetal-type acid-dissociating groups", "tertiary alkyl ester-type acid-dissociating groups", and "tertiary alkoxycarbonyl acid-dissociating groups".

[0117] • Acetal-type acid dissociation groups: As an acid-dissociating group that protects the carboxyl or hydroxyl group in the aforementioned polar group, examples of acid-dissociating groups represented by the following formula (a1-r-1) (hereinafter sometimes referred to as "acetal-type acid-dissociating groups") can be given.

[0118] [Chemical Formula 9] [In the formula, Ra'] 1 Ra' 2 It can be a hydrogen atom or an alkyl group. Ra' 3 It is a hydrocarbon group, Ra' 3 Can be used with Ra' 1 Ra' 2 Any one of them can bond together to form a ring. In formula (a1-r-1), Ra' is preferred. 1 and Ra' 2 At least one of them is a hydrogen atom, and more preferably both are hydrogen atoms.

[0119] In Ra' 1 or Ra' 2 When the alkyl group is alkyl, examples of such alkyl groups include those mentioned in the description of α-substituted acrylates as substituents that can bond to the carbon atom at the α-position, and preferably alkyl groups with 1 to 5 carbon atoms. Specifically, linear or branched alkyl groups are preferred. More specifically, examples include methyl, ethyl, propyl, isopropyl, n-butyl, isobutyl, tert-butyl, pentyl, isopentyl, neopentyl, etc., more preferably methyl or ethyl, and particularly preferably methyl.

[0120] In equation (a1-r-1), Ra' 3 The hydrocarbon group can be exemplified by straight-chain or branched alkyl groups, or cyclic hydrocarbon groups.

[0121] The linear alkyl group preferably has 1 to 5 carbon atoms, more preferably 1 to 4 carbon atoms, and even more preferably 1 or 2 carbon atoms. Specifically, examples include methyl, ethyl, n-propyl, n-butyl, and n-pentyl. Among these, methyl, ethyl, or n-butyl are preferred, and methyl or ethyl are more preferred.

[0122] The branched alkyl group preferably has 3 to 10 carbon atoms, more preferably 3 to 5 carbon atoms. Specifically, examples include isopropyl, isobutyl, tert-butyl, isopentyl, neopentyl, 1,1-diethylpropyl, 2,2-dimethylbutyl, etc., with isopropyl being the most preferred.

[0123] In Ra' 3 In the case of a cyclic hydrocarbon group, the hydrocarbon group can be an aliphatic hydrocarbon group or an aromatic hydrocarbon group. In addition, it can be a polycyclic group or a monocyclic group.

[0124] Regarding the aliphatic hydrocarbon group as a monocyclic group, it is preferably a group obtained by removing one hydrogen atom from a monocyclic alkane. As this monocyclic alkane, it is preferably a monocyclic alkane with 3 to 6 carbon atoms, specifically cyclopentane, cyclohexane, etc.

[0125] Regarding the aliphatic hydrocarbon group as a polycyclic group, it is preferred to be a group obtained by removing one hydrogen atom from a polycyclic alkane. As for the polycyclic alkane, it is preferred to be a polycyclic alkane with 7 to 12 carbon atoms, specifically examples include adamantane, norbornane, isobornane, tricyclodecane, tetracyclododecane, etc.

[0126] In Ra' 3 When the cyclic hydrocarbon group is an aromatic hydrocarbon group, the aromatic hydrocarbon group is a hydrocarbon group having at least one aromatic ring.

[0127] 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 carbon atoms, even more preferably 6 to 15 carbon atoms, and particularly preferably 6 to 12 carbon atoms.

[0128] 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, sulfur, and nitrogen atoms. Examples of aromatic heterocycles specifically include pyridine rings and thiophene rings.

[0129] As Ra' 3 The aromatic hydrocarbon group in the compound can specifically include groups (aryl or heteroaryl) obtained by removing one hydrogen atom from the aforementioned aromatic hydrocarbon ring or aromatic heterocycle; groups obtained by removing one hydrogen atom from an aromatic compound containing two or more aromatic rings (e.g., biphenyl, fluorene, etc.); and groups obtained by substituting one hydrogen atom of the aforementioned aromatic hydrocarbon ring or aromatic heterocycle with an alkylene group (e.g., benzyl, phenethyl, 1-naphthylmethyl, 2-naphthylmethyl, 1-naphthylethyl, 2-naphthylethyl, etc., arylalkyl groups, etc.). The alkylene group bonded to the aforementioned aromatic hydrocarbon ring or aromatic heterocycle preferably has 1 to 4 carbon atoms, more preferably 1 to 2 carbon atoms, and particularly preferably 1 carbon atom.

[0130] Ra' 3 The cyclic hydrocarbon group in the hydrocarbon may have substituents. Examples of such substituents include -R. P1 -R P2 -OR P1 -R P2 -CO-R P1 -R P2 -CO-OR P1 -R P2 -O-CO-R P1 -R P2 -OH, -R P2 -CN or -R P2 -COOH (hereinafter, these substituents will also be collectively referred to as "Ra") 05 ")wait.

[0131] Here, R P1 It can be a monovalent chain saturated hydrocarbon group with 1 to 10 carbon atoms, a monovalent aliphatic cyclic saturated hydrocarbon group with 3 to 20 carbon atoms, or a monovalent aromatic hydrocarbon group with 6 to 30 carbon atoms. Additionally, R... P2It is a single bond, a divalent chain saturated hydrocarbon group with 1 to 10 carbon atoms, a divalent aliphatic cyclic saturated hydrocarbon group with 3 to 20 carbon atoms, or a divalent aromatic hydrocarbon group with 6 to 30 carbon atoms. Among them, R... P1 and R P2 Some or all of the hydrogen atoms in the chain-like saturated hydrocarbon group, aliphatic cyclic saturated hydrocarbon group, and aromatic hydrocarbon group may be replaced by fluorine atoms. The aforementioned cyclic hydrocarbon group may have one or more of the above-mentioned substituents individually, or it may have one or more of the above-mentioned substituents.

[0132] Examples of monovalent chain saturated hydrocarbon groups with 1 to 10 carbon atoms include methyl, ethyl, propyl, butyl, pentyl, hexyl, heptyl, octyl, and decyl.

[0133] Examples of monocyclic aliphatic cyclic saturated hydrocarbon groups with 3 to 20 carbon atoms include monocyclic aliphatic saturated hydrocarbon groups such as cyclopropyl, cyclobutyl, cyclopentyl, cyclohexyl, cycloheptyl, cyclooctyl, cyclodecyl, and cyclododecyl; bicyclic [2.2.2]octyl; and tricyclic [5.2.1.0]... 2,6 ] decyl, tricyclic [3.3.1.1] 3,7 ] decyl, tetracyclic [6.2.1.1 3,6 .0 2,7 Dodecyl, adamantyl, and other polycyclic aliphatic saturated hydrocarbon groups.

[0134] Examples of monovalent aromatic hydrocarbon groups with 6 to 30 carbon atoms include groups obtained by removing one hydrogen atom from the aromatic hydrocarbon rings of benzene, biphenyl, fluorene, naphthalene, anthracene, and phenanthrene.

[0135] In Ra' 3 With Ra' 1 Ra' 2 When any of the elements are bonded together to form a ring, the cyclic group is preferably a 4- to 7-membered ring, more preferably a 4- to 6-membered ring. Specific examples of this cyclic group include tetrahydropyranyl and tetrahydrofuranyl.

[0136] • Tertiary alkyl ester type acid dissociable groups: As an acid-dissociating group that protects the carboxyl group in the above-mentioned polar groups, examples of acid-dissociating groups represented by the following general formula (a1-r-2) can be cited.

[0137] It should be noted that, for convenience, substances whose acid-dissociating groups are composed of alkyl groups as represented by the following formula (a1-r-2) are sometimes referred to as "tertiary alkyl ester type acid-dissociating groups".

[0138] [Chemical Formula 10] [In the formula, Ra']4 ~Ra' 6 Each represents a hydrocarbon group, Ra' 5 Ra' 6 They can bond together to form a ring. As Ra' 4 Examples of hydrocarbon groups represented include straight-chain or branched alkyl groups, chain-like or cyclic alkenyl groups, or cyclic hydrocarbon groups.

[0139] Ra' 4 The linear or branched alkyl groups and cyclic hydrocarbon groups (aliphatic hydrocarbon groups as monocyclic groups, aliphatic hydrocarbon groups as polycyclic groups, and aromatic hydrocarbon groups) mentioned above can be exemplified by Ra'. 3 The same group as the straight-chain or branched alkyl or cyclic hydrocarbon group.

[0140] Ra' 4 The chain or cyclic alkenyl group is preferably an alkenyl group with 2 to 10 carbon atoms.

[0141] As Ra' 5 Ra' 6 Hydrocarbon groups, such as those related to the aforementioned Ra' 3 The same group as the hydrocarbon group.

[0142] In Ra' 5 With Ra' 6 When they bond together to form a ring, suitable examples of acid-dissociating groups represented by the above formula (a1-r-2) are groups represented by the following formula (a1-r2-1), groups represented by the following formula (a1-r2-2), and groups represented by the following formula (a1-r2-3).

[0143] On the other hand, in Ra' 4 ~Ra' 6 In the case where the hydrocarbon groups are independent and not bonded to each other, the group represented by the following formula (a1-r-2) can be suitably cited as the acid-dissociating group represented by the above formula (a1-r-2).

[0144] [Chemical Formula 11] In the formula (a1-r2-1), Ra 031 Yab represents alkyl groups. 0 Represents a carbon atom. Xab 0 Indicates Yab 0A group that forms an alicyclic hydrocarbon group together with Ya, wherein some or all of the hydrogen atoms in the alicyclic hydrocarbon group can be substituted. In formula (a1-r2-2), Ya is a carbon atom. Xa is a group that forms a cyclic hydrocarbon group with Ya. Some or all of the hydrogen atoms in the cyclic hydrocarbon group can be substituted. Ra 101 ~Ra 103 Each is independently a monovalent chain saturated hydrocarbon group consisting of hydrogen atoms and 1 to 10 carbon atoms, or a monovalent aliphatic cyclic saturated hydrocarbon group consisting of 3 to 20 carbon atoms. Some or all of the hydrogen atoms in this chain saturated hydrocarbon group or aliphatic cyclic saturated hydrocarbon group may be substituted. Ra 101 ~Ra 103 Two or more of these atoms can bond together to form a ring structure. In formula (a1-r2-3), Yaa is a carbon atom. Xaa is a group that forms an aliphatic cyclic group with Yaa. Ra 104 It is an aromatic hydrocarbon group that can have substituents. In formula (a1-r2-4), Ra' 12 and Ra' 13 Each is an independent, monovalent, chain-like saturated hydrocarbon group with 1 to 10 carbon atoms. Some or all of the hydrogen atoms in this chain-like saturated hydrocarbon group can be substituted. Ra' 14 It is a hydrocarbon group that can have substituents. Indicates a connection key. In the above formula (a1-r2-1), Ra 031 Preferably, it is a chain-like alkyl group, and more preferably a straight-chain or branched alkyl group with 1 to 12 carbon atoms that can be partially replaced by halogen atoms or heteroatom-containing groups.

[0145] As Ra 031 The linear alkyl group in the compound has 1 to 12 carbon atoms, preferably 1 to 10 carbon atoms, and particularly preferably 1 to 5 carbon atoms.

[0146] As Ra 031 Branched alkyl groups, such as those mentioned above Ra', can be cited as examples. 4 The same group.

[0147] Ra 031 The alkyl group can be partially replaced by a halogen atom or a heteroatom-containing group. For example, some of the hydrogen atoms constituting the alkyl group can be replaced by a halogen atom or a heteroatom-containing group. In addition, some of the carbon atoms constituting the alkyl group (such as methylene) can be replaced by a heteroatom-containing group.

[0148] Examples of heteroatoms mentioned here include oxygen, sulfur, and nitrogen atoms. Examples of heteroatom-containing groups include (-O-), -C(=O)-O-, -OC(=O)-, -C(=O)-, -OC(=O)-O-, -C(=O)-NH-, -NH-, -S-, -S(=O)2-, -S(=O)2-O-, etc.

[0149] In the formula (a1-r2-1), Xab 0 with Yab 0 The alicyclic hydrocarbon group formed together is preferably Ra', which is the same as the one in the above formula (a1-r-1). 3 A group obtained by further removing one or more hydrogen atoms from a monocyclic or polycyclic group, i.e., an aliphatic hydrocarbon group (alicyclic hydrocarbon group). Preferably, it is an alicyclic hydrocarbon group, more preferably a monocyclic alicyclic hydrocarbon group, and even more preferably a group obtained by removing two or more hydrogen atoms from a monocyclic alkane. As for the monocyclic alkane, it is preferably a monocyclic alkane with 3 to 8 carbon atoms, specifically cyclopentane, cyclohexane, cycloheptane, cyclooctane, etc.

[0150] In formula (a1-r2-2), Ra', which is a cyclic hydrocarbon group formed by Xa and Ya together, can be cited as an example. 4 A group obtained by further removing one or more hydrogen atoms from a cyclic monovalent hydrocarbon group (aliphatic hydrocarbon group).

[0151] The cyclic hydrocarbon group formed by Xa and Ya together can have substituents. Examples of such substituents include those related to Ra' mentioned above. 4 The cyclic hydrocarbon group in the hydrocarbon can have the same substituents.

[0152] In equation (a1-r2-2), Ra is used as... 101 ~Ra 103 The monovalent chain saturated hydrocarbon group containing 1 to 10 carbon atoms includes, for example, methyl, ethyl, propyl, butyl, pentyl, hexyl, heptyl, octyl, decyl, etc.

[0153] As Ra 101 ~Ra 103 The monocyclic saturated hydrocarbon groups with 3 to 20 carbon atoms are aliphatic cyclic saturated hydrocarbon groups, such as cyclopropyl, cyclobutyl, cyclopentyl, cyclohexyl, cycloheptyl, cyclooctyl, cyclodecyl, and cyclododecyl monocyclic aliphatic saturated hydrocarbon groups; bicyclic [2.2.2]octyl, tricyclic [5.2.1.0]... 2,6 ] decyl, tricyclic [3.3.1.1] 3,7 ] decyl, tetracyclic [6.2.1.1 3,6 .0 2 ,7Dodecyl, adamantyl, and other polycyclic aliphatic saturated hydrocarbon groups, etc.

[0154] Ra 101 ~Ra 103 From the viewpoint of ease of synthesis, the preferred components are a hydrogen atom and a monovalent chain saturated hydrocarbon group having 1 to 10 carbon atoms, more preferably a hydrogen atom, methyl, or ethyl group, and particularly preferably a hydrogen atom.

[0155] As for the above Ra 101 ~Ra 103 The substituents represented by the chain-like saturated hydrocarbon group or the aliphatic cyclic saturated hydrocarbon group can be exemplified by those related to the Ra group described above. 05 The same group.

[0156] As Ra 101 ~Ra 103 The group consisting of two or more carbon-carbon double bonds bonded together to form a cyclic structure includes, for example, cyclopentenyl, cyclohexenyl, methylcyclopentenyl, methylcyclohexenyl, cyclopentyleneidene, and cyclohexyleneidene. From the viewpoint of ease of synthesis, cyclopentenyl, cyclohexenyl, and cyclopentyleneidene are preferred.

[0157] In formula (a1-r2-3), the aliphatic cyclic group formed by Xaa and Yaa together is preferably Ra', which is the aliphatic cyclic group in formula (a1-r-2) above. 4 A group obtained by further removing one or more hydrogen atoms from a monocyclic or polycyclic group, i.e., an aliphatic hydrocarbon group.

[0158] In equation (a1-r2-3), Ra is used as... 104 The aromatic hydrocarbon group in the text can be exemplified by groups obtained by removing one or more hydrogen atoms from an aromatic hydrocarbon ring having 5 to 30 carbon atoms. Among them, Ra... 104 Preferably, it is a group obtained by removing one or more hydrogen atoms from an aromatic hydrocarbon ring having 6 to 15 carbon atoms; more preferably, it is a group obtained by removing one or more hydrogen atoms from benzene, naphthalene, anthracene, or phenanthrene; even more preferably, it is a group obtained by removing one or more hydrogen atoms from benzene, naphthalene, or anthracene; particularly preferably, it is a group obtained by removing one or more hydrogen atoms from benzene or naphthalene; and most preferably, it is a group obtained by removing one or more hydrogen atoms from benzene.

[0159] Ra in equation (a1-r2-3) 104 It may have substituents, such as methyl, ethyl, propyl, hydroxyl, carboxyl, halogen atom, alkoxy (methoxy, ethoxy, propoxy, butoxy, etc.), alkoxy carbonyl, etc.

[0160] In formula (a1-r2-4), Ra' 12 and Ra'13 Each is an independent monovalent chain saturated hydrocarbon group with 1 to 10 carbon atoms. As Ra' 12 and Ra' 13 Chain-like saturated hydrocarbon groups with 1 to 10 carbon atoms in a monovalent form, such as those related to Ra mentioned above, can be cited as examples. 101 ~Ra 103 It is the same as the monovalent chain saturated hydrocarbon group with 1 to 10 carbon atoms. Some or all of the hydrogen atoms in this chain saturated hydrocarbon group can be replaced.

[0161] Ra' 12 and Ra' 13 More preferably, it is an alkyl group having 1 to 5 carbon atoms, further preferably methyl or ethyl, and particularly preferably methyl.

[0162] In the above Ra' 12 and Ra' 13 When the chain-like saturated hydrocarbon group is substituted, examples of substituents include those related to Ra mentioned above. 05 The same group.

[0163] In formula (a1-r2-4), Ra' 14 It is a hydrocarbon group that can have substituents. As Ra' 14 The hydrocarbon group in the text can be a straight-chain or branched alkyl group, or a cyclic hydrocarbon group.

[0164] Ra' 14 The linear alkyl group in the form preferably has 1 to 5 carbon atoms, more preferably 1 to 4, and even more preferably 1 or 2. Specifically, examples include methyl, ethyl, n-propyl, n-butyl, and n-pentyl. Among these, methyl, ethyl, or n-butyl are preferred, and methyl or ethyl are more preferred.

[0165] Ra' 14 The branched alkyl group preferably has 3 to 10 carbon atoms, more preferably 3 to 5. Specifically, examples include isopropyl, isobutyl, tert-butyl, isopentyl, neopentyl, 1,1-diethylpropyl, 2,2-dimethylbutyl, etc., with isopropyl being the most preferred.

[0166] In Ra' 14 In the case of a cyclic hydrocarbon group, the hydrocarbon group can be an aliphatic hydrocarbon group or an aromatic hydrocarbon group. In addition, it can be a polycyclic group or a monocyclic group.

[0167] Regarding the aliphatic hydrocarbon group as a monocyclic group, it is preferably a group obtained by removing one hydrogen atom from a monocyclic alkane. As this monocyclic alkane, it is preferably a monocyclic alkane with 3 to 6 carbon atoms, specifically cyclopentane, cyclohexane, etc.

[0168] Regarding the aliphatic hydrocarbon group as a polycyclic group, it is preferably a group obtained by removing one hydrogen atom from a polycyclic alkane. As for the polycyclic alkane, it is preferably a polycyclic alkane with 7 to 12 carbon atoms, specifically examples include adamantane, norbornane, isobornane, and tricyclic [5.2.1.0]. 2,6 Decane, tetracyclododecane, etc.

[0169] As Ra' 14 Aromatic hydrocarbon groups in Ra can be cited as examples. 104 The same group as the aromatic hydrocarbon group in it. Among them, Ra' 14 Preferably, it is a group obtained by removing one or more hydrogen atoms from an aromatic hydrocarbon ring having 6 to 15 carbon atoms; more preferably, it is a group obtained by removing one or more hydrogen atoms from benzene, naphthalene, anthracene, or phenanthrene; even more preferably, it is a group obtained by removing one or more hydrogen atoms from benzene, naphthalene, or anthracene; particularly preferably, it is a group obtained by removing one or more hydrogen atoms from naphthalene or anthracene; and most preferably, it is a group obtained by removing one or more hydrogen atoms from naphthalene.

[0170] As Ra' 14 Possible substituents include those related to Ra. 104 It can have the same substituents.

[0171] Ra' in equation (a1-r2-4) 14 In the case of a naphthyl group, the position where it bonds to the tertiary carbon atom in the aforementioned formula (a1-r2-4) can be any position between the 1st and 2nd positions of the naphthyl group.

[0172] Ra' in equation (a1-r2-4) 14 In the case of anthracene group, the position of bonding with the tertiary carbon atom in the aforementioned formula (a1-r2-4) can be any of the 1, 2, or 9 positions of the anthracene group.

[0173] The following are specific examples of the groups represented by the aforementioned formula (a1-r2-1).

[0174] [Chemical Formula 12] [Chemical Formula 13] [Chemical Formula 14] The following are specific examples of the groups represented by the aforementioned formula (a1-r2-2).

[0175] [Chemical Formula 15] [Chemical Formula 16] [Chemical Formula 17] The following are specific examples of the groups represented by the aforementioned formula (a1-r2-3).

[0176] [Chemical Formula 18] The following are specific examples of the groups represented by the aforementioned formula (a1-r2-4).

[0177] [Chemical Formula 19] • Dissociable groups of tertiary alkoxy carbonyl acids: As an acid-dissociating group that protects the hydroxyl group in the aforementioned polar group, an example of an acid-dissociating group represented by the following formula (a1-r-3) can be cited (hereinafter sometimes referred to as "tertiary alkoxycarbonyl acid-dissociating group" for convenience).

[0178] [Chemical Formula 20] [In the formula, Ra'] 7 ~Ra' 9 Each represents an alkyl group. In equation (a1-r-3), Ra' 7 ~Ra' 9 Each is preferably an alkyl group having 1 to 5 carbon atoms, and more preferably having 1 to 3 carbon atoms.

[0179] In addition, the total number of carbon atoms of each alkyl group is preferably 3 to 7, more preferably 3 to 5, and most preferably 3 to 4.

[0180] As an acid-dissociable group, among the groups represented by the above general formulas (a1-r2-1) to (a1-r2-4), the groups represented by the above general formulas (a1-r2-1) or (a1-r2-4) are preferred.

[0181] As a structural unit (a1), specifically, the structural unit represented by the following general formula (a1-1) can be cited.

[0182] (The structural unit (a1) is represented by the general formula (a1-1)) In the resist composition according to the first embodiment of the present invention, the substrate component (A1) is preferably a polymeric compound containing a structural unit (a1) represented by the following general formula (a1-1).

[0183] [Chemical Formula 21] [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. Va] 1 It is a divalent hydrocarbon group that can have an ether bond. a1 It is an integer between 0 and 2. Ra 1 This indicates an acid-dissociable group. In the aforementioned formula (a1-1), the alkyl group of R having 1 to 5 carbon atoms is preferably a straight-chain or branched alkyl group having 1 to 5 carbon atoms. Specifically, examples include methyl, ethyl, propyl, isopropyl, n-butyl, isobutyl, tert-butyl, pentyl, isopentyl, neopentyl, etc. The haloalkyl group having 1 to 5 carbon atoms is a group obtained by substituting some or all of the hydrogen atoms of the aforementioned alkyl group having 1 to 5 carbon atoms with halogen atoms. Examples of halogen atoms include fluorine atoms, chlorine atoms, bromine atoms, iodine atoms, etc., with fluorine atoms being particularly preferred.

[0184] 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, a hydrogen atom or a methyl group is most preferred.

[0185] In the aforementioned equation (a1-1), Va 1 The divalent hydrocarbon group in it can be either an aliphatic hydrocarbon group or an aromatic hydrocarbon group.

[0186] As Va 1 The divalent hydrocarbon group in the aliphatic hydrocarbon group can be saturated or unsaturated, but is usually preferred to be saturated.

[0187] More specifically, examples of this aliphatic hydrocarbon group include straight-chain or branched aliphatic hydrocarbon groups, or aliphatic hydrocarbon groups containing rings in their structure.

[0188] The aforementioned 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.

[0189] As a straight-chain aliphatic hydrocarbon group, a straight-chain alkylene group is preferred. Specifically, examples include methylene [-CH2-], ethylene [-(CH2)2-], trimethylene [-(CH2)3-], tetramethylene [-(CH2)4-], pentamethylene [-(CH2)5-], etc.

[0190] The aforementioned 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.

[0191] As a branched aliphatic hydrocarbon group, a branched alkylene group is preferred. Specifically, examples include alkylmethylene groups such as -CH(CH3)-, -CH(CH2CH3)-, -C(CH3)2-, -C(CH3)(CH2CH3)-, -C(CH3)(CH2CH2CH3)-, and -C(CH2CH3)2-; alkylethylene groups such as -CH(CH3)CH2-, -CH(CH3)CH(CH3)-, -C(CH3)2CH2-, -CH(CH2CH3)CH2-, and -C(CH2CH3)2-CH2-; alkyltrimethylene groups such as -CH(CH3)CH2CH2- and -CH2CH(CH3)CH2-; and alkylalkylene groups such as -CH(CH3)CH2CH2CH2- and -CH2CH(CH3)CH2CH2-. The alkyl group in the alkyl alkylene group is preferably a straight-chain alkyl group having 1 to 5 carbon atoms.

[0192] Examples of aliphatic hydrocarbon groups containing rings in their structures include alicyclic hydrocarbon groups (groups obtained by removing two hydrogen atoms from an aliphatic hydrocarbon ring), groups obtained by attaching an alicyclic hydrocarbon group to the end of a straight-chain or branched aliphatic hydrocarbon group, and groups intermediate in the middle of a straight-chain or branched aliphatic hydrocarbon group. Examples of straight-chain or branched aliphatic hydrocarbon groups include groups identical to the aforementioned straight-chain or branched aliphatic hydrocarbon groups.

[0193] The aforementioned alicyclic hydrocarbon group preferably has 3 to 20 carbon atoms, and more preferably 3 to 12 carbon atoms.

[0194] The aforementioned alicyclic hydrocarbon group can be polycyclic or monocyclic. As a monocyclic alicyclic hydrocarbon group, it is preferably a group obtained by removing two hydrogen atoms from a monocyclic alkane. As this monocyclic alkane, it is preferably a monocyclic alkane with 3 to 6 carbon atoms, specifically cyclopentane, cyclohexane, etc. As a polycyclic alicyclic hydrocarbon group, it is preferably a group obtained by removing two hydrogen atoms from a polycyclic alkane. As this polycyclic alkane, it is preferably a polycyclic alkane with 7 to 12 carbon atoms, specifically adamantane, norbornane, isobornane, tricyclic [5.2.1.0] 2,6 Decane, tetracyclododecane, etc.

[0195] As Va 1 The aromatic hydrocarbon group in the divalent hydrocarbon group is a hydrocarbon group with an aromatic ring.

[0196] The number of carbon atoms in such aromatic hydrocarbon groups is preferably 3 to 30, more preferably 5 to 30, further preferably 5 to 20, particularly preferably 6 to 15, and most preferably 6 to 12. This number of carbon atoms does not include the number of carbon atoms in the substituents.

[0197] Aromatic rings, which are present in aromatic hydrocarbon groups, can specifically be exemplified by aromatic hydrocarbon rings such as those of benzene, biphenyl, fluorene, naphthalene, anthracene, and phenanthrene; and aromatic heterocycles, which are 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.

[0198] Specifically, examples of this aromatic hydrocarbon group include groups (arylenes) obtained by removing two hydrogen atoms from the aforementioned aromatic hydrocarbon ring; groups (aryl groups) obtained by replacing one hydrogen atom of one hydrogen atom of one hydrogen atom of an aryl group obtained by removing one hydrogen atom from the aforementioned aromatic hydrocarbon ring with an alkylene group (for example, groups obtained by further removing one hydrogen atom from an aryl group in arylalkyl groups such as benzyl, phenethyl, 1-naphthylmethyl, 2-naphthylmethyl, 1-naphthylethyl, 2-naphthylethyl, etc.). The aforementioned alkylene group (the alkyl chain in an arylalkyl group) preferably has 1 to 4 carbon atoms, more preferably 1 to 2, and particularly preferably 1.

[0199] In the aforementioned equation (a1-1), Ra 1 This indicates an acid-dissociating group. Examples of acid-dissociating groups include the acid-dissociating groups described above, preferably those represented by formulas (a1-r2-1) to (a1-r2-4), and more preferably those represented by formulas (a1-r2-1) or (a1-r2-4).

[0200] In the aforementioned equation (a1-1), n a1 n is an integer between 0 and 2. a1 Preferably 0 or 1, more preferably 0.

[0201] The aforementioned formula (a1-1) is preferably the following formula (a1-2).

[0202] [Chemical Formula 22] (In general formula (a1-2), R represents a hydrogen atom, an alkyl group having 1 to 5 carbon atoms, or a haloalkyl group having 1 to 5 carbon atoms. Va) 3 This indicates a divalent hydrocarbon group that can have an ether bond. na3 represents an integer from 0 to 2. Ra 031 Yab represents alkyl groups. 0 Represents a carbon atom. Xab 0 Indicates Yab 0 (A group that forms an alicyclic hydrocarbon group, wherein some or all of the hydrogen atoms in the alicyclic hydrocarbon group can be replaced.) In general formula (a1-2), R and Va 3 Relative to R and Va in equation (a1-1) 1 same.

[0203] In the general formula (a1-2), na3 is an integer from 0 to 2, preferably 0 or 1, and more preferably 0.

[0204] In general formula (a1-2), Ra 031 Xab 0 ,Yab 0 respectively with Ra in equation (a1-r2-1) 031 Xab 0 ,Yab 0 same.

[0205] In general formula (a1-2), Ra 031 In the above-mentioned case, the preferred form is a chain alkyl group, more preferably a monovalent chain alkyl group having 1 to 3 carbon atoms, and more preferably methyl, ethyl, propyl or isopropyl.

[0206] The specific details of structural unit (a1) are given below.

[0207] In the following formulas, R α It represents a hydrogen atom, a methyl group, or a trifluoromethyl group.

[0208] [Chemical Formula 23] [Chemical Formula 24] [Chemical Formula 25] [Chemical Formula 26] [Chemical Formula 27] [Chemical Formula 28] [Chemical Formula 29] [Chemical Formula 30] [Chemical Formula 31] [Chemical Formula 32] The resin (A1) may have one or more structural units (a1).

[0209] In the resin (A1), the proportion of structural unit (a1) relative to the total (100 mol%) of all structural units constituting the resin (A1) is preferably 5 to 50 mol%, more preferably 10 to 40 mol%, and even more preferably 10 to 35 mol%.

[0210] By setting the proportion of structural unit (a1) to the lower limit of the aforementioned preferred range, photolithography characteristics such as high sensitivity, resolution, and improved roughness are enhanced. Furthermore, by setting it to the upper limit, a balance with other structural units can be achieved, resulting in favorable photolithography characteristics.

[0211] <Structural Unit (st)> In addition to structural units (a10), the resin (A1) can also have a structure having structural units (st) derived from styrene or styrene derivatives.

[0212] A structural unit (st) is a structural unit derived from styrene or styrene derivatives. "Structural units derived from styrene" refers to structural units formed by the breaking of olefinic double bonds in styrene. "Structural units derived from styrene derivatives" refers to structural units formed by the breaking of olefinic double bonds in styrene derivatives.

[0213] "Styrene derivatives" refer to compounds obtained by substituting at least some of the hydrogen atoms of styrene with substituents. Examples of styrene derivatives include compounds obtained by substituting the hydrogen atom at the α-position of styrene with substituents, compounds obtained by substituting one or more hydrogen atoms of the benzene ring of styrene with substituents, and compounds obtained by substituting the hydrogen atom at the α-position of styrene and one or more hydrogen atoms of the benzene ring of styrene with substituents.

[0214] Examples of substituents that replace the hydrogen atom at the α-position of styrene include alkyl groups having 1 to 5 carbon atoms or haloalkyl groups having 1 to 5 carbon atoms.

[0215] As for the aforementioned alkyl group having 1 to 5 carbon atoms, it is preferably a straight-chain or branched alkyl group having 1 to 5 carbon atoms. Specifically, examples include methyl, ethyl, propyl, isopropyl, n-butyl, isobutyl, tert-butyl, pentyl, isopentyl, neopentyl, etc.

[0216] The aforementioned alkyl halogroups with 1 to 5 carbon atoms are groups obtained by substituting some or all of the hydrogen atoms of the aforementioned alkyl groups with 1 to 5 carbon atoms with halogen atoms. Examples of such halogen atoms include fluorine atoms, chlorine atoms, bromine atoms, and iodine atoms, with fluorine atoms being particularly preferred.

[0217] The substituent used to replace the hydrogen atom at the α-position of styrene is preferably an alkyl group or a fluoroalkyl group with 1 to 5 carbon atoms, more preferably an alkyl group or a fluoroalkyl group with 1 to 3 carbon atoms, and methyl is even more preferred for industrial availability.

[0218] Examples of substituents that replace the hydrogen atoms of the benzene ring in styrene include alkyl groups, alkoxy groups, halogen atoms, and haloalkyl groups.

[0219] Regarding the alkyl group used as the aforementioned substituent, it is preferably an alkyl group having 1 to 5 carbon atoms, and more preferably methyl, ethyl, propyl, n-butyl, or tert-butyl.

[0220] Regarding the alkoxy group used as the aforementioned substituent, it 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.

[0221] Regarding the halogen atom that can be used as a substituent, examples include fluorine, chlorine, bromine, and iodine atoms, with fluorine atoms being the preferred option.

[0222] Regarding the alkyl halogroups that are the aforementioned substituents, examples can be given of groups obtained by replacing some or all of the hydrogen atoms of the aforementioned alkyl group with the aforementioned halogen atoms.

[0223] The substituent used to replace the hydrogen atoms of the benzene ring of styrene is preferably an alkyl group having 1 to 5 carbon atoms, more preferably methyl or ethyl, and even more preferably methyl.

[0224] As a structural unit (st), it is preferably a structural unit derived from styrene, or a structural unit derived from a styrene derivative in which the hydrogen atom at the α-position of styrene is replaced by an alkyl group of 1 to 5 carbon atoms or a haloalkyl group of 1 to 5 carbon atoms, more preferably a structural unit derived from styrene, or a structural unit derived from a styrene derivative in which the hydrogen atom at the α-position of styrene is replaced by a methyl group, and even more preferably a structural unit derived from styrene.

[0225] The resin (A1) may have one or more structural units (st).

[0226] When the resin (A1) has structural units (st), the proportion of structural units (st) relative to the total (100 mol%) of all structural units constituting the resin (A1) is preferably 1 to 30 mol%, more preferably 3 to 30 mol%.

[0227] <Structural Unit (a20)> In addition to structural unit (a10), the resin (A1) can also have a structure with structural unit (a20).

[0228] The structural unit (a20) is the structural unit represented by the following general formula (a20-1).

[0229] [Chemical Formula 33] [In the formula, R] x2 It is a hydrogen atom, an alkyl group having 1 to 5 carbon atoms, or a haloalkyl group having 1 to 5 carbon atoms. x2 It is a divalent linker. Ra x2 It is an aliphatic hydrocarbon group. In the aforementioned equation (a20-1), R x2 It is a hydrogen atom, an alkyl group having 1 to 5 carbon atoms, or a haloalkyl group having 1 to 5 carbon atoms.

[0230] As R x2 Preferably, it is a hydrogen atom, an alkyl group having 1 to 5 carbon atoms, or a fluoroalkyl group having 1 to 5 carbon atoms. From the perspective of industrial availability, it is more preferably a hydrogen atom, a methyl group, or a trifluoromethyl group, and even more preferably a hydrogen atom or a methyl group. It is particularly preferably a hydrogen atom.

[0231] In the aforementioned formula (a20-1), Ya x2 It is a divalent linker.

[0232] In the aforementioned equation (a20-1), Ya is... x2 The divalent linking group is not particularly limited, and divalent hydrocarbon groups with substituents and divalent linking groups containing heteroatoms can be cited as suitable linking groups.

[0233] Examples of substituent-containing divalent hydrocarbon groups and heteroatom-containing divalent linking groups include those related to the above-mentioned Ya. x1 The same group as the divalent hydrocarbon group and the divalent linking group containing heteroatoms.

[0234] In the aforementioned equation (a20-1), Ya is... x2 The preferred components are ester bonds [-C(=O)-O-, -OC(=O)-], ether bonds (-O-), straight-chain or branched alkylene groups, or combinations thereof, with ester bonds [-C(=O)-, -OC(=O)-] being more preferred.

[0235] In the aforementioned formula (a20-1), Ra x2 It is an aliphatic hydrocarbon group. As Ra x2 Aliphatic hydrocarbon groups can be exemplified by straight-chain or branched alkyl groups, or cyclic aliphatic hydrocarbon groups.

[0236] The linear alkyl group preferably has 1 to 5 carbon atoms, more preferably 2 to 5 carbon atoms, and even more preferably 3 to 5 carbon atoms. Specifically, examples include methyl, ethyl, n-propyl, n-butyl, and n-pentyl.

[0237] The branched alkyl group preferably has 3 to 10 carbon atoms, more preferably 3 to 5 carbon atoms. Specifically, examples include isopropyl, isobutyl, tert-butyl, isopentyl, neopentyl, 1,1-diethylpropyl, 2,2-dimethylbutyl, etc., with isopropyl being the most preferred.

[0238] The cyclic aliphatic hydrocarbon group can be a polycyclic group or a monocyclic group.

[0239] The aliphatic hydrocarbon group that is a monocyclic group is preferably a group obtained by removing one hydrogen atom from a monocyclic alkane. The monocyclic alkane is preferably a monocyclic alkane with 3 to 6 carbon atoms, and examples include cyclopentane and cyclohexane.

[0240] Regarding the aliphatic hydrocarbon group as a polycyclic group, it is preferred to be a group obtained by removing one hydrogen atom from a polycyclic alkane. The polycyclic alkane is preferably a polycyclic alkane with 7 to 12 carbon atoms, and examples include adamantane, norbornane, isobornane, tricyclodecane, tetracyclododecane, etc.

[0241] Furthermore, cyclic hydrocarbon groups can contain heteroatoms, similar to heterocycles. Examples of heteroatoms include oxygen, sulfur, and nitrogen atoms. Specific examples of such heterocycles include aliphatic heterocycles such as tetrahydrofuran, tetrahydropyran, and tetrahydrothiophene.

[0242] It should be noted that Ra x2 The aliphatic hydrocarbon groups in the text are unsubstituted aliphatic hydrocarbon groups, excluding Ra. x2 A hydrocarbon group in which some or all of the hydrogen atoms are replaced by a group with heteroatoms.

[0243] In the aforementioned formula (a20-1), regarding Ra x2 Of the above, preferably are straight-chain or branched alkyl groups having 1 to 5 carbon atoms, groups obtained by removing one hydrogen atom from a monocyclic alkane, or groups obtained by removing one hydrogen atom from a polycyclic alkane; more preferably are straight-chain or branched alkyl groups having 1 to 5 carbon atoms, groups obtained by removing one hydrogen atom from a monocyclic alkane, or adamantyl alkyl groups; even more preferably are straight-chain or branched alkyl groups having 1 to 5 carbon atoms, or groups obtained by removing one hydrogen atom from a monocyclic alkane; and particularly preferably are straight-chain or branched alkyl groups having 1 to 5 carbon atoms.

[0244] The following shows a specific example of the structural unit (a20) represented by the aforementioned formula (a20-1).

[0245] In the following formulas, R α It represents a hydrogen atom, a methyl group, or a trifluoromethyl group.

[0246] [Chemical Formula 34] As a structural unit (a20), the above-mentioned structural unit is preferably represented by any one of the above-mentioned general formulas (a20-01-1), (a20-01-3), (a20-01-4), and (a20-02-1), and more preferably by any one of the above-mentioned general formulas (a20-01-1), (a20-01-4), and (a20-02-1).

[0247] The resin (A1) in the resist composition according to the first embodiment of the present invention may have one or more structural units (a20).

[0248] When the resin (A1) has structural units (a20), the proportion of structural units (a20) relative to the total (100 mol%) of all structural units constituting the resin (A1) is preferably 2 to 70 mol%, more preferably 3 to 60 mol%, even more preferably 5 to 50 mol%, and particularly preferably 10 to 40 mol%.

[0249] <Other structural units> The resin (A1) may also have structural units other than the above-mentioned structural units (a10), structural units (a1), structural units (st), and structural units (a20).

[0250] Other structural units include, for example, structural units (a2) containing lactone cyclic groups, cyclic groups containing -SO2-, or cyclic groups containing carbonates, and structural units (a3) ​​containing aliphatic hydrocarbon groups containing polar groups. As structural units (a2) and (a3), most structural units known to date as resin components for resist compositions can be used.

[0251] 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 1,000 to 50,000, more preferably 2,000 to 30,000, and even more preferably 3,000 to 20,000.

[0252] If the Mw of component (A1) is below the preferred upper limit of the range, it has sufficient solubility in the resist solvent for use as a resist; if it is above the preferred lower limit of the range, it has good resistance to dry etching and good resist pattern cross-sectional shape.

[0253] (A1) The dispersion of the component (Mw / Mn) 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. It should be noted that Mn represents the number-average molecular weight.

[0254] [The corrosion resist composition according to the second embodiment] The resist composition according to the second embodiment of the present invention contains a substrate component (A2) comprising an alkali-soluble resin (A2), an acid-generating agent component (B) that generates acid by exposure, and a crosslinking agent (C). The alkali-soluble resin (A2) comprises a structural unit (a10) represented by the following general formula (a10-1), the aforementioned component (B) comprises a compound represented by the following general formula (b-1), and the aforementioned crosslinking agent (C) comprises at least one crosslinking agent selected from the group consisting of melamine-based crosslinking agents, urea-based crosslinking agents, alkylene urea-based crosslinking agents, glycourea-based crosslinking agents, and epoxy-based crosslinking agents.

[0255] [Chemical Formula 35] In general 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. x1 It is a single bond or a divalent linker. Wa x1 For (n) ax1 +1) Aromatic hydrocarbon group. ax1 Integers greater than or equal to 1. [Chemical Formula 36] In general formula (b-1), Ra represents an optional organic group. m+ This represents an organic cation with a valence of m. m represents an integer greater than or equal to 1. (A2) Ingredients In the resist composition according to the second embodiment of the present invention, as described above, component (A2) comprises an alkali-soluble resin (A2) (hereinafter also referred to as "resin (A2)"), which comprises a structural unit (a10) represented by the above general formula (a10-1).

[0256] As a structural unit (a10), the same structural unit as the structural unit (a10) in the resist composition according to the first embodiment described above can be cited.

[0257] The resin (A2) may have one or more structural units (a10).

[0258] When the resin (A2) has structural units (a10), the proportion of structural units (a10) relative to the total (100 mol%) of all structural units constituting the resin (A2) is preferably 30 to 100 mol%, more preferably 40 to 100 mol%, and even more preferably 50 to 100 mol%.

[0259] As a resin (A2), in addition to the structural unit (a10), it may also have a structure having at least one of the structural units (structural unit (a20)) represented by the above general formula (a20-1) and the structural units (st) derived from styrene or styrene derivatives.

[0260] As structural units (a20) and (st), examples can be the same structural units as those in the resist composition described in the first embodiment above.

[0261] The resin (A2) may have one or more structural units (st).

[0262] When the resin (A2) has structural units (st), the proportion of structural units (st) relative to the total (100 mol%) of all structural units constituting the resin (A2) is preferably 1 to 30 mol%, more preferably 3 to 30 mol.

[0263] In the second embodiment of the present invention, when the resin (A2) in the resist composition has structural unit (a20), the proportion of structural unit (a20) in the resin (A2) relative to the total of all structural units constituting the resin (A2) (100 mol%) is preferably 2 to 70 mol%, more preferably 3 to 60 mol%, further preferably 5 to 50 mol%, and particularly preferably 10 to 40 mol%.

[0264] By setting the ratio of the structural unit (a20) to or above the aforementioned preferred lower limit, the resolution and CDU can be further improved.

[0265] On the other hand, by setting the ratio of the structural unit (a20) to below the above-mentioned preferred upper limit value, the resolution can be further improved.

[0266] The resin (A2) may have one or more structural units (a20).

[0267] Other Structural Units The resin (A2) may also have structural units other than the above-mentioned structural units (a10), structural units (st), and structural units (a20).

[0268] Other structural units include, for example, structural units containing a protecting group (a1), structural units containing a cyclic group containing a lactone, a cyclic group containing -SO2-, or a cyclic group containing a carbonate (a2), and structural units containing an aliphatic hydrocarbon group containing a polar group (a3). Most structural units known to date as resin components for resist compositions can be used as structural units (a1), (a2), and (a3).

[0269] In the resist composition according to the second embodiment of the present invention, component (A2) may be used alone or in combination with two or more components.

[0270] (A2) The weight-average molecular weight (Mw) of the component (based on polystyrene conversion standard by gel permeation chromatography (GPC)) is not particularly limited, but is preferably 1,000 to 20,000, more preferably 1,500 to 10,000, and even more preferably 2,000 to 5,000.

[0271] If the Mw of component (A2) is below the preferred upper limit of this range, it has sufficient solubility in resist solvents and alkaline developers for use as a resist; if it is above the preferred lower limit of this range, it has good resistance to dry etching and good resist pattern cross-sectional shape.

[0272] (A2) The dispersion of the component (Mw / Mn) is not particularly limited, but is preferably 1.0 to 4.0, more preferably 1.0 to 3.0, and particularly preferably 1.0 to 2.0. It should be noted that Mn represents the number-average molecular weight.

[0273] Acid-producing component (Component (B)) The resist composition according to the first embodiment of the present invention and the resist composition according to the second embodiment of the present invention (hereinafter, sometimes simply referred to as resist composition) respectively contain an acid-generating agent component (B) (hereinafter also referred to as "(B) component") that generates acid by exposure, and the acid-generating agent component (B) includes an acid-generating agent (B1) (hereinafter, sometimes referred to as "(B1) component") formed from a compound represented by the following general formula (b-1).

[0274] [Chemical Formula 37] In general formula (b-1), Ra represents an optional organic group. m+ This represents an organic cation with a valence of m. m represents an integer greater than or equal to 1. [Anion portion (C6F5-SO2-N)] - -SO2-Ra] In the aforementioned formula (b-1), Ra represents an optional organic group. Examples of organic groups that can be substituents include monovalent hydrocarbon groups. This hydrocarbon group can be an aliphatic hydrocarbon group or an aromatic hydrocarbon group.

[0275] Aliphatic hydrocarbon groups in Ra The aliphatic hydrocarbon group represents a hydrocarbon group that is not aromatic. This aliphatic hydrocarbon group can be saturated or unsaturated, but is generally preferred to be saturated.

[0276] Examples of aliphatic hydrocarbon groups include straight-chain or branched aliphatic hydrocarbon groups, or aliphatic hydrocarbon groups containing rings in their structure.

[0277] ...straight-chain or branched aliphatic hydrocarbon groups Examples of linear or branched aliphatic hydrocarbon groups include alkyl, alkenyl, and alkynyl groups. Examples of alkyl groups include methyl, ethyl, propyl, isopropyl, butyl, isobutyl, S-butyl, T-butyl, pentyl, hexyl, heptyl, octyl, 2-ethylhexyl, nonyl, and decyl groups, which have 1 to 20 carbon atoms (preferably 1 to 10, more preferably 1 to 6). Examples of alkenyl groups include vinyl, allyl, and butenyl groups, which have 2 to 20 carbon atoms (preferably 2 to 10, more preferably 2 to 6). Examples of alkynyl groups include ethynyl and propynyl groups, which have 2 to 20 carbon atoms (preferably 2 to 10, more preferably 2 to 6).

[0278] The aforementioned straight-chain or branched aliphatic hydrocarbon groups may or may not have substituents. Examples of substituents include fluorine atoms, fluoroalkyl groups with 1 to 5 carbon atoms substituted with fluorine atoms, and carbonyl groups. Fluorine atoms are preferred.

[0279] ...aliphatic hydrocarbon groups containing rings in their structure Examples of aliphatic hydrocarbon groups containing rings in the aforementioned structure include alicyclic hydrocarbon groups, groups obtained by alicyclic hydrocarbon groups bonded to the end of straight-chain or branched aliphatic hydrocarbon groups, and groups with alicyclic hydrocarbon groups intermediate in the middle of straight-chain or branched aliphatic hydrocarbon groups.

[0280] Examples of alicyclic hydrocarbon groups include cycloalkyl groups with 3 to 8-membered rings such as cyclopropyl, cyclobutyl, cyclopentyl, cyclohexyl, cycloheptyl, and cyclooctyl; cycloalkenyl groups with 3 to 8-membered rings such as cyclopentenyl and cyclohexenyl; and bridged cyclic hydrocarbon groups with 4 to 20 carbon atoms (preferably 7 to 12 carbon atoms) such as adamantyl and norbornyl.

[0281] Cyclic aliphatic hydrocarbon groups may or may not have substituents. Examples of substituents include alkyl groups, alkoxy groups, halogen atoms, haloalkyl groups, haloalkoxy groups, hydroxyl groups, and carbonyl groups.

[0282] Regarding the alkyl group used as the aforementioned substituent, it is preferably an alkyl group having 1 to 5 carbon atoms, and most preferably methyl, ethyl, n-propyl, isopropyl, n-butyl, or tert-butyl.

[0283] Regarding the alkoxy group used as the aforementioned substituent, it is preferably an alkoxy group having 1 to 5 carbon atoms, preferably methoxy, ethoxy, n-propoxy, isopropoxy, n-butoxy, or tert-butoxy, and most preferably methoxy or ethoxy.

[0284] Regarding the halogen atom that can be used as a substituent, examples include fluorine, chlorine, bromine, and iodine atoms, with fluorine atoms being the preferred option.

[0285] Regarding the halogenated alkoxy group that serves as the aforementioned substituent, examples can be given of groups obtained by replacing some or all of the hydrogen atoms of the aforementioned alkoxy group with the aforementioned halogen atoms.

[0286] Regarding the alkyl halogroups that are the aforementioned substituents, examples can be given of groups obtained by replacing some or all of the hydrogen atoms of the aforementioned alkyl group with the aforementioned halogen atoms.

[0287] In a cyclic aliphatic hydrocarbon group, a portion of the carbon atoms constituting its ring structure can be replaced by substituents containing heteroatoms. Preferred substituents containing heteroatoms are -O-, -C(=O)-O-, -S-, -S(=O)2-, and -S(=O)2-O-.

[0288] Aromatic hydrocarbon groups in Ra The aromatic hydrocarbon group is a hydrocarbon group having at least one aromatic ring.

[0289] The aromatic ring is not particularly limited to a cyclic conjugated system having 4n+2 π electrons; it can be monocyclic or polycyclic. The number of carbon atoms in the aromatic ring is preferably 5 to 30, more preferably 5 to 20, further preferably 6 to 15, and particularly preferably 6 to 12. This number of carbon atoms does not include the number of carbon atoms in the substituents. Specifically, examples of aromatic rings include aromatic hydrocarbon rings such as benzene, naphthalene, anthracene, and phenanthrene; and aromatic heterocycles obtained 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.

[0290] As aromatic heterocycles, examples include pyridine rings and thiophene rings.

[0291] Specifically, examples of aromatic hydrocarbon groups include groups (aryl or heteroaryl) obtained by removing one hydrogen atom from the aforementioned aromatic hydrocarbon ring or aromatic heterocycle; groups obtained by removing one hydrogen atom 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 the aforementioned aromatic hydrocarbon ring or aromatic heterocycle with an alkyl group (e.g., benzyl, phenethyl, 1-naphthylmethyl, 2-naphthylmethyl, 1-naphthylethyl, 2-naphthylethyl, etc., arylalkyl groups). The alkylene group bonded to the aforementioned aryl or heteroaryl group preferably has 1 to 4 carbon atoms, more preferably 1 to 2, and particularly preferably 1.

[0292] In the aforementioned aromatic hydrocarbon group, the hydrogen atoms present in the aromatic hydrocarbon group can be replaced by substituents. For example, the hydrogen atoms bonded to the aromatic ring in the aromatic hydrocarbon group can be replaced by substituents. Examples of such substituents include halogen atoms, hydrocarbon groups that may have substituents, alkoxy groups, haloalkoxy groups, hydroxyl groups, etc. Examples of hydrocarbon groups that may have substituents include alkyl groups, alkenyl groups, alkynyl groups, etc., preferably alkyl groups having 1 to 5 carbon atoms. Examples of such substituents in hydrocarbon groups that may have substituents include halogen atoms, preferably fluorine atoms.

[0293] Regarding the halogen atom, alkoxy group, haloalkyl group, and haloalkoxy group that are the aforementioned substituents, examples can be given as substituents that replace the hydrogen atoms of the aforementioned cyclic aliphatic hydrocarbon groups.

[0294] In this embodiment, Ra is preferably an aryl, alkyl, or haloalkyl group substituted with a halogen atom, haloalkyl, or haloalkoxy group, and more preferably an aryl group substituted with a halogen atom.

[0295] As an alkyl group, it is preferably an alkyl group having 1 to 5 carbon atoms, and more preferably methyl, ethyl, n-propyl, isopropyl, n-butyl, or tert-butyl.

[0296] As a haloalkyl group, examples include groups obtained by substituting some or all of the hydrogen atoms of the alkyl group with halogen atoms, and preferably groups obtained by substituting all of the hydrogen atoms of the alkyl group with halogen atoms.

[0297] Examples of haloalkoxy groups include those obtained by replacing some or all of the hydrogen atoms of the alkoxy group with halogen atoms, and preferably those obtained by replacing all of the hydrogen atoms of the alkoxy group with halogen atoms.

[0298] Examples of halogen atoms include fluorine, chlorine, bromine, and iodine, with fluorine being the preferred choice.

[0299] Aryl groups with 6 to 20 carbon atoms can be cited as examples, with phenyl and naphthyl groups being preferred.

[0300] The anionic portion of component (B1) is preferably an anion represented by the following formula (an-b-3).

[0301] [Chemical Formula 38] [In formula (an-b-3), R1 to R5 are each independently a hydrogen atom, a halogen atom, an alkoxy group, a haloalkyl group, a hydroxyl group, a carbonyl group, a nitro group, or a hydrocarbon group that may have substituents. Any two or more of R1 to R5 can be bonded together to form a ring.] Examples of halogen atoms represented by R1 to R5 in the general formula (an-b-3) include fluorine atoms, chlorine atoms, bromine atoms, and iodine atoms, with fluorine atoms being the most preferred.

[0302] Examples of hydrocarbon groups that can have substituents, represented by R1 to R5, include alkyl, alkenyl, and ynyl groups. Examples of alkyl, alkenyl, and ynyl groups include alkyl, alkenyl, and ynyl groups that are aliphatic hydrocarbon groups in Ra, preferably alkyl groups having 1 to 5 carbon atoms. Examples of substituents that can have substituents, including alkyl, alkoxy, halogen atoms, haloalkyl, hydroxyl, carbonyl, and nitro groups, are preferably halogen atoms, and more preferably fluorine atoms.

[0303] When any two or more of R1 to R5 are bonded to each other to form a ring, they can form an aromatic ring or an aliphatic ring together with the phenyl bonded to R1 to R5, preferably an aromatic ring or an aliphatic ring with 6 to 20 carbon atoms.

[0304] The following are specific examples of the anionic portion in component (B1). It should be noted that the anionic portion in component (B1) is not limited to these specific examples.

[0305] [Chemical Formula 39] [Cation section: M] m+ ] In the aforementioned general formula (b-1), M m+ The organic cation is an m-valent organic cation, preferably an m-valent ononium cation. Among them, sulfonium cation and iodoonium cation are preferred.

[0306] m is an integer greater than or equal to 1.

[0307] As M m+ The organic cations in it are preferably ononium cations, more preferably sulfonium cations or iodonium cations.

[0308] As a preferred cation portion M m+Organic cations represented by any of the following general formulas (ca-1) to (ca-3) can be cited.

[0309] [Chemical Formula 40] In general formulas (ca-1) to (ca-3), R 201 ~R 207 Each can independently represent an aryl group, an alkyl group, or an alkenyl group that may have substituents, where some carbon atoms can be replaced by heteroatoms. R 201 ~R 203 R 206 ~R 207 They can bond with each other and form a ring together with the sulfur atoms in the formula. R 208 ~R 209 Each independently represents an alkyl group having 1 to 5 hydrogen atoms or carbon atoms, R 210 It can be an aryl group that may have a substituent, an alkyl group that may have a substituent, an alkenyl group that may have a substituent, or a cyclic group containing -SO2- that may have a substituent, L 201 This represents -C (=O)- or -C (=O)-O-. As R 201 ~R 207 The aryl group in the formula can be aryl groups with 6 to 20 carbon atoms, preferably phenyl or naphthyl.

[0310] As R 201 ~R 207 The alkyl group in the alkyl group is preferably a chain or cyclic alkyl group and has 1 to 30 carbon atoms.

[0311] As R 201 ~R 207 The alkenyl group in the form of the alkenyl group is preferably an alkenyl group with 2 to 10 carbon atoms.

[0312] As R 201 ~R 207 and R 210 Possible substituents include, for example, alkyl, halogen atoms, haloalkyl, carbonyl, cyano, amino, aryl, and groups represented by the general formula [-Yca0-Rca0] (where Yca0 is a single bond or a divalent linked group, and Rca0 is a hydrogen atom or a hydrocarbon group).

[0313] The divalent linking group in YcaO, which is represented by the general formula [-YcaO-RcaO], is preferably -S-, ester bond [-C(=O)-O-, -OC(=O)-], ether bond (-O-), straight-chain or branched alkylene group, or a combination thereof, and more preferably a group formed from a combination of ether bond (-O-) and straight-chain or branched alkylene group.

[0314] In the above general formula [-Yca0-Rca0], the hydrocarbon group in Rca0 can be the same group as the hydrocarbon group in Ra, preferably an aliphatic hydrocarbon group, more preferably a straight-chain or branched aliphatic hydrocarbon group, or an aliphatic hydrocarbon group containing a ring in the structure.

[0315] As a group represented by the general formula [-Yca0-Rca0], examples can be given of groups represented by the following formulas (ca-r-1) to (ca-r-7).

[0316] [Chemical Formula 41] [In the formula, R'] 201 Each group can be an independent hydrogen atom, a cyclic group that may have substituents, a chain-like alkyl group that may have substituents, or a chain-like alkenyl group that may have substituents. As R' 201 The cyclic group represented may have substituents, preferably a cyclic hydrocarbon group, which may be an aromatic hydrocarbon group or an aliphatic hydrocarbon group.

[0317] Examples of aromatic hydrocarbon groups include aryl groups obtained by removing one hydrogen atom from an aromatic hydrocarbon ring or an aromatic compound containing two or more aromatic rings, with phenyl and naphthyl being preferred.

[0318] Examples of aliphatic hydrocarbon groups include groups obtained by removing one hydrogen atom from monocyclic or polycyclic alkanes, preferably cyclopropyl, cyclobutyl, cyclopentyl, cyclohexyl, cycloheptyl, cyclooctyl, adamantyl, and norbornyl.

[0319] As R' 201 The alkyl group represented may have substituents and can be either straight-chain or branched.

[0320] As a straight-chain alkyl group, the number of carbon atoms is preferably 1 to 20, more preferably 1 to 15, and most preferably 1 to 10. Specifically, examples include methyl, ethyl, propyl, butyl, pentyl, hexyl, heptyl, octyl, nonyl, decyl, undecyl, dodecyl, tridecyl, isotriadecyl, tetradecyl, pentadecyl, hexadecyl, isohexadecanyl, heptadecanyl, octadecyl, nonadecanyl, eicosyl, dodecyl, and dodecyl.

[0321] As R' 201The represented chain alkenyl group, which may have substituents, can be either straight-chain or branched, and the number of carbon atoms is preferably 2 to 10, more preferably 2 to 5, further preferably 2 to 4, and particularly preferably 3. Examples of straight-chain alkenyl groups include vinyl, allyl, and butenyl. Examples of branched alkenyl groups include 1-methylpropenyl and 2-methylpropenyl.

[0322] Of the above-mentioned chain-like alkenyl groups, propenyl groups are particularly preferred.

[0323] As R' 201 The cyclic groups represented may have substituents, and other groups may be the same as the acid-dissociable groups represented by the above formula (a1-r2-1).

[0324] As R' 201 The substituents in the cyclic group, chain alkyl group, or chain alkenyl group can be exemplified by alkyl, alkoxy, halogen atom, haloalkyl, hydroxyl, carbonyl, nitro, etc.

[0325] Regarding the alkyl group used as a substituent, it is preferably an alkyl group having 1 to 6 carbon atoms, and most preferably methyl, ethyl, propyl, n-butyl, tert-butyl, cyclopropyl, cyclobutyl, cyclopentyl, or cyclohexyl.

[0326] Regarding the alkoxy group as a substituent, it is preferred to be an alkoxy group having 1 to 5 carbon atoms, more preferably methoxy, ethoxy, n-propoxy, isopropoxy, n-butoxy, or tert-butoxy, and most preferably methoxy or ethoxy.

[0327] Regarding halogen atoms used as substituents, examples include fluorine atoms, chlorine atoms, bromine atoms, and iodine atoms, with fluorine atoms being the preferred choice.

[0328] Regarding alkyl halogens as substituents, examples include alkyl groups with 1 to 5 carbon atoms, such as methyl, ethyl, propyl, n-butyl, tert-butyl, etc., in which some or all of the hydrogen atoms are replaced by the aforementioned halogen atoms.

[0329] R 201 ~R 203 R 206 ~R 207 Some carbon atoms can be replaced by heteroatoms, which, when bonded together with the sulfur atom in the formula to form a ring, can be via heteroatoms such as sulfur, oxygen, and nitrogen atoms, carbonyl groups, -SO-, -SO2-, -SO3-, -COO-, -CONH-, or -N(R) N )-(the R NThe ring is bonded to functional groups such as alkyl groups having 1 to 5 carbon atoms. As for the ring formed, in the case of a ring whose ring skeleton includes a sulfur atom, it is preferably a 3- to 10-membered ring, particularly preferably a 5- to 7-membered ring, including the sulfur atom. Specific examples of the formed ring include tetrahydrothiophene rings, sulfide cyclopentane rings, thiophene rings, thiazole rings, benzothiophene rings, thiathracene rings, dibenzothiophene rings, 9H-thioxanthene rings, thioxanone rings, thiathracene rings, phenoxathiazole rings, thiaxane rings, and thiaxane-onium rings.

[0330] R 208 ~R 209 Each of the above independently represents an alkyl group having 1 to 5 hydrogen atoms or carbon atoms, preferably an alkyl group having 1 to 3 hydrogen atoms or carbon atoms. In R 208 ~R 209 When each alkyl group is independently formed, they can bond with each other to form a ring.

[0331] R 210 It can be an aryl group that may have a substituent, an alkyl group that may have a substituent, an alkenyl group that may have a substituent, or a cyclic group containing -SO2- that may have a substituent.

[0332] As R 210 The aryl group in the formula can be an unsubstituted aryl group with 6 to 20 carbon atoms, preferably phenyl or naphthyl.

[0333] As R 210 The alkyl group in the alkyl group is preferably a chain or cyclic alkyl group and has 1 to 30 carbon atoms.

[0334] As R 210 The alkenyl group in the form of the group preferably has 2 to 10 carbon atoms.

[0335] In R 210 Among the cyclic groups containing -SO2- that can have substituents, "cyclic group containing -SO2-" refers to a cyclic group whose ring skeleton contains a ring containing -SO2-. Specifically, it is a cyclic group in which the sulfur atom (S) in -SO2- forms part of the ring skeleton of the cyclic group. The ring containing -SO2- in its ring skeleton is counted as the first ring. If it consists only of this ring, it is a monocyclic group. If it has other ring structures, regardless of its structure, it is called a polycyclic group. Cyclic groups containing -SO2- can be monocyclic or polycyclic.

[0336] Cyclic groups containing -SO2- are particularly preferred to be cyclic groups containing -O-SO2- in their ring skeleton, that is, cyclic groups containing a sultone ring in which -OS- in -O-SO2- forms part of the ring skeleton.

[0337] The cation represented by formula (ca-1) is preferably the cation represented by the following formula (ca-b-2).

[0338] [Chemical Formula 42] In formula (ca-b-2), Rb 01 ~Rb 03 Each can be an aryl group, an alkyl group, or an alkenyl group, each with substituents, and some carbon atoms can be replaced by heteroatoms. Rb 02 and Rb 03 It can bond with the sulfur atom in the formula to form a ring. Lb 01 It is a single bond or a divalent linker. In equation (ca-b-2), Rb is used as... 01 Examples of R in the general formula (ca-1) can be cited. 201 The aryl, alkyl, or alkenyl groups that may have substituents can have a portion of their carbon atoms replaced with heteroatoms. More preferably, these are unsubstituted aryl groups, or aryl groups having alkyl groups or groups represented by the above general formula [-Yca0-Rca0] (where Yca0 is a single bond or a divalent linking group, and Rca0 is a hydrogen atom or a hydrocarbon group) as substituents.

[0339] In equation (ca-b-2), Rb is used as... 02 ~Rb 03 Examples of R in the general formula (ca-1) can be cited. 201 The examples given are aryl groups that may have substituents, alkyl groups that may have substituents, or alkenyl groups that may have substituents.

[0340] Rb 02 and Rb 03 Some carbon atoms can be replaced by heteroatoms, which, when bonded together with the sulfur atom in the formula to form a ring, can be via heteroatoms such as sulfur, oxygen, and nitrogen atoms, carbonyl groups, -SO-, -SO2-, -SO3-, -COO-, -CONH-, or -N(R) N )-(the R N The ring is bonded to functional groups such as alkyl groups having 1 to 5 carbon atoms. As for the ring formed, in the case of a ring whose ring skeleton includes a sulfur atom, it is preferably a 3- to 10-membered ring, particularly preferably a 5- to 7-membered ring, including the sulfur atom. Specific examples of the formed ring include tetrahydrothiophene rings, sulfide cyclopentane rings, thiophene rings, thiazole rings, benzothiophene rings, dibenzothiophene rings, 9H-thioxanthene rings, thioxanone rings, thiathrone rings, phenoxathiazole rings, and thiaxane rings.

[0341] Lb01 It is a single bond or a divalent linker.

[0342] As Lb 01 The divalent linking group is preferably a carbonyl (-CO-), 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 group formed from a combination of a carbonyl (-CO-) and a straight-chain or branched alkylene group.

[0343] As a group formed from a combination of a carbonyl group (-CO-) and a straight-chain or branched alkylene group, specifically, examples of the general formula [ -Yca1-Yca2- The groups indicated by ] (Yca1 is a straight-chain or branched alkylene group. Yca2 is a carbonyl group (-CO-). This represents the linking bond with the sulfur atom in formula (ca-b-2). Rb in equation (ca-b-2) 01 (The connecting key of the bond).

[0344] The cation represented by formula (ca-b-2) is preferably the cation represented by formula (ca-b-3).

[0345] [Chemical Formula 43] In the general formula (ca-b-3), Rb 01 It can be an aryl group, an alkyl group, or an alkenyl group that can have substituents, and some carbon atoms can be replaced with heteroatoms. Yb 01 This is a group that forms an aliphatic ring together with the sulfur atom in the formula. The sulfur atom in the formula and Yb 01 The resulting aliphatic ring may contain ether bonds and may have substituents. Lb 01 It is a single bond or a divalent linker. Rb in general formula (ca-b-3) 01 Rb in the aforementioned general formula (ca-b-2) 01 same.

[0346] Lb in general formula (ca-b-3) 01 Lb in the aforementioned general formula (ca-b-2) 01 same.

[0347] Yb in general formula (ca-b-3) 01This is a group that forms an aliphatic ring together with the sulfur atom in the formula. The aliphatic ring may have substituents; examples of such substituents include Rb in the aforementioned general formula (ca-b-2). 01 It can have the same substituents.

[0348] Yb in general formula (ca-b-3) 01 Preferably, it is a group that, together with the sulfur atom in the formula, forms a tetrahydrothiophene ring or a sulfide cyclopentane ring.

[0349] The following are specific examples of the cationic portion of component (B), but are not limited to these.

[0350] For example, as a suitable cation represented by formula (ca-1), specifically, any of the following formulas (ca-1-1) to (ca-1-67) can be cited as cations.

[0351] [Chemical Formula 44] [Chemical Formula 45] [Chemical Formula 46] [In the formula, g1, g2, and g3 represent the number of repetitions, where g1 is an integer from 1 to 5, g2 is an integer from 0 to 20, and g3 is an integer from 0 to 20.] [Chemical Formula 47] [In the formula, R”] 201 As a substituent, as a substituent, and as the aforementioned R 201 ~R 207 and R 210 The substituents that can be present are the same as those listed above. As a suitable cation represented by the aforementioned formula (ca-3), specifically, cations represented by any of the following formulas (ca-3-1) to (ca-3-7) can be cited.

[0352] [Chemical Formula 48] The following substance is preferred as the cationic portion of component (B) above.

[0353] [Chemical Formula 49] [Chemical Formula 50] [In the formula, R”] 201The substituent is an alkyl group, a halogen atom, a haloalkyl group, a carbonyl group, a cyano group, an amino group, an aryl group, or a group represented by each of the above general formulas (ca-r-1) to (ca-r-7). As the cation portion of component (B), the cations described above are preferably those represented by any one of the chemical formulas (ca-1-1), (ca-1-16), (ca-01-1) to (ca-01-14), more preferably those represented by any one of the chemical formulas (ca-01-1) to (ca-01-3), (ca-01-9), (ca-01-11) to (ca-01-13), and even more preferably those represented by any one of the chemical formulas (ca-01-1) to (ca-01-3), (ca-01-11).

[0354] The compound represented by the above general formula (b-1) is preferably the compound represented by the following general formula (b-2).

[0355] [Chemical Formula 51] In general formula (b-2), Ra represents an optional organic group. Rb 01 ~Rb 03 Each can be an aryl group, an alkyl group, or an alkenyl group, each with substituents, and some carbon atoms can be replaced by heteroatoms. Rb 02 and Rb 03 It can bond with the sulfur atom in the formula to form a ring. Lb 01 It is a single bond or a divalent linker. Ra in general formula (b-2) is the same as Ra in general formula (b-1).

[0356] Rb in general formula (b-2) 01 ~Rb 03 and Lb 01 Rb in the above formula (ca-b-2) 01 ~Rb 03 and Lb 01 same.

[0357] The compound represented by the above general formula (b-2) is preferably the compound represented by the following general formula (b-3).

[0358] [Chemical Formula 52] In general formula (b-3), R1 to R5 are each independently a hydrogen atom, a halogen atom, an alkoxy group, a haloalkyl group, a hydroxyl group, a carbonyl group, a nitro group, or a hydrocarbon group that may have substituents. Any two or more of R1 to R5 can bond with each other to form a ring. Rb 01~Rb 03 Each can be an aryl group, an alkyl group, or an alkenyl group, each with substituents, and some carbon atoms can be replaced by heteroatoms. Rb 02 and Rb 03 It can bond with the sulfur atom in the formula to form a ring. Lb 01 It is a single bond or a divalent linker. Examples of halogen atoms represented by R1 to R5 in general formula (b-3) include fluorine atoms, chlorine atoms, bromine atoms, and iodine atoms, with fluorine atoms being the most preferred.

[0359] Examples of hydrocarbon groups that can have substituents, represented by R1 to R5, include alkyl, alkenyl, and ynyl groups. Examples of alkyl, alkenyl, and ynyl groups include alkyl, alkenyl, and ynyl groups that are aliphatic hydrocarbon groups in Ra, preferably alkyl groups having 1 to 5 carbon atoms. Examples of substituents that can have substituents, including alkyl, alkoxy, halogen atoms, haloalkyl, hydroxyl, carbonyl, and nitro groups, are preferably halogen atoms, and more preferably fluorine atoms.

[0360] When any two or more of R1 to R5 are bonded to each other to form a ring, they can form an aromatic ring or an aliphatic ring together with the phenyl bonded to R1 to R5, preferably an aromatic ring or an aliphatic ring with 6 to 20 carbon atoms.

[0361] Rb in general formula (b-3) 01 ~Rb 03 and Lb 01 Rb in the above formula (ca-b-2) 01 ~Rb 03 and Lb 01 same.

[0362] The compound represented by the above general formula (b-3) is preferably the compound represented by the following general formula (b-4).

[0363] [Chemical Formula 53] In general formula (b-4), R1 to R5 are each independently a hydrogen atom, a halogen atom, an alkoxy group, a haloalkyl group, a hydroxyl group, a carbonyl group, a nitro group, or a hydrocarbon group that may have substituents. Any two or more of R1 to R5 can bond together to form a ring. Rb 01 It can be an aryl group, an alkyl group, or an alkenyl group that can have substituents, and some carbon atoms can be replaced with heteroatoms. Yb 01 This is a group that forms an aliphatic ring together with the sulfur atom in the formula. The sulfur atom in the formula and Yb 01 The resulting aliphatic ring may contain ether bonds and may have substituents. Lb01 It is a single bond or a divalent linker. R1 to R5 in general formula (b-4) are the same as R1 to R5 in general formula (b-3) above.

[0364] Rb in general formula (b-4) 01 Rb in the above formula (ca-b-2) 01 same.

[0365] Lb in general formula (b-4) 01 Lb in the above formula (ca-b-2) 01 same.

[0366] Yb in general formula (b-4) 01 Yb in (ca-b-3) above 01 same.

[0367] The following are specific examples of suitable (B) components.

[0368] [Chemical Formula 54] The compounds represented by general formula (b-1) can be manufactured using known methods.

[0369] In the resist composition of this embodiment, component (B) can be used alone or in combination with two or more components.

[0370] In the resist composition of this embodiment, the content of component (B) is preferably 1 to 40 parts by mass relative to 100 parts by mass of component (A1) or component (A2), more preferably 1 to 30 parts by mass, and even more preferably 1 to 25 parts by mass.

[0371] If the content of component (B) is above the lower limit of the above-mentioned preferred range, a resist pattern with good sensitivity, resolution, and CDU can be easily formed during resist pattern formation. On the other hand, if it is below the upper limit of the above-mentioned preferred range, a uniform solution can be easily obtained when the components of the resist composition are dissolved in an organic solvent, and the storage stability of the resist composition is further improved.

[0372] Regarding ingredient (B2) The resist composition of this embodiment may contain an acid-generating component other than component (B) above (hereinafter referred to as "component (B2)") without impairing the effect of the present invention.

[0373] As for component (B2), there are no particular limitations, and any acid-generating agent proposed so far as an acid-generating agent used in chemically reinforced resist compositions may be used.

[0374] Examples of such acid-producing agents include onium salt-based acid-producing agents such as iodonium salts and sulfonium salts; sulfonate oxime-based acid-producing agents; dialkyl or diarylsulfonyl diazomethanes and poly(disulfonyl)diazomethanes; nitrobenzyl sulfonate-based acid-producing agents; iminosulfonate-based acid-producing agents; and disulfone-based acid-producing agents.

[0375] In the resist composition of this embodiment, component (B2) can be used alone or in combination with two or more components.

[0376] When the resist composition contains component (B2), the content of component (B2) in the resist composition is preferably 50 parts by mass or less, more preferably 1 to 40 parts by mass, and even more preferably 5 to 30 parts by mass, relative to 100 parts by mass of component (A1) or component (A2).

[0377] By setting the content of component (B2) within the above-mentioned range, pattern formation is sufficiently achieved. Furthermore, when the components of the resist composition are dissolved in an organic solvent, a homogeneous solution is easily obtained, resulting in good storage stability of the resist composition, which is therefore preferred.

[0378] (C) Ingredients The resist composition according to the second embodiment of the present invention contains a crosslinking agent (C) (hereinafter referred to as "(C) component").

[0379] (C) The component is at least one crosslinking agent selected from the group consisting of melamine-based crosslinking agents, urea-based crosslinking agents, alkylene urea-based crosslinking agents, glycourea-based crosslinking agents and epoxy-based crosslinking agents.

[0380] 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.

[0381] Examples of urea-based 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 dimethoxymethylurea, diethoxymethylurea, dipropoxymethylurea, and dibutoxymethylurea, with dimethoxymethylurea being preferred.

[0382] Compounds represented by the following general formula (CA-1) can be cited as crosslinking agents for alkylene urea systems.

[0383] [Chemical Formula 55] In formula (CA-1), Rc 1 With Rc 2 Each is independently a hydroxyl or lower alkoxy group, Rc 3 With Rc 4 Each is independently a hydrogen atom, a hydroxyl group, or a lower alkoxy group, and vc is an integer from 0 to 2. 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.

[0384] 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.

[0385] vc is an integer from 0 to 2, preferably 0 or 1.

[0386] 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.

[0387] The compound represented by the above general formula (CA-1) can be obtained by condensing an alkylene urea with formalin and reacting the product with a lower alcohol.

[0388] Specific examples of alkylene urea crosslinking agents include 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.

[0389] Examples of glycourea-based crosslinking agents include glycourea derivatives obtained by substituting one or both of a hydroxyalkyl group and an alkoxyalkyl 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.

[0390] Specific examples of glycourea-based 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.

[0391] As an epoxy-based crosslinking agent, any crosslinking agent containing epoxy groups is acceptable; there are no particular limitations, and any choice can be made. Preferably, it has two or more epoxy groups. Having two or more epoxy groups improves the crosslinking reactivity.

[0392] The number of epoxy groups is preferably two or more, more preferably two to four, and most preferably two.

[0393] The following are suitable substances for use as epoxy crosslinking agents.

[0394] [Chemical Formula 56] As component (C), a crosslinking agent having a -NCH2-OCH3 group is preferred, more preferably a compound selected from the group consisting of compounds represented by formula (c1-1) or (c1-2), compounds having a -NCH2-OCH3 group and a melamine backbone, and mono-, di-, tri- and / or tetra-methoxymethylated glycourea, and even more preferably a crosslinking agent selected from the group consisting of compounds having a -NCH2-OCH3 group and a melamine backbone, and mono-, di-, tri- and / or tetra-methoxymethylated glycourea.

[0395] [Chemical Formula 57] [In the formula, nc1 and nc2 are each independent integers from 1 to 3.] (C) Components can be used alone or in combination of two or more.

[0396] In the resist composition according to the second embodiment of the present invention, the content of component (C) is preferably 1 to 50 parts by mass relative to 100 parts by mass of component (A2), 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.

[0397] If the content of component (C) is above the lower limit, cross-linking formation is sufficient, further improving resolution performance and photolithography characteristics. Additionally, a good resist pattern with less swelling can be obtained. Furthermore, if it is below the upper limit, the resist composition exhibits good storage stability, making it easier to suppress the degradation of sensitivity over time.

[0398] (D) Ingredients The resist compositions according to the first and second embodiments of the present invention preferably further contain an acid diffusion control agent component (hereinafter referred to as "(D) component"). The (D) component is a component in the resist composition that functions as a quencher for capturing acid generated by exposure.

[0399] Examples of components (D) include nitrogen-containing organic compounds (D1) (hereinafter referred to as "(D1) component") and photodegradable bases (D2) that lose acid diffusion control through exposure decomposition, which do not belong to the (D1) component (hereinafter referred to as "(D2) component").

[0400] 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.

[0401] From the viewpoint of improving the transmittance of the resist film to the exposure light source when forming a thick resist pattern, component (D1) is preferred as component (D).

[0402] Regarding component (D1) (D1) is an alkaline component, a nitrogen-containing organic compound that acts as an acid diffusion control agent in the resist composition.

[0403] As for component (D1), there are no particular limitations on any substance that functions as an acid diffusion control agent, and any known substance can be used. Among them, aliphatic amines or aromatic amines are preferred, and aliphatic amines are more preferred.

[0404] Aliphatic amines are amines having one or more aliphatic groups, preferably with 1 to 12 carbon atoms in the aliphatic group.

[0405] 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.

[0406] Specific examples of alkylamines and alkylolamines include monoalkylamines such as n-hexylamine, n-heptylamine, n-octylamine, n-nonylamine, and n-decylamine; dialkylamines such as diethylamine, di-n-propylamine, di-n-heptylamine, di-n-octylamine, and dicyclohexylamine; trialkylamines such as trimethylamine, triethylamine, tri-n-propylamine, tri-n-butylamine, tri-n-pentylamine, tri-n-hexylamine, tri-n-heptylamine, tri-n-octylamine, tri-n-nonylamine, tri-n-decylamine, and tri-n-dodecylamine; and alkylolamines such as diethanolamine, triethanolamine, diisopropanolamine, triisopropanolamine, di-n-octylamine, and tri-octylamine. Among these, trialkylamines with 6 to 30 carbon atoms are further preferred, and tri-n-pentylamine or tri-octylamine are particularly preferred.

[0407] 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).

[0408] Examples of aliphatic monocyclic amines include piperidine and piperazine.

[0409] As an aliphatic polycyclic amine, an aliphatic polycyclic amine with 6 to 10 carbon atoms is preferred. Specifically, examples include 1,5-diazabicyclo[4.3.0]non-5-ene, 1,8-diazabicyclo[5.4.0]-7-undecene, hexamethylenetetramine, and 1,4-diazabicyclo[2.2.2]octane.

[0410] Other aliphatic amines include tris(2-methoxymethoxyethyl)amine, tri{2-(2-methoxyethoxy)ethyl}amine, tri{2-(2-methoxyethoxymethoxy)ethyl}amine, tri{2-(1-methoxyethoxy)ethyl}amine, tri{2-(1-ethoxyethoxy)ethyl}amine, tri{2-(1-ethoxypropoxy)ethyl}amine, tri[2-{2-(2-hydroxyethoxy)ethoxy}ethyl]amine, triethanolamine triacetate, etc., with triethanolamine triacetate being preferred.

[0411] In addition, aromatic amines can also be used as (D1) components.

[0412] Examples of aromatic amines include 4-dimethylaminopyridine, 2,6-di-tert-butylpyridine, pyrrole, indole, pyrazole, imidazole or their derivatives, tribenzylamine, 2,6-diisopropylaniline, N-tert-butoxycarbonylpyrrolidine, etc.

[0413] (D1) Components can be used alone or in combination of two or more.

[0414] When the resist composition contains component (D1), the content of component (D1) in the resist composition is typically in the range of 0.01 to 5 parts by mass relative to 100 parts by mass of component (A1) or component (A2). By setting it within the above range, the resist pattern shape, long-term storage stability, etc., are improved.

[0415] Regarding component (D2) As a (D2) component, there are no particular limitations as long as it is a substance that decomposes due to exposure and loses its acid diffusion control, and does not belong to the (D1) component; it can be used arbitrarily from known substances.

[0416] By including a component (D2) that is not part of component (D1) in the resist composition, the contrast between the exposed and unexposed areas of the resist film can be further improved when forming the resist pattern.

[0417] Component (D2) can be used as an acid-producing agent, either based on or in place of component (B) above.

[0418] As component (D2), there is no particular limitation as long as it is a substance that decomposes upon exposure and loses its acid diffusion control. Preferably, it is one or more compounds selected from the group consisting of compounds represented by the following general formula (d2-1) (hereinafter referred to as "(d2-1) component"), compounds represented by the following general formula (d2-2) (hereinafter referred to as "(d2-2) component"), and compounds represented by the following general formula (d2-3) (hereinafter referred to as "(d2-3) component"). Among them, components (d2-1) to (d2-3) do not include components belonging to general formula (b-1).

[0419] The components (d2-1) to (d2-3) decompose in the exposed part of the resist film and lose their acid diffusion control (alkalinity), so they cannot function as quenchers, but they function as quenchers in the unexposed part of the resist film.

[0420] [Chemical Formula 58] [In the formula, Rd] 1 ~Rd 4 It can be a cyclic group that may have substituents, a chain-like alkyl group that may have substituents, or a chain-like alkenyl group that may have substituents. Wherein, Rd in formula (d2-2) 2 In Yd, an unbonded fluorine atom is attached to the carbon atom adjacent to the S atom. 1 It is a single bond or a divalent linker. m is an integer greater than or equal to 1, M m+ Each is an organic cation with an independent valence of m. {(d2-1) component} • Anion section In equation (d2-1), Rd 1 It can be a cyclic group that may have substituents, a chain-like alkyl group that may have substituents, or a chain-like alkenyl group that may have substituents, and examples of the aforementioned R' can be made respectively. 201 The same group.

[0421] Among them, as Rd 1 Preferably, the substituent is an aromatic hydrocarbon group, an aliphatic cyclic group, or a chain alkyl group. Examples of substituents that may be present in these groups include hydroxyl, oxo, alkyl, aryl, fluorine, fluoroalkyl, lactone-containing cyclic groups, ether bonds, ester bonds, or combinations thereof. When an ether bond or ester bond is included as a substituent, an alkylene group may be present; in this case, the linking group represented by each of the following formulas (y-al-1) to (y-al-8) is preferred.

[0422] [Chemical Formula 59] [In the formula, V'] 101 It is a single bond or an alkylene group having 1 to 5 carbon atoms, V' 102 It is a divalent saturated hydrocarbon group with 1 to 30 carbon atoms. In the above formula, V' 102 The divalent saturated hydrocarbon group is preferably an alkylene group having 1 to 30 carbon atoms. As V' 102 The alkylene group in the form of carbon atoms is preferably an alkylene group having 1 to 30 carbon atoms, more preferably an alkylene group having 1 to 10 carbon atoms, and even more preferably an alkylene group having 1 to 5 carbon atoms.

[0423] Examples of the aforementioned aromatic hydrocarbon groups include phenyl, naphthyl, and polycyclic structures containing a bicyclooctane skeleton (polycyclic structures formed from a bicyclooctane skeleton and other ring structures).

[0424] As the aforementioned aliphatic cyclic group, more preferably it is composed of adamantane, norbornene, isoboronane, or tricyclic [5.2.1.0]. 2,6 A group obtained by removing one or more hydrogen atoms from polycyclic alkanes such as decane and tetracyclododecane.

[0425] As for the aforementioned chain-like alkyl group, it is preferred that the number of carbon atoms is 1 to 10. Specifically, examples include straight-chain alkyl groups such as methyl, ethyl, propyl, butyl, pentyl, hexyl, heptyl, octyl, nonyl, and decyl; and branched-chain alkyl groups such as 1-methylethyl, 1-methylpropyl, 2-methylpropyl, 1-methylbutyl, 2-methylbutyl, 3-methylbutyl, 1-ethylbutyl, 2-ethylbutyl, 1-methylpentyl, 2-methylpentyl, 3-methylpentyl, and 4-methylpentyl.

[0426] When the aforementioned chain-like alkyl group is a fluoroalkyl group having a fluorine atom or a fluoroalkyl group as a substituent, the number of carbon atoms in the fluoroalkyl group is preferably 1 to 11, more preferably 1 to 8, and even more preferably 1 to 4. The fluoroalkyl group may contain atoms other than fluorine atoms. Examples of atoms other than fluorine atoms include oxygen atoms, sulfur atoms, and nitrogen atoms.

[0427] As Rd 1 Preferably, it is a fluoroalkyl group in which some or all of the hydrogen atoms of the linear alkyl group are replaced by fluorine atoms, and particularly preferably it is a fluoroalkyl group in which all of the hydrogen atoms of the linear alkyl group are replaced by fluorine atoms (linear perfluoroalkyl group).

[0428] The following shows a preferred example of the anionic portion of component (d2-1).

[0429] [Chemical Formula 60] • Cation section In equation (d2-1), M m+ It is an organic cation with an m valence.

[0430] As M m+ The organic cation can be suitably represented by the same cation as any of the aforementioned general formulas (ca-1) to (ca-3), more preferably the cation represented by the aforementioned general formula (ca-1), and even more preferably the cation represented by any of the aforementioned formulas (ca-1-1) to (ca-1-67).

[0431] (d2-1) Components can be used alone or in combination of two or more.

[0432] {(d2-2) component} • Anion section In equation (d2-2), Rd 2 It can be a cyclic group that may have substituents, a chain-like alkyl group that may have substituents, or a chain-like alkenyl group that may have substituents; examples include those related to the aforementioned R'. 201 The same group.

[0433] Among them, Rd 2 The carbon atom adjacent to the S atom in the (d2-2) component has no bonded fluorine atom (no fluorine substitution). As a result, the anion of the (d2-2) component becomes a moderately weak acid anion, which enhances the quenching ability of the (D) component.

[0434] As Rd 2Preferably, it is a chain-like alkyl group that may have substituents, or an aliphatic cyclic group that may have substituents. As a chain-like alkyl group, the number of carbon atoms is preferably 1 to 10, more preferably 3 to 10. As an aliphatic cyclic group, it is more preferably adamantane, norbornene, isoboronane, or tricyclic [5.2.1.0] 2,6 A group obtained by removing one or more hydrogen atoms from decane, tetracyclododecane, etc. (which may have substituents); a group obtained by removing one or more hydrogen atoms from camphor, etc.

[0435] Rd 2 The hydrocarbon group may have substituents, and examples of such substituents include Rd of the aforementioned formula (d2-1). 1 The hydrocarbon group (aromatic hydrocarbon group, aliphatic cyclic group, chain alkyl group) can have the same substituents as the hydrocarbon group.

[0436] The following shows a preferred example of the anionic portion of component (d2-2).

[0437] [Chemical Formula 61] • Cation section In equation (d2-2), M m+ An organic cation with a valence of m, and M in the aforementioned formula (d2-1) m+ same.

[0438] (d2-2) Components can be used alone or in combination of two or more.

[0439] {(d2-3) components} • Anion section In equation (d2-3), Rd 3 It can be a cyclic group that may have substituents, a chain-like alkyl group that may have substituents, or a chain-like alkenyl group that may have substituents; examples include those related to the aforementioned R'. 201 The same group is preferably a cyclic group containing a fluorine atom, a chain-like alkyl group, or a chain-like alkenyl group. Among these, fluoroalkyl groups are preferred, and more preferably those similar to the aforementioned Rd. 1 The same fluoroalkyl group.

[0440] In equation (d2-3), Rd 4 It can be a cyclic group that may have substituents, a chain-like alkyl group that may have substituents, or a chain-like alkenyl group that may have substituents; examples include those related to the aforementioned R'. 201 The same group.

[0441] Preferably, the groups are alkyl, alkoxy, alkenyl, or cyclic groups that may have substituents.

[0442] Rd 4The alkyl group is preferably a straight-chain or branched alkyl group having 1 to 5 carbon atoms. Examples include methyl, ethyl, propyl, isopropyl, n-butyl, isobutyl, tert-butyl, pentyl, isopentyl, and neopentyl. 4 Some of the hydrogen atoms in an alkyl group can also be replaced by hydroxyl, cyano, etc.

[0443] Rd 4 The alkoxy group in the alkoxy group is preferably an alkoxy group with 1 to 5 carbon atoms. Specifically, examples of alkoxy groups with 1 to 5 carbon atoms include methoxy, ethoxy, n-propoxy, isopropoxy, n-butoxy, and tert-butoxy. Among these, methoxy and ethoxy are preferred.

[0444] Rd 4 Examples of alkenyl groups in R' are those mentioned above. 201 The alkenyl group is preferably vinyl, propenyl (allyl), 1-methylpropenyl, or 2-methylpropenyl. These groups may further have alkyl groups having 1 to 5 carbon atoms or haloalkyl groups having 1 to 5 carbon atoms as substituents.

[0445] Regarding Rd 4 Regarding the cyclic group in it, examples such as the aforementioned R' can be cited. 201 The cyclic group in the same cyclic group is preferably from cyclopentane, cyclohexane, adamantane, norbornane, isobornane, tricyclic [5.2.1.0]. 2,6 Alicyclic groups obtained by removing one or more hydrogen atoms from cycloalkanes such as decane and tetracyclododecane, or aromatic groups such as phenyl and naphthyl groups. In Rd 4 In the case of alicyclic groups, the resist composition dissolves well in organic solvents, thereby resulting in good photolithographic properties. Furthermore, in Rd... 4 When the resist group is aromatic, the resist composition exhibits excellent light absorption efficiency, sensitivity, and lithographic properties in photolithography using EUV or similar exposure sources.

[0446] In equation (d2-3), Yd 1 It is a single bond or a divalent linker.

[0447] As Yd 1 The divalent linking group in the formula (a10-1) is not particularly limited, and examples include Ya in the formula (a10-1). x1 The divalent linking group in the example is the same group as the group mentioned above.

[0448] The following shows a preferred example of the anionic portion of component (d2-3).

[0449] [Chemical Formula 62] [Chemical Formula 63] • Cation section In equation (d2-3), M m+ An organic cation with a valence of m, and M in the aforementioned formula (d1-1) m+ same.

[0450] (d2-3) Components can be used alone or in combination of two or more.

[0451] (D2) Component can be any one of the above components (d2-1) to (d2-3), or it can be a combination of two or more.

[0452] When the resist composition contains component (D2), the content of component (D2) in the resist composition is preferably 0.5 to 25 parts by mass relative to 100 parts by mass of component (A1) or component (A2), more preferably 1 to 20 parts by mass, and even more preferably 2.5 to 15 parts by mass.

[0453] If the content of component (D2) is above the preferred lower limit, it is easy to obtain particularly good photolithography characteristics and resist pattern shape. On the other hand, if it is below the upper limit, sensitivity can be well maintained and throughput is also excellent.

[0454] (D2) Manufacturing method of component: The manufacturing methods for the aforementioned components (d2-1) and (d2-2) are not particularly limited and can be manufactured using known methods.

[0455] Furthermore, there are no particular limitations on the manufacturing method of component (d2-3). For example, it can be manufactured by the same method as described in US 2012-0149916.

[0456] <Any ingredient> The resist composition of this embodiment may further contain any component other than (A1) or (A2), (B), (C), and (D).

[0457] As such arbitrary components, for example, the (S) component, etc.

[0458] Organic Solvent Components (S) 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").

[0459] As component (S), any substance capable of dissolving the various components used to form a homogeneous solution may be used, and any optional substance may be appropriately selected from substances known in the past as solvents for chemically reinforced resist compositions.

[0460] In the resist composition of this embodiment, component (S) can be used alone or as a mixed solvent of two or more components. Preferably, it is PGMEA, PGME, γ-butyrolactone, EL, or cyclohexanone.

[0461] Furthermore, as component (S), a mixed solvent obtained by mixing PGMEA with a polar solvent is preferred. The mixing ratio (mass ratio) can be appropriately determined considering factors such as the compatibility of PGMEA with the polar solvent.

[0462] In addition, as component (S), at least one of PGMEA and EL, and a mixed solvent 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.

[0463] The amount of component (S) used is not particularly limited, and the concentration can be appropriately set according to the coating film thickness to allow for coating of substrates, etc. Generally, component (S) is used in a manner where the concentration of solid components in the resist composition is in the range of 0.1 to 20% by mass, preferably 0.2 to 15% by mass.

[0464] In the resist composition of this embodiment, additives with a commensurate nature can be further included as desired, such as additional resins, dissolution inhibitors, plasticizers, stabilizers, colorants, anti-halo agents, dyes, etc., for improving the performance of the resist film.

[0465] The resist composition of the first embodiment of the present invention contains the above-described components (A1) and (B), and any of the aforementioned components as needed.

[0466] For example, resist compositions containing components (A1), (B), and (D) may be suitably provided. Furthermore, resist compositions containing components (A1), (B), (D), and (S) may also be suitably provided.

[0467] The resist composition of the second embodiment of the present invention contains the above-described components (A2), (B), and (C), and any of the above-described components as needed.

[0468] For example, resist compositions containing components (A2), (B), (C), and (D) may be suitably provided. Furthermore, resist compositions containing components (A2), (B), (C), (D), and (S) may also be suitably provided.

[0469] As explained above, the resist composition of this embodiment contains an acid-generating component (B) comprising the compound represented by the above general formula (b-1). Regarding the compound represented by general formula (b-1), due to the electron-withdrawing effect of pentafluorobenzene, the anion is stabilized, thereby increasing the acid strength (lowering pKa) and achieving high sensitivity.

[0470] (Resist pattern formation method) Other embodiments of the present invention involve a method for forming a resist pattern comprising the following steps: a step of forming a resist film on a support using the resist composition of the above embodiments; a step of exposing the aforementioned resist film; and a step of developing the exposed resist film to form a resist pattern.

[0471] 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.

[0472] First, the resist composition of the above embodiment is applied to the support using a spin coater or the like, and for example, a baking (pre-baking (PAB)) treatment is performed at a temperature of 80 to 150°C for 40 to 120 seconds, preferably 50 to 90 seconds, thereby forming a resist film.

[0473] Next, selective exposure is performed on the resist film using an exposure apparatus such as an electron beam tracing device or an EUV exposure device, by exposure through a mask with a predetermined pattern (mask pattern) or by tracing based on direct electron beam irradiation without the mask pattern. Then, for example, a baking (post-exposure baking (PEB)) treatment is performed at a temperature of 80–150°C for 40–120 seconds, preferably 50–90 seconds.

[0474] Next, the aforementioned resist film is subjected to a development process. In the case of an alkaline development process, an alkaline developer is used for the development process; in the case of a solvent development process, a developer containing an organic solvent (organic developer) is used.

[0475] After development, rinsing is preferably performed. In the case of alkaline development, rinsing with pure water is preferred, while in the case of solvent development, rinsing with a rinsing solution containing organic solvents is preferred.

[0476] In the case of solvent development process, after the aforementioned development or rinsing treatment, a process can be performed to remove the developer or rinsing solution adhering to the pattern by supercritical fluid.

[0477] Drying is performed after development or rinsing. Alternatively, baking (post-baking) may be performed after the above development process, depending on the circumstances.

[0478] In this way, a resist pattern can be formed.

[0479] There are no particular limitations on the support structure; any known support structure can be used, such as a substrate for electronic components or a support on which a specified wiring pattern is formed. More specifically, examples include silicon wafers, metal substrates made of copper, chromium, iron, aluminum, or glass substrates. For the wiring pattern material, for example, copper, aluminum, nickel, or gold can be used.

[0480] There are no particular limitations on the wavelength used in the exposure; ArF excimer lasers, KrF excimer lasers, F2 excimer lasers, EUV (extreme ultraviolet), VUV (vacuum ultraviolet), EB (electron ray), X-rays, soft X-rays, and other types of radiation can be used. The aforementioned photoresist composition is highly useful for use with KrF excimer lasers, ArF excimer lasers, EB, or EUV.

[0481] The exposure method for the resist film can be conventional exposure (dry exposure) in an inert gas such as air or nitrogen, or liquid immersion lithography, but liquid immersion lithography is preferred.

[0482] 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).

[0483] The preferred immersion medium is a solvent having a refractive index greater than that of air and less than that of the resist film being exposed. There are no particular limitations on the refractive index of such a solvent, as long as it falls within the aforementioned range.

[0484] Solvents with a refractive index greater than that of air and less than that of the aforementioned resist film include, for example, water, fluorine-based inert liquids, silicon-based solvents, and hydrocarbon-based solvents.

[0485] Water is preferably used as the immersion medium.

[0486] Examples of alkaline developing solutions used in alkaline developing processes include 0.1 to 10% by mass aqueous solutions of tetramethylammonium hydroxide (TMAH).

[0487] The organic solvent contained in the organic developing solution used in solvent-based developing processes can be any organic solvent that can dissolve either component (A1) or component (A2) (the component (A1) or component (A2) 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, and ether solvents, as well as hydrocarbon solvents.

[0488] Examples of ester solvents include methyl acetate, butyl acetate, ethyl acetate, isopropyl acetate, amyl acetate, isoamyl acetate, isoamyl acetate, propylene glycol monomethyl ether acetate, ethylene glycol monoethyl ether acetate, diethylene glycol monobutyl ether acetate, diethylene glycol monoethyl ether acetate, ethyl-3-ethoxypropionate, 3-methoxybutyl acetate, 3-methyl-3-methoxybutyl acetate, methyl formate, ethyl formate, butyl formate, propyl formate, ethyl lactate, butyl lactate, propyl lactate, butyl butyrate, methyl 2-hydroxyisobutyrate, isoamyl acetate, isobutyl isobutyrate, and butyl propionate.

[0489] Examples of nitrile solvents include acetonitrile, propionitrile, valerate, and butyronitrile.

[0490] Organic-based developers can incorporate known additives as needed. Examples of such additives include surfactants. There are no particular limitations on the surfactant; for example, ionic, nonionic fluorinated, and / or silicone surfactants can be used.

[0491] 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 (spinning immersion method), spraying the developing solution onto the surface of the support (spraying method), and continuously discharging the developing solution from the developing solution nozzle while scanning at a certain speed on a support rotating at a certain speed (dynamic distribution method), etc.

[0492] 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 (spinning immersion method), spraying the developing solution onto the surface of the support (spraying method), and continuously discharging the developing solution from the developing solution nozzle while scanning at a certain speed on a support rotating at a certain speed (dynamic distribution method), etc.

[0493] Rinsing treatment (cleaning treatment) using rinsing solution can be carried out by known rinsing methods. Examples of such rinsing methods include continuously discharging 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).

[0494] The resist composition of the above embodiments and the various materials used in the pattern forming method of the above embodiments (e.g., resist solvent, developer, rinsing solution, antireflective film forming composition, surface coating forming composition, etc.) are preferably free from impurities such as metals, halogen-containing metal salts, acids, alkalis, and components containing sulfur or phosphorus atoms. Examples of impurities containing metal atoms include Na, K, Ca, Fe, Cu, Mn, Mg, Al, Cr, Ni, Zn, Ag, Sn, Pb, Li, or their salts. The content of these impurities is preferably 200 ppb or less, more preferably 1 ppb or less, further preferably 100 ppt (parts per trillion) or less, particularly preferably 10 ppt or less, and most preferably substantially free of impurities (below the detection limit of the measuring device).

[0495] In the resist pattern forming method of the present embodiment described above, since the resist composition involved in the first or second embodiment of the present invention is used, high sensitivity can be achieved when forming the resist pattern, and the photolithography characteristics are excellent, so that a resist pattern with good shape can be formed.

[0496] Example The present invention will be further described in detail below by way of examples, but the present invention is not limited to these examples.

[0497] <Synthetic Examples of Polymer Compounds (A)-1 to (A)-6> Each polymer compound was synthesized using monomers that derive structural units from the polymer compounds (A)-1 to (A)-6 shown below, in a specified molar ratio.

[0498] The methods used to obtain the polymer compounds are also described. 13 The copolymer composition ratio (the proportion of each structural unit in the polymer compound (molar ratio)) determined by C-NMR, the weight-average molecular weight (Mw) converted from standard polystyrene by GPC determination, and the molecular weight dispersion (PDI) (Mw / Mn) are also determined.

[0499] [Chemical Formula 64] <Example of the synthesis of compound (B)-1> [Chemical Formula 65] Under a nitrogen atmosphere, precursor (Bpre1) (15.00 g, 30.0 mmol) and salt-exchange compound A (8.98 g, 30.0 mmol) were dissolved in dichloromethane (100 g) in a 300 mL round-bottom flask. Ultrapure water (50 g) was added, and the reaction was carried out at room temperature for 30 minutes. After the reaction was complete, the aqueous phase was removed, and the organic phase was washed four times with ultrapure water (50 g). The organic phase was concentrated and dried using a rotary evaporator to give compound (B)-1 (20.3 g, yield = 91.2%).

[0500] <Synthesis of compounds (B)-2 to (B)-7> By changing the precursor compound and the salt exchange compound described above, compounds (B)-2 to (B)-7 were obtained in the same manner as in the "Synthesis Example of Compound (B)-1" described above.

[0501] The obtained compounds were subjected to NMR analysis, and their structures were identified based on the following analytical results.

[0502] [Chemical Formula 66] Table 1 shows the NMR results of compounds (B)-1 to (B)-6.

[0503] [Table 1] [Evaluation of Negative Resist Compositions 1] <Preparation of Negative Resist Composition 1> (Examples 1-1 to 1-16, Comparative Examples 1-1 to 1-4) The components shown in Tables 2 and 3 were mixed and dissolved in a solvent (a mixed solvent of 225 parts by mass of propylene glycol monomethyl ether acetate (PGMEA) and 225 parts by mass of propylene glycol monomethyl ether (PGME)) to prepare the resist compositions of each example.

[0504] [Table 2] [Table 3] In Tables 2 and 3, the abbreviations have the following meanings. The values ​​in [] represent the amount of each component (parts by mass).

[0505] (A)-1 to (A)-6: The above polymer compounds (A)-1 to (A)-6 (B)-1 to (B)-6: Acid-producing agents formed from each of the above compounds (B)-1 to (B)-6. (B)-11 to (B)-12: Compare the acid-producing agents formed by each of compounds (B)-11 to (B)-12 below. [Chemical Formula 67] (C)-1: A crosslinking agent formed from the compound represented by the following chemical formula (C)-1.

[0506] (D)-1: An acid diffusion control agent formed from the compound represented by the following chemical formula (D)-1.

[0507] [Chemical Formula 68] <Formation of Negative Resist Pattern 1> On an 8-inch silicon wafer treated with hexamethyldisilazane (HMDS) at 110°C for 60 seconds, the resist compositions of each example were applied using a spin coater. The wafers were then pre-baked (PAB) at 90°C for 60 seconds on a hot plate to dry, thereby forming a negative resist film with a thickness of 2 μm.

[0508] Next, using a KrF exposure device NSR-S203B (Nikon; NA (numerical aperture) = 0.60, σ = 0.68), the aforementioned resist film was selectively irradiated with a KrF excimer laser (248 nm) through a mask pattern (binary mask).

[0509] Next, a post-exposure heating (PEB) treatment was performed at 110°C for 60 seconds.

[0510] 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. Then, the mixture was rinsed with pure water for 30 seconds and spun dry.

[0511] Then, bake at 100°C for 60 seconds.

[0512] As a result, an isolated spacing pattern with a width of 500 nm was formed.

[0513] [Sensitivity Evaluation 1] [Evaluation of Optimal Exposure (Eop)] Determine the optimal exposure Eop (mJ / cm) for forming an isolated spaced pattern with a width of 500 nm in the above <Formation of Negative Resist Pattern 1>. 2 This is used as the "sensitivity (mJ / cm)".2 The following is shown in Table 4.

[0514] [Resolution Evaluation 1] Determine the optimal exposure Eop (mJ / cm) for forming an isolated spaced pattern with a width of 500 nm in the above <Formation of Negative Resist Pattern 1>. 2 Then, using a scanning electron microscope S-9380 (manufactured by Hitachi High Technology Co., Ltd.), the spacing width (nm) of the pattern that could be resolved when the exposure was gradually reduced from the optimal exposure to form the isolated spacing pattern was determined. This is shown as “resolution (nm)” in Table 4.

[0515] [Evaluation of in-plane uniformity (CDU) of pattern dimensions 1] The optimal exposure Eop (mJ / cm) obtained through the resolution evaluation 1 above. 2 The entire wafer surface was exposed, and the resulting pattern CD (interval width) was measured using a scanning electron microscope S-9380 (manufactured by Hitachi High Technology Corporation). Then, three times the standard deviation (σ) calculated from the measurement results (3σ) was determined. This result is presented as "CDU (nm)" in Table 4.

[0516] The smaller the 3σ value, the higher the uniformity of the dimensions (CD) of the multiple spaces formed in the resist film.

[0517] [Table 4] As shown in Table 4, it was confirmed that the resist composition of the examples had better sensitivity, resolution, and CDU compared to the resist composition of the comparative examples.

[0518] [Evaluation of Negative Resist Compositions 2] <Preparation of Negative Resist Composition 2> (Examples 2-1 to 2-6, Comparative Examples 2-1 to 2-2) The components shown in Table 5 were mixed and dissolved in a solvent (a mixed solvent of 550 parts by mass of propylene glycol monomethyl ether acetate (PGMEA) and 550 parts by mass of propylene glycol monomethyl ether (PGME)) to prepare the resist compositions of each example.

[0519] [Table 5] In Table 5, each abbreviation has the following meaning. The value in [] is the amount of the mixture (parts by mass).

[0520] (A)-3: The above-mentioned polymer compound (A)-3 (B)-1 to (B)-6: Acid-producing agents formed from each of the above compounds (B)-1 to (B)-6. (B)-11 to (B)-12: Acid-producing agents formed from each of the above-mentioned comparative compounds (B)-11 to (B)-12. (C)-1: A crosslinking agent formed from the compound represented by the above chemical formula (C)-1.

[0521] (D)-1: An acid diffusion control agent formed from the compound represented by the above chemical formula (D)-1.

[0522] <Formation of Negative Resist Pattern 2> On an 8-inch silicon wafer, an organic antireflective film composition “DUV-42P” (trade name, manufactured by Nissan Chemical Co., Ltd.) is applied using a spin coater, fired at 180°C for 60 seconds on a hot plate, and then dried to form an organic antireflective film with a thickness of 65 nm.

[0523] On the organic antireflective film, the resist composition of each example was coated by a spin coater, and then pre-baked (PAB) at 100°C for 60 seconds on a hot plate to dry, thereby forming a resist film with a thickness of 500 nm.

[0524] Next, using a KrF exposure apparatus NSR-S203 (Nikon; NA (numerical aperture) = 0.68, 2 / 3 ring), the aforementioned resist film was selectively irradiated with a KrF excimer laser (248 nm) through the mask pattern.

[0525] Then, it is subjected to PEB treatment at 120°C for 60 seconds, followed by alkaline development at 23°C for 60 seconds in a 2.38% by mass TMAH aqueous solution NMD-3 (trade name, manufactured by Tokyo Ohka Kogyo Co., Ltd.). Afterwards, it is rinsed with pure water for 30 seconds and then spin-dried.

[0526] Then, bake at 100°C for 60 seconds.

[0527] As a result, an isolated spacing pattern with a width of 160 nm was formed.

[0528] [Sensitivity Evaluation 2] [Evaluation of Optimal Exposure (Eop)] Determine the optimal exposure Eop (mJ / cm) for forming an isolated spaced pattern with a width of 160 nm in the above <Formation of Negative Resist Pattern 2>. 2 This is used as the "sensitivity (mJ / cm)". 2 The following is shown in Table 6.

[0529] [Resolution Evaluation 2] Determine the optimal exposure Eop (mJ / cm) for forming an isolated spaced pattern with a width of 160 nm in the above <Formation of Negative Resist Pattern 2>. 2 Then, using a scanning electron microscope S-9380 (manufactured by Hitachi High Technology Co., Ltd.), the spacing width (nm) of the pattern that could be resolved when the exposure was gradually reduced from the optimal exposure to form the isolated spacing pattern was determined. This is shown as “resolution (nm)” in Table 6.

[0530] [Evaluation of in-plane uniformity (CDU) of pattern dimensions 2] The optimal exposure Eop (mJ / cm) obtained through the resolution evaluation 2 above. 2 The entire wafer surface was exposed, and the resulting pattern CD (interval width) was measured using a scanning electron microscope S-9380 (manufactured by Hitachi High Technology Corporation). Then, three times the standard deviation (σ) calculated from the measurement results (3σ) was determined. This result is presented as "CDU (nm)" in Table 6.

[0531] The smaller the 3σ value, the higher the uniformity of the dimensions (CD) of the multiple spaces formed in the resist film.

[0532] [Table 6] As shown in Table 6, it was confirmed that the resist composition of the examples had better sensitivity, resolution, and CDU compared to the resist composition of the comparative examples.

[0533] <Synthetic Examples of Polymers (A)-11 to (A)-13> Each polymer compound was synthesized using monomers that derive structural units from the polymers (A)-11 to (A)-13 shown below, in a specified molar ratio.

[0534] The methods used to obtain the polymer compounds are also described. 13 The copolymer composition ratio (the proportion of each structural unit in the polymer compound (molar ratio)) determined by C-NMR, the weight-average molecular weight (Mw) converted from standard polystyrene by GPC determination, and the molecular weight dispersion (PDI) (Mw / Mn) are also determined.

[0535] [Chemical Formula 69] [Evaluation of positive resist compositions 1] <Preparation of Positive Resist Composition 1> (Examples 3-1 to 3-8, Comparative Examples 3-1 to 3-2) The components shown in Table 7 were mixed and dissolved in a solvent (a mixed solvent of 67 parts by mass of propylene glycol monomethyl ether acetate (PGMEA) and 67 parts by mass of propylene glycol monomethyl ether (PGME)) to prepare the resist compositions of each example.

[0536] [Table 7] In Table 7, each abbreviation has the following meaning. The value in [] is the amount of the mixture (parts by mass).

[0537] (A)-11~(A)-13: The above-mentioned polymers (A)-11~(A)-13 (B)-1 to (B)-6: Acid-producing agents formed from each of the above compounds (B)-1 to (B)-6. (B)-11 to (B)-12: Acid-producing agents formed from each of the above-mentioned comparative compounds (B)-11 to (B)-12. (D)-1: An acid diffusion control agent formed from the compound represented by the above chemical formula (D)-1.

[0538] <Formation of Positive Resist Pattern 1> On an 8-inch silicon wafer treated with hexamethyldisilazane (HMDS) at 110°C for 60 seconds, the resist compositions of each example were applied using a spin coater. The wafers were then pre-baked (PAB) at 150°C for 90 seconds on a hot plate to dry, thereby forming a positive resist film with a thickness of 10 μm.

[0539] Next, using a KrF exposure device NSR-S203B (Nikon; NA (numerical aperture) = 0.60, σ = 0.68), the aforementioned resist film was selectively irradiated with a KrF excimer laser (248 nm) through a mask pattern (binary mask).

[0540] Next, a post-exposure heating (PEB) treatment was performed at 110°C for 90 seconds.

[0541] 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. Then, the mixture was rinsed with pure water for 30 seconds and spun dry.

[0542] Then, bake at 100°C for 60 seconds.

[0543] As a result, isolated interval patterns with a width of 3 μm were formed.

[0544] [Sensitivity Evaluation 3] [Evaluation of Optimal Exposure (Eop)] Determine the optimal exposure Eop (mJ / cm) for forming an isolated spaced pattern with a width of 3μm in the above <Formation of Positive Resist Pattern 1>. 2 This is used as the "sensitivity (mJ / cm)". 2 The following is shown in Table 8.

[0545] [Resolution Evaluation 3] Determine the optimal exposure Eop (mJ / cm) for forming an isolated spaced pattern with a width of 3μm in the above <Formation of Positive Resist Pattern 1>. 2 Then, using a scanning electron microscope S-9380 (manufactured by Hitachi High Technology Co., Ltd.), the spacing width (μm) of the pattern that could be resolved when the exposure was gradually reduced from the optimal exposure to form the isolated spacing pattern was determined. This is shown as “resolution (μm)” in Table 8.

[0546] [Evaluation of in-plane uniformity (CDU) of pattern dimensions 3] The optimal exposure Eop (mJ / cm) obtained through the resolution evaluation 3 above. 2 The entire wafer surface was exposed, and the resulting pattern CD (interval width) was measured using a scanning electron microscope S-9380 (manufactured by Hitachi High Technology Corporation). Then, three times the standard deviation (σ) calculated from the measurement results (3σ) was determined. This result is presented as "CDU (nm)" in Table 8.

[0547] The smaller the 3σ value, the higher the uniformity of the dimensions (CD) of the multiple spaces formed in the resist film.

[0548] [Table 8] The results shown in Table 8 confirm that the resist composition of the examples has better sensitivity, resolution, and CDU compared to the resist composition of the comparative examples.

[0549] [Evaluation of Positive Resist Compositions 2] <Preparation of Positive Resist Composition 2> (Examples 4-1 to 4-6, Comparative Examples 4-1 to 4-2) The components shown in Table 9 were mixed and dissolved in a solvent (a mixed solvent of 600 parts by mass of propylene glycol monomethyl ether acetate (PGMEA) and 600 parts by mass of propylene glycol monomethyl ether (PGME)) to prepare the resist compositions of each example.

[0550] [Table 9] In Table 9, each abbreviation has the following meaning. The value in [] is the amount of the mixture (parts by mass).

[0551] (A)-11: The above-mentioned polymer compound (A)-11 (B)-1 to (B)-6: Acid-producing agents formed from each of the above compounds (B)-1 to (B)-6. (B)-11 to (B)-12: Acid-producing agents formed from each of the above-mentioned comparative compounds (B)-11 to (B)-12. (D)-1: An acid diffusion control agent formed from the compound represented by the above chemical formula (D)-1.

[0552] <Formation of Positive Resist Pattern 2> On a 6-inch silicon wafer, an organic antireflective film composition “DUV-42P” (manufactured by Nissan Chemical Co., Ltd.) is applied using a spin coater, fired at 180°C for 60 seconds on a hot plate, and then dried to form an organic antireflective film with a thickness of 65 nm.

[0553] Each resist composition is applied to the antireflective film using a spin coater, and then pre-baked (PAB) at 110°C for 60 seconds on a hot plate to dry, thereby forming a resist film with a thickness of 500 nm.

[0554] Using a KrF exposure apparatus NSR-S203B [Nikon; NA (numerical aperture) = 0.68, Sigma = 0.75], KrF excimer laser (248 nm) was selectively irradiated through a binaly mask. Then, a PEB treatment was performed at 110°C for 60 seconds.

[0555] Next, alkaline development was performed at 23°C for 60 seconds in a 2.38% by mass TMAH aqueous solution (trade name: NMD-3, manufactured by Tokyo Ohka Kogyo Co., Ltd.). Then, the sample was rinsed with pure water for 30 seconds and spun dry.

[0556] Then, bake at 100°C for 60 seconds.

[0557] As a result, in any example, a 1:1 line and spacing (LS) pattern with a line width of 170 nm and a spacing of 340 nm was formed.

[0558] [Sensitivity Rating 4] [Evaluation of Optimal Exposure (Eop)] Determine the optimal exposure Eop (mJ / cm²) for forming an LS pattern with a linewidth of 170 nm and a spacing of 340 nm in the above <Forming Positive Resist Pattern 2>.2 This is used as the "sensitivity (mJ / cm)". 2 The following is shown in Table 10.

[0559] [Resolution Rating 4] Observing the line dimensions in <Formation of Positive Resist Pattern 2> above, the optimal exposure Eop (mJ / cm) for forming an LS pattern with a linewidth of 170nm and a spacing of 340nm is determined. 2 Then, using a scanning electron microscope S-9380 (manufactured by Hitachi High Technology Co., Ltd.), the spacing width (nm) of the pattern that could be resolved when the exposure was gradually reduced from the optimal exposure to form the LS pattern was determined. This is shown as “resolution (nm)” in Table 10.

[0560] [Evaluation of In-Plane Uniformity (CDU) of Pattern Dimensions 4] The optimal exposure Eop (mJ / cm) obtained through the resolution evaluation 4 above. 2 The entire wafer surface was exposed, and the resulting pattern CD (interval width) was measured using a scanning electron microscope S-9380 (manufactured by Hitachi High Technology Corporation). Then, three times the standard deviation (σ) calculated from the measurement results (3σ) was determined. This result is presented as "CDU (nm)" in Table 10.

[0561] The smaller the 3σ value, the higher the uniformity of the dimensions (CD) of the multiple spaces formed in the resist film.

[0562] [Table 10] The results shown in Table 10 confirm that the resist composition of the examples has better sensitivity, resolution, and CDU compared to the resist composition of the comparative examples.

[0563] Industrial availability According to the present invention, a resist composition and a method for forming a resist pattern with good sensitivity, resolution and CDU can be provided.

[0564] Although the invention has been described in detail and with reference to specific embodiments, it will be apparent to those skilled in the art that various changes and modifications can be made without departing from the spirit and scope of the invention.

[0565] This application is based on Japanese Patent Application No. 2024-057451, filed on March 29, 2024, the contents of which are incorporated herein by reference.

Claims

1. A photoresist composition that generates acid upon exposure and whose solubility in a developer varies with the action of the acid, said photoresist composition comprising a substrate component (A1) whose solubility in a developer varies with the action of the acid, and an acid-generating component (B) that generates acid upon exposure, said acid-generating component (B) comprising a compound represented by the following general formula (b-1). [Chemical Formula 1] In general formula (b-1), Ra represents an optional organic group, and M m+ This represents an organic cation with a valence of m.

2. A photoresist composition comprising: a substrate component (A2) including an alkali-soluble resin (A2); an acid-generating agent component (B) that generates acid upon exposure; and a crosslinking agent (C), wherein the alkali-soluble resin (A2) has a structural unit (a10) represented by the following general formula (a10-1), the acid-generating agent component (B) comprises a compound represented by the following general formula (b-1), and the crosslinking agent (C) comprises at least one crosslinking agent selected from the group consisting of melamine-based crosslinking agents, urea-based crosslinking agents, alkylene urea-based crosslinking agents, glycourea-based crosslinking agents, and epoxy-based crosslinking agents. [Chemical Formula 2] In the general 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; Ya x1 It is a single bond or a divalent linker; Wa x1 For (n) ax1 +1) Aromatic hydrocarbon group; n ax1 Integers greater than or equal to 1 [Chemical Formula 3] In general formula (b-1), Ra represents an optional organic group, and M m+ This represents an organic cation with a valence of m.

3. The resist composition according to claim 1 or 2, wherein, The compound represented by the general formula (b-1) is the compound represented by the following general formula (b-2). [Chemical Formula 4] In general formula (b-2), Ra represents an optional organic group; Rb 01 ~Rb 03 Each can be independently an aryl group, an alkyl group, or an alkenyl group that can have substituents, and some carbon atoms can be replaced by heteroatoms; Rb 02 and Rb 03 It can bond with the sulfur atom in the formula to form a ring; Lb 01 It is a single bond or a divalent linker.

4. The resist composition according to claim 3, wherein, The compound represented by the general formula (b-2) is the compound represented by the following general formula (b-3). [Chemical Formula 5] In general formula (b-3), R1 to R5 are each independently a hydrogen atom, a halogen atom, an alkoxy group, a haloalkyl group, a hydroxyl group, a carbonyl group, a nitro group, or a hydrocarbon group that may have substituents; any two or more of R1 to R5 can be bonded to each other to form a ring; Rb 01 ~Rb 03 Each can be independently an aryl group, an alkyl group, or an alkenyl group that can have substituents, and some carbon atoms can be replaced by heteroatoms; Rb 02 and Rb 03 It can bond with the sulfur atom in the formula to form a ring; Lb 01 It is a single bond or a divalent linker.

5. The resist composition as claimed in claim 4, wherein, The compound represented by the general formula (b-3) is the compound represented by the following general formula (b-4). [Chemical Formula 6] In general formula (b-4), R1 to R5 are each independently a hydrogen atom, a halogen atom, an alkoxy group, a haloalkyl group, a hydroxyl group, a carbonyl group, a nitro group, or a hydrocarbon group that may have substituents; any two or more of R1 to R5 can be bonded together to form a ring; Rb 01 It can be an aryl group, an alkyl group, or an alkenyl group that can have substituents, and some carbon atoms can be replaced with heteroatoms; Yb 01 This is a group that forms an aliphatic ring together with the sulfur atom in the formula; the sulfur atom in the formula and Yb 01 The resulting aliphatic ring may contain ether bonds and may have substituents; Lb 01 It is a single bond or a divalent linker.

6. A method for forming a resist pattern, comprising: The process of forming a resist film on a support using the resist composition of claim 1 or 2; The process of exposing the resist film; The process of developing the resist film to form a resist pattern.

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