Photosensitive or radiosensitive linear resin compositions, patterning methods, resist films, and methods for manufacturing electronic devices.

Abstract

The present application provides a radiation-sensitive or radiation-sensitive resin composition capable of obtaining a pattern with excellent LWR performance. Also, a resist film, a pattern forming method, and a manufacturing method of an electronic device related to the above radiation-sensitive or radiation-sensitive resin composition are provided. The radiation-sensitive or radiation-sensitive resin composition contains: a salt containing a sulfonium cation having an aryl group substituted with a group containing an acid-decomposable group and having at least 3 fluorine atoms; and a resin that increases in polarity by decomposition by the action of an acid, the group containing an acid-decomposable group contains a group that increases in polarity by decomposition by the action of an acid, and the group containing an acid-decomposable group does not contain a fluorine atom.

Description

Technical Field

[0001] This invention relates to a photosensitive radioactive or radiosensitive linear resin composition, a patterning method, a resist film, and a method for manufacturing electronic devices. Background Technology

[0002] In the manufacturing processes of semiconductor devices such as ICs (Integrated Circuits) and LSIs (Large Scale Integrated Circuits), micro-processing is performed using photolithography with photosensitive compositions.

[0003] As a photolithography method, one example is the method of forming a resist film by means of a photosensitive composition, exposing the obtained film, and then developing it.

[0004] For example, Patent Document 1 discloses an anti-corrosion composition comprising the following compounds.

[0005] [Chemical Formula 1]

[0006]

[0007] Previous technical documents

[0008] Patent documents

[0009] Patent Document 1: Japanese Patent Application Publication No. 2017-015777 Summary of the Invention

[0010] The technical problem to be solved by the invention

[0011] The inventors have specifically studied the technology disclosed in Patent Document 1, and the results show that the composition described in Patent Document 1 has room for improvement in the LWR (line width roughness) performance of the obtained pattern.

[0012] Therefore, the objective of this invention is to provide a photosensitive radioactive or radiosensitive linear resin composition that can produce patterns with excellent LWR performance.

[0013] Furthermore, the present invention also aims to provide a resist film, a patterning method, and a method for manufacturing electronic devices related to the above-mentioned photosensitive or radiosensitive linear resin composition.

[0014] means for solving technical problems

[0015] The inventors have discovered that the above-mentioned problems can be solved by the following structure.

[0016] [1] A photosensitive or radiosensitive linear resin composition comprising:

[0017] A salt comprising a sulfonium cation, said sulfonium cation having an aryl group substituted with a group containing an acid-degrading group and having at least three fluorine atoms; and

[0018] Resins increase their polarity through decomposition by the action of acids.

[0019] Groups containing acid-decomposing groups include those whose polarity increases through decomposition by acid.

[0020] Groups containing acid-degrading groups do not contain fluorine atoms.

[0021] [2] The photosensitive radioactive or radiosensitive linear resin composition according to [1], wherein,

[0022] The sulfonium cation is a triarylsulfonium cation.

[0023] [3] The photosensitive radioactive or radiosensitive linear resin composition according to [1] or [2], wherein,

[0024] Groups whose polarity increases due to decomposition by acid are represented by the general formula (a-1) or (a-2) described later.

[0025] [4] The photosensitive radioactive or radiosensitive linear resin composition according to [3], wherein,

[0026] The group whose polarity increases due to decomposition by the action of acid is represented by the general formula (a-1) described later.

[0027] [5] The photosensitive radioactive or radiosensitive linear resin composition according to any one of [1] to [4], wherein,

[0028] Sulfonium cations have a group whose polarity increases through decomposition by the action of acids.

[0029] [6] The photosensitive radioactive or radiosensitive linear resin composition according to any one of [1] to [5], wherein,

[0030] The sulfonium cation contains an aryl group that is substituted by at least one of fluorine atoms and fluoroalkyl groups.

[0031] [7] The photosensitive radioactive or radiosensitive linear resin composition according to any one of [1] to [6], wherein,

[0032] A salt containing a sulfonium cation has two or more cation sites and the same number of anion sites as the cation sites, wherein at least one of the cation sites is the sulfonium cation.

[0033] [8] A resist film formed using any one of [1] to [7] of a photosensitive radioactive or radiosensitive linear resin composition.

[0034] [9] A pattern forming method, comprising the following steps:

[0035] The process of forming a resist film on a substrate using any one of [1] to [7];

[0036] The process of exposing the above-mentioned resist film; and

[0037] The process of developing the exposed resist film with a developer to form a pattern.

[0038]

[10] A method for manufacturing an electronic device, comprising the pattern forming method described in [9].

[0039] Invention Effects

[0040] According to the present invention, a photosensitive radioactive or radiosensitive linear resin composition that can produce patterns with excellent LWR performance can be provided.

[0041] Furthermore, according to the present invention, it is possible to provide a resist film, a patterning method, and a method for manufacturing electronic devices related to the above-mentioned photosensitive or radiosensitive linear resin composition. Detailed Implementation

[0042] Hereinafter, an example of a method for implementing the present invention will be described.

[0043] In addition, in this specification, the numerical range indicated by “~” refers to the range of values ​​recorded before and after “~” as the lower and upper limits.

[0044] In this specification, the designations of groups (atomic groups) that do not specify whether they are substituted or unsubstituted include both substituted groups and unsubstituted groups. For example, "alkyl" includes not only unsubstituted alkyl groups (unsubstituted alkyl groups) but also substituted alkyl groups (substituted alkyl groups).

[0045] Unless otherwise stated, the substituent is preferably a monovalent substituent.

[0046] In this specification, "organic group" refers to a group containing at least one carbon atom.

[0047] In this specification, examples of halogen atoms include fluorine, chlorine, bromine, and iodine.

[0048] Unless otherwise stated, the bonding direction of the divalent groups marked in this specification is not limited. For example, when Y in a compound represented by the general formula "XYZ" is -COO-, Y can be -CO-O- or -O-CO-. Furthermore, the above compound can be "X-CO-OZ" or "XO-CO-Z".

[0049] In this specification, "(meth)acrylic acid" is a general term encompassing acrylic acid and methacrylic acid, specifically referring to "at least one of acrylic acid and methacrylic acid". Similarly, "(meth)acrylic acid" refers to "at least one of acrylic acid and methacrylic acid".

[0050] In this manual, "photochemical rays" or "radiation" refers to, for example, the bright-line spectrum of a mercury lamp, far-ultraviolet light represented by an excimer laser, extreme ultraviolet light (EUV light), X-rays, and electron beams (EB). In this manual, "light" refers to photochemical rays or radiation.

[0051] Unless otherwise stated, “exposure” in this specification includes not only exposure using bright-line spectra of mercury lamps, far-ultraviolet light represented by excimer lasers (ArF excimer lasers, etc.), X-rays and EUV light, but also depictions using particle beams such as electron beams and ion beams.

[0052] In this specification, the weight-average molecular weight (Mw), number-average molecular weight (Mn), and dispersion (hereinafter also referred to as "molecular weight distribution") of the resin (Mw / Mn) are defined as polystyrene equivalents determined by GPC using a GPC (Gel Permeation Chromatography) apparatus (HLC-8120GPC manufactured by TOSOH CORPORATION) (solvent: tetrahydrofuran, flow rate (sample injection volume): 10 μL, column: TSK gel Multipore HXL-M manufactured by TOSOH CORPORATION, column temperature: 40 °C, flow rate: 1.0 mL / min, detector: refractive index detector).

[0053] 1×10 -10 m.

[0054] In this specification, the acid dissociation constant (pKa) refers to the pKa in aqueous solution, specifically, a value calculated using software package 1 described below based on a database of Hammett substituent constants and known literature values. All pKa values ​​described in this specification are values ​​calculated using this software package.

[0055] Software package 1: Advanced Chemistry Development (ACD / Labs) Software V8.14 for Solaris (1994-2007ACD / Labs).

[0056] On the other hand, pKa can also be determined using molecular orbital algorithms. As a specific method, one example is calculating H in the solvent based on thermodynamic cycles. + The method for calculating the dissociation free energy. (In addition, water is usually used as the solvent mentioned above in this specification; DMSO (dimethyl sulfoxide) is used when water cannot be used to determine the pKa.)

[0057] Regarding H + Methods for calculating the dissociation free energy include, for example, the density functional method (DFT), but various other methods have been reported in the literature and are not limited to this. Furthermore, several software programs exist capable of implementing the DFT, such as Gaussian16.

[0058] As mentioned above, pKa in this specification refers to the value obtained by using software package 1 to calculate a database of substituent constants based on Hammett and known literature values. However, when pKa cannot be calculated by this method, the value obtained by Gaussian16 based on DFT (density functional method) is used.

[0059] [Photosensitive or radiosensitive linear resin composition]

[0060] The photosensitive or radiosensitive linear resin composition of the present invention (hereinafter also referred to as "resist composition") will be described.

[0061] The resist composition of the present invention can be a positive resist composition or a negative resist composition. Furthermore, it can be a resist composition for alkaline development or a resist composition for organic solvent development.

[0062] The compositions of the present invention are typically chemically amplified resist compositions.

[0063] The resist composition of the present invention comprises a salt (hereinafter also referred to as "specific compound") and a resin (hereinafter also simply referred to as "acid-degradable resin"). The salt comprises a sulfonium cation having an aryl group substituted with an acid-degradable group and having at least three fluorine atoms. The resin undergoes decomposition by acid, thereby increasing its polarity. The aforementioned acid-degradable group comprises a group whose polarity increases upon decomposition by acid (hereinafter also simply referred to as "acid-degradable group"), and the aforementioned acid-degradable group does not contain fluorine atoms.

[0064] Although the mechanism by which this structure solves the problem of the present invention may not be clear, it is speculated as follows.

[0065] The specific compound is a salt containing a specified sulfonium cation and typically functions as a photoacid generator. In this specific compound, the sulfonium cation possesses an acid-degrading group and a specified number of fluorine atoms. Because this specific compound exhibits excellent decomposition efficiency during exposure and excellent compatibility with acid-degrading resins, the resulting pattern exhibits good light-reflecting ratio (LWR) performance. In particular, along with the polar groups generated by the acid-degrading resin, the acid-degrading group of the sulfonium cation decomposes to generate polar groups. This results in increased solubility of the exposed portion in alkaline developers and decreased solubility in organic solvent developers, exhibiting a tendency to improve LWR in both positive and negative patterns.

[0066] Hereinafter, in this specification, the situation in which a pattern with excellent LWR performance can be obtained will also be referred to as the excellent effect of the present invention.

[0067] [Components of the resist composition]

[0068] The following is a detailed description of the components that may be contained in an anti-corrosion composition.

[0069] <Salts containing sulfonium cations>

[0070] The resist composition of the present invention contains specific compounds.

[0071] Certain compounds are commonly used as photoacid generators. Photoacid generators are compounds that produce acid upon irradiation (exposure) by photochemical rays or radiation (preferably EUV light or ArF).

[0072] The photoacid generator is preferably in the form of a low molecular weight compound.

[0073] When the photoacid generator is in the form of a low molecular weight compound, the molecular weight is preferably 3000 or less, more preferably 2000 or less, and even more preferably 1200 or less.

[0074] The preferred compounds are those that produce organic acids through exposure.

[0075] Examples of the aforementioned organic acids include sulfonic acids (aliphatic sulfonic acids, aromatic sulfonic acids, and camphor sulfonic acid, etc.), carboxylic acids (aliphatic carboxylic acids, aromatic carboxylic acids, and aralkyl carboxylic acids, etc.), carbonyl sulfonyl imine acids, bis(alkyl sulfonyl) imine acids, and tri(alkyl sulfonyl) methylated acids, etc.

[0076] The volume of acid produced by a specific compound is not particularly limited, but from the viewpoint of suppressing the diffusion of acid generated during exposure into the non-exposed areas and improving resolution, it is preferable to... The above, better The above further optimizes The above are particularly preferred. That's all. Furthermore, from the viewpoint of sensitivity or solubility in the coating solvent, the volume of acid produced by the specific compound is preferably... The following is preferred The following are further optimizations. the following.

[0077] The volumes mentioned above were calculated using "WinMOPAC" manufactured by Fujitsu Limited. To calculate these volumes, the chemical structures of the acids involved in each example were first input. Then, using this structure as the initial structure, molecular force field calculations using the MM (Molecular Mechanics) method were performed to determine the most stable stereocoordinates for each acid. Subsequently, molecular orbital calculations using the PM (Parameterized Model number) method were performed on these most stable stereocoordinates, thereby allowing the calculation of the "accessible volume" for each acid.

[0078] The structure of the acid produced by a specific compound is not particularly limited. However, from the viewpoint of suppressing acid diffusion and improving resolution, it is preferable that the acid produced by the specific compound has a strong interaction with the acid-degrading resin described later. From this perspective, when the acid produced by the photoacid generator is an organic acid, it is preferable that the organic acid has polar groups in addition to organic acid groups such as sulfonic acid groups, carboxylic acid groups, carbonyl sulfonyl imide groups, disulfonyl imide groups, and trisulfonyl methyl acid groups.

[0079] Examples of polar groups include ether, ester, amide, acyl, sulfonyl, sulfonyloxy, sulfonamide, thioether, thioester, urea, carbonate, carbamate, hydroxyl, and mercapto.

[0080] The number of polar groups in the generated acid is not particularly limited, but it is preferably one or more, more preferably two or more. However, from the viewpoint of suppressing excessive development, the number of polar groups is preferably less than six, more preferably less than four.

[0081] (Sumonium cation)

[0082] A specific compound comprises a sulfonium cation (hereinafter also simply referred to as "specific cation") having an aryl group substituted with an acid-degrading group. The acid-degrading group comprises an acid-degrading group, and the acid-degrading group does not contain fluorine atoms. That is, the sulfonium cation contained in the specific compound comprises an acid-degrading group without fluorine atoms and has at least three fluorine atoms. In other words, the sulfonium cation contained in the specific compound has an aryl group substituted with an acid-degrading group without fluorine atoms and at least three fluorine atoms. Preferably, the sulfonium cation has an aryl group substituted with an acid-degrading group without fluorine atoms and an aryl group substituted with a group having at least three fluorine atoms or at least three fluorine atoms.

[0083] The sulfonium cation may have an aryl group substituted with a group containing an acid-decomposing group, and may also have a straight-chain or branched alkyl group or an aryl group that may have substituents. The alkyl group may be cyclic. The aryl group may be monocyclic or polycyclic.

[0084] Examples of substituents for the aforementioned alkyl and aryl groups include halogen atoms (e.g., fluorine and iodine atoms), alkyl groups that may have halogen atoms, alkyl groups that may have halogen atoms and polar groups (e.g., alcohol groups), alkoxy groups that may have halogen atoms, and aryl groups that may have halogen atoms. From the viewpoint of further enhancing the effects of the present invention, the substituents are preferably selected from at least one of fluorine atoms, iodine atoms, unsubstituted alkyl groups, fluoroalkyl groups, fluorool groups, and fluoroalkoxy groups, and more preferably from at least one of fluorine atoms and fluoroalkyl groups.

[0085] In addition, as the aforementioned fluoroalkyl group, examples of compounds represented by general formula (S-1) that may have fluoroalkyl groups can be cited.

[0086] Furthermore, the definition of a fluorool group will be described in detail later. Preferably, the fluorool group is represented by *-C(Ry)2(OH). Ry represents a fluoroalkyl group.

[0087] The number of carbon atoms in the above-mentioned alkyl, alkoxy, and fluoroalkyl groups is preferably 1 to 10, more preferably 1 to 8, and even more preferably 1 to 5.

[0088] Examples of sulfonium cations include triarylsulfonium cations, diarylalkylsulfonium cations, aryldialkylsulfonium cations, diarylcycloalkylsulfonium cations, and aryldicycloalkylsulfonium cations.

[0089] From the viewpoint of achieving better results with the present invention, triarylsulfonium cation is preferred as the sulfonium cation.

[0090] Furthermore, as another preferred embodiment of the sulfonium cation, the sulfonium cation preferably contains an aryl group substituted by at least one selected from fluorine atoms and fluoroalkyl groups.

[0091] ((aryl groups substituted with groups containing acid-degrading groups))

[0092] The sulfonium cation in a particular compound has an aryl group that is substituted by a group containing an acid-degrading group.

[0093] The aryl group can be monocyclic or polycyclic. Preferably, it is monocyclic.

[0094] Groups containing acid-degrading groups are included. Acid-degrading groups will be described in detail later. There is no particular limit to the number of acid-degrading groups in a group containing acid-degrading groups; it can be more than one. There is no particular upper limit, but it is usually less than two.

[0095] Furthermore, groups containing acid-degrading groups do not contain fluorine atoms. That is, groups containing acid-degrading groups do not contain fluorine atoms.

[0096] Furthermore, the aryl group substituted by the aforementioned group containing an acid-decomposing group may further have substituents in addition to the group containing an acid-decomposing group. That is, the aromatic hydrocarbon ring in the aryl group may further have substituents other than the group containing an acid-decomposing group. There are no particular limitations on the types of substituents mentioned above, and examples include halogen atoms (e.g., fluorine atoms and iodine atoms), alkyl groups that may have halogen atoms, alkyl groups that may have halogen atoms and polar groups (e.g., alcohol groups), alkoxy groups that may have halogen atoms, and aryl groups that may have halogen atoms. In other words, in the aryl group substituted by the group containing an acid-decomposing group, groups containing halogen atoms such as fluorine atoms may be further substituted as substituents.

[0097] Furthermore, examples of substituents can be found in the alkyl and aryl groups that the aforementioned sulfonium cation may possess.

[0098] The aryl group substituted with a group containing an acid-degrading group is preferably a group represented by the general formula (T-1). In the following formula, -L T1 -R T1 The part represented is equivalent to a group containing acid-decomposing groups.

[0099] [Chemical Formula 2]

[0100] *-Ar T1 -(L T1 -R T1 ) n

[0101] (T--1)

[0102] In the general formula (T-1), * represents the bonding position. n represents an integer from 1 to 5.

[0103] Ar T1 This indicates an aromatic hydrocarbon cyclic group that can have substituents.

[0104] As a product of Ar T1 The aromatic hydrocarbon cyclic groups represented can be exemplified by those described later by Ar. S1 ~Ar S3 The aromatic hydrocarbon cyclic group is represented.

[0105] L T1 It represents a single bond or a divalent linker that may have substituents that do not contain fluorine atoms.

[0106] As a result of L T1 Examples of divalent linking groups include -O-, -OC-, -CO-, -COO-, -OCO-, -S―, -CS-, -SO-, and -SO2-; hydrocarbon groups that may have substituents without fluorine atoms (e.g., alkylene, cycloalkylene, alkenyl, and aryl groups); and linking groups formed by the linkage of multiple of these. Among these, L... T1 Preferably, it is -O-, -OC-, -CS―, -COO-, unsubstituted hydrocarbon group, or a linking group or single bond formed by multiple of these.

[0107] In addition, examples of substituents mentioned above include nitro, carboxyl, hydroxyl, amino, and cyano.

[0108] R T1 This indicates an acid-degrading group. This acid-degrading group does not contain a fluorine atom.

[0109] An acid-degradable group refers to a group that decomposes to produce a polar group through the action of an acid. Preferably, the acid-degradable group has a structure protected by a release group, where the polar group is removed by the action of an acid. That is, the salt containing the sulfonium cation of the present invention has a group that decomposes to produce a polar group through the action of an acid. The increased polarity due to the action of an acid increases the solubility in alkaline developing solutions while decreasing the solubility in organic solvents.

[0110] As a polar group, an alkaline-soluble group is preferred. Examples of such groups include carboxyl, hydroxyl, phenolic hydroxyl, sulfonic acid, phosphoric acid, sulfonamide, sulfonylimide, (alkylsulfonyl)(alkylcarbonyl)methylene, (alkylsulfonyl)(alkylcarbonyl)imide, bis(alkylcarbonyl)methylene, bis(alkylcarbonyl)imide, bis(alkylsulfonyl)methylene, bis(alkylsulfonyl)imide, tri(alkylcarbonyl)methylene, and tri(alkylsulfonyl)methylene.

[0111] The polar group is preferably selected from at least one of carboxyl, hydroxyl, phenolic hydroxyl and sulfonic acid groups, and more preferably carboxyl, hydroxyl or phenolic hydroxyl.

[0112] As a detaching group that is released by the action of an acid, examples include groups represented by general formulas (S1) to (S3).

[0113] General formula (S1): -C(Rx) S1 (Rx) S2 (Rx) S3 )

[0114] General formula (S2): -C(=O)OC(Rx) S1 (Rx) S2 (Rx) S3 )

[0115] General formula (S3): -C(R) S1 (R) S2 (OR) S3 )

[0116] In general formulas (S1) and (S2), Rx S1 ~Rx S3 Each can independently represent a straight-chain or branched alkyl group that may have substituents without fluorine atoms, or a cycloalkyl group (monocyclic or polycyclic) that may have substituents without fluorine atoms. Additionally, when Rx... S1 ~Rx S3 When all Rx are straight-chain or branched alkyl groups that can have substituents without fluorine atoms, S1 ~Rx S3 In this mixture, at least two are preferably methyl or ethyl.

[0117] Among them, Rx S1 ~Rx S3 Preferably, each Rx represents a straight-chain or branched alkyl group that may have substituents without fluorine atoms, and Rx represents a linear or branched alkyl group. S1 ~Rx S3 More preferably, each can be independently represented as a straight-chain alkyl group having substituents that do not contain fluorine atoms.

[0118] Rx S1 ~Rx S3 Two of them can also bond together to form a single ring or multiple rings.

[0119] As Rx S1 ~Rx S3 The alkyl group is preferably an alkyl group with 1 to 10 carbon atoms, such as tert-butyl, tert-heptyl, methyl, ethyl, n-propyl, isopropyl, n-butyl, and isobutyl.

[0120] As for the cycloalkyl groups Rx1 to Rx3, monocyclic cycloalkyl groups such as cyclopentyl and cyclohexyl, and polycyclic cycloalkyl groups such as norbornyl, tetracyclic decyl, tetracyclic dodecyl, and adamantyl are preferred.

[0121] As Rx S1 ~Rx S3 The ring formed by the two bonds in Rx is preferably a cycloalkyl group. S1 ~Rx S3 The cycloalkyl group formed by the bonding of two atoms is preferably a monocyclic cycloalkyl group such as cyclopentyl or cyclohexyl, or a polycyclic cycloalkyl group such as norbornyl, tetracyclic decyl, tetracyclic dodecyl or adamantyl, and more preferably a monocyclic cycloalkyl group with 5 to 6 carbon atoms.

[0122] Rx S1 ~Rx S3 In the cycloalkyl group formed by the two bonds, for example, one of the methylene groups constituting the ring may be replaced by a heteroatom such as an oxygen atom other than a fluorine atom, or a group having a heteroatom other than a fluorine atom such as a carbonyl group.

[0123] The groups represented by general formula (S1) or (S2), preferably, for example, Rx1 can be methyl or ethyl, and Rx2 and Rx3 are bonded to each other to form the above-mentioned cycloalkyl group.

[0124] In general formula (S3), R S1 ~R S3 Each can be used independently to represent a hydrogen atom or a monovalent organic group. R S2 ~R S3 They can bond with each other to form rings. Examples of monovalent organic groups include straight-chain or branched alkyl groups that can have substituents without fluorine atoms, and cycloalkyl groups that can have substituents without fluorine atoms. R S1 Hydrogen atoms are preferred.

[0125] Furthermore, the aforementioned alkyl and cycloalkyl groups may also include groups having heteroatoms such as oxygen atoms other than fluorine atoms and / or heteroatoms such as carbonyl groups other than fluorine atoms. For example, in the aforementioned alkyl and cycloalkyl groups, one or more methylene groups may be substituted with groups having heteroatoms such as oxygen atoms other than fluorine atoms and / or heteroatoms such as carbonyl groups other than fluorine atoms.

[0126] Furthermore, R S3 It can bond with another substituent in the main chain of the repeating unit to form a ring.

[0127] From the viewpoint of better performance of the present invention, groups represented by general formula (a-1) or (a-2) are preferred as acid-degrading groups, and groups represented by general formula (a-1) are more preferred.

[0128] [Chemical Formula 3]

[0129]

[0130] In general formula (a-1), * represents the bonding site. R a1 This indicates a straight-chain or branched alkyl group that may have substituents without fluorine atoms, or a cycloalkyl group that may have substituents without fluorine atoms.

[0131] From the viewpoint that the present invention offers superior performance, R a1 The alkyl group represented is a linear or branched alkyl group that may have substituents without fluorine atoms, preferably a branched alkyl group that may have substituents without fluorine atoms. The aforementioned alkyl group may be a linear or branched alkyl group with substituents without fluorine atoms, or it may be an unsubstituted linear or branched alkyl group. As the substituents without fluorine atoms in the aforementioned alkyl group, it is preferably an alkyl group containing heteroatoms such as oxygen atoms other than fluorine atoms or heteroatoms such as oxygen atoms other than fluorine atoms. From the viewpoint of better effects of the present invention, the aforementioned alkyl group is preferably an unsubstituted linear or branched alkyl group.

[0132] The number of carbon atoms in the alkyl group is preferably 1 to 20, more preferably 2 to 10, and even more preferably 2 to 8.

[0133] As a result of R a1 Alkyl groups, for example, include tert-butyl, tert-heptyl, methyl, ethyl, n-propyl, isopropyl, n-butyl, isobutyl, sec-butyl, n-pentyl, isopentyl, neopentyl, tert-pentyl, n-hexyl, 1-methylpentyl, 4-methyl-2-pentyl, 2-ethylbutyl, n-heptyl, 1-methylhexyl, n-octyl, 1-methylheptyl, and 2-ethylhexyl.

[0134] From the viewpoint of achieving better results with the present invention, as a product of R a1 The alkyl group represented is preferably tert-butyl or tert-heptyl.

[0135] By R a1 The cycloalkyl group represented by the cycloalkyl group, which may have substituents without fluorine atoms, can be monocyclic or polycyclic. Furthermore, the aforementioned cycloalkyl group can be a cycloalkyl group with substituents without fluorine atoms, or it can be an unsubstituted cycloalkyl group. Preferably, it is a cycloalkyl group with substituents without fluorine atoms. As the substituent in the aforementioned cycloalkyl group, alkyl groups having 1 to 6 carbon atoms are preferred, and methyl or ethyl groups are more preferred.

[0136] The number of carbon atoms in the above-mentioned cycloalkyl group is preferably 4 to 25, more preferably 4 to 20, and even more preferably 4 to 15.

[0137] As a result of Ra1 Examples of cycloalkyl groups include cyclopentyl groups such as methylcyclopentyl or ethylcyclopentyl, cyclohexyl groups such as methylcyclohexyl or ethylcyclohexyl, cycloheptyl, cyclooctyl, cyclodecyl, norbornyl, tricyclodecyl, tetracyclododecyl, and adamantyl groups such as methyladamantyl or ethyladamantyl.

[0138] From the viewpoint of achieving better results with the present invention, as a product of R a1 The cycloalkyl group represented is preferably at least one selected from cyclopentyl, cyclohexyl, cycloheptyl and adamantyl, more preferably methylcyclopentyl, ethylcyclopentyl, methylcyclohexyl, ethylcyclohexyl, methyladamantyl or ethyladamantyl.

[0139] [Chemical Formula 4]

[0140]

[0141] In general formula (a-2), * denotes the bonding site. R a2 This indicates a straight-chain or branched alkyl group that may have substituents without fluorine atoms, or a cycloalkyl group that may have substituents without fluorine atoms.

[0142] As a result of R a2 The term "alkyl group" can refer to a straight-chain or branched alkyl group having substituents that do not contain fluorine atoms, and its meaning is the same as that of the alkyl group described above. a1 The same applies to straight-chain or branched alkyl groups that can have substituents that do not contain fluorine atoms.

[0143] As a result of R a2 The term can refer to cycloalkyl groups having substituents that do not contain fluorine atoms, for example, the cycloalkyl group described above consisting of R... a1 This indicates a cycloalkyl group that may have substituents that do not contain fluorine atoms.

[0144] R a3 It refers to a hydrogen atom, a straight-chain or branched alkyl group that may have substituents that do not contain fluorine atoms, or a cycloalkyl group that may have substituents that do not contain fluorine atoms.

[0145] As a result of R a3 The term "alkyl group" can refer to a straight-chain or branched alkyl group having substituents that do not contain fluorine atoms, and its meaning is the same as that of the alkyl group described above. a1 The same applies to straight-chain or branched alkyl groups that can have substituents that do not contain fluorine atoms.

[0146] As a result of R a3 The term "cycloalkyl" refers to a cycloalkyl group that may have substituents without fluorine atoms, and its meaning is the same as that of the cycloalkyl group described above. a1 The same applies to cycloalkyl groups that can have substituents that do not contain fluorine atoms.

[0147] Ra2 and R a3 They can bond together to form a ring.

[0148] R a2 and R a3 The rings formed by bonding together can be single rings or multiple rings. Among them, single rings are preferred.

[0149] As R a2 and R a3 Monocyclic rings formed by bonding together can include, for example, cycloalkanes with 3 to 6 carbon atoms. More specifically, examples include cyclopropane, cyclobutane, cyclopentane, and cyclohexane rings. Some of the carbon atoms in these rings can be replaced by heteroatoms such as oxygen atoms (excluding fluorine atoms).

[0150] Additionally, R a2 and R a3 The rings formed by the bonding of the atoms do not contain fluorine atoms.

[0151] (Number of fluorine atoms)

[0152] The sulfonium cation contained in a specific compound has at least three fluorine atoms in the portion excluding the groups containing acid-degrading groups. That is, the substituents in the sulfonium cation, excluding the groups containing acid-degrading groups, have a total of three or more fluorine atoms, while the groups containing acid-degrading groups do not have fluorine atoms.

[0153] The number of fluorine atoms is preferably 6 or more. There is no particular upper limit to the number of fluorine atoms, but it is preferably 30 or less, more preferably 25 or less, and even more preferably 20 or less.

[0154] Additionally, for example, when the sulfonium cation has a trifluoromethyl group, the number of fluorine atoms is 3.

[0155] Furthermore, when the sulfonium cation has a substituent containing a fluorine atom, the number of substituents containing a fluorine atom can be one or more.

[0156] Sulfonium cations may have substituents other than the groups containing acid-degrading groups and substituents having fluorine atoms (e.g., unsubstituted alkyl groups).

[0157] Sulfonium cations can be used alone or in combination with two or more.

[0158] Furthermore, it can contain more than two sulfonium cations of the same type.

[0159] The following are specific examples of sulfonium cations, but the invention is not limited thereto.

[0160] [Chemical Formula 5]

[0161]

[0162] [Chemical Formula 6]

[0163]

[0164] [Chemical Formula 7]

[0165]

[0166] [Chemical Formula 8]

[0167]

[0168] [Chemical Formula 9]

[0169]

[0170] [Chemical Formula 10]

[0171]

[0172] (Organic anions)

[0173] The specific compound preferably contains an organic anion. The organic anion can be a monovalent anion or an anion with a valence of more than two valences.

[0174] Organic anions are preferably anions with significantly low ability to induce nucleophilic reactions; specifically, non-nucleophilic anions can be cited.

[0175] Examples of non-nucleophilic anions include sulfonic acid anions (aliphatic sulfonic acid anions, aromatic sulfonic acid anions, and camphor sulfonic acid anions), carboxylic acid anions (aliphatic carboxylic acid anions, aromatic carboxylic acid anions, and aralkyl carboxylic acid anions), sulfonyl imide anions, bis(alkylsulfonyl) imide anions, and tri(alkylsulfonyl) methylated anions.

[0176] The aliphatic site in the aliphatic sulfonic acid anion and the aliphatic carboxylic acid anion can be a straight-chain or branched alkyl group or a cycloalkyl group, preferably a straight-chain or branched alkyl group with 1 to 30 carbon atoms or a cycloalkyl group with 3 to 30 carbon atoms.

[0177] The aforementioned alkyl group can be, for example, a fluoroalkyl group (which may or may not have substituents other than fluorine atoms. It can be a perfluoroalkyl group).

[0178] The aryl group in the aromatic sulfonic acid anion and the aromatic carboxylic acid anion is preferably an aryl group with 6 to 14 carbon atoms, such as phenyl, tolyl and naphthyl.

[0179] The alkyl, cycloalkyl, and aryl groups mentioned above may have substituents. There are no particular limitations on the substituents; specifically, examples include halogen atoms such as nitro, fluorine or chlorine atoms, carboxyl, hydroxyl, amino, cyano, alkoxy (preferably 1 to 15 carbon atoms), alkyl (preferably 1 to 10 carbon atoms), cycloalkyl (preferably 3 to 15 carbon atoms), aryl (preferably 6 to 14 carbon atoms), alkoxycarbonyl (preferably 2 to 7 carbon atoms), acyl (preferably 2 to 12 carbon atoms), alkoxycarbonyloxy (preferably 2 to 7 carbon atoms), alkylthio (preferably 1 to 15 carbon atoms), alkylsulfonyl (preferably 1 to 15 carbon atoms), alkyliminosulfonyl (preferably 1 to 15 carbon atoms), and aryloxysulfonyl (preferably 6 to 20 carbon atoms).

[0180] The aralkyl group in the aralkyl carboxylic acid anion is preferably an aralkyl group with 7 to 14 carbon atoms, such as benzyl, phenethyl, naphthylmethyl, naphthylethyl and naphthylbutyl.

[0181] Examples of sulfonyl imide anions include saccharin anion.

[0182] The alkyl group in the bis(alkylsulfonyl)imide anion and the tri(alkylsulfonyl)methyl anion is preferably an alkyl group having 1 to 5 carbon atoms. Examples of substituents for these alkyl groups include halogen atoms, alkyl groups substituted with halogen atoms, alkoxy groups, alkylthio groups, alkoxysulfonyl groups, aryloxysulfonyl groups, and cycloalkylaryloxysulfonyl groups, with fluorine atoms or alkyl groups substituted with fluorine atoms being preferred.

[0183] Furthermore, the alkyl groups in the bis(alkylsulfonyl)imide anion can bond with each other to form a ring structure. As a result, the acid strength increases.

[0184] Other examples of non-nucleophilic anions include phosphorus fluoride (e.g., PF6). - ), boron fluoride (e.g., BF4) - ) and antimony fluoride (e.g., SbF6) - ).

[0185] As a non-nucleophilic anion, it is preferably an aliphatic sulfonic acid anion in which at least the α-position of the sulfonic acid is substituted with a fluorine atom, an aromatic sulfonic acid anion in which the fluorine atom or a group having a fluorine atom is substituted, a bis(alkylsulfonyl)imide anion in which the alkyl group is substituted with a fluorine atom, or a tri(alkylsulfonyl)methylation anion in which the alkyl group is substituted with a fluorine atom. More preferably, it is a perfluoroaliphatic sulfonic acid anion (preferably with 4 to 8 carbon atoms) or a benzenesulfonic acid anion having a fluorine atom, and even more preferably, it is a nonafluorobutanesulfonic acid anion, a perfluorooctanesulfonic acid anion, a pentafluorobenzenesulfonic acid anion, or a 3,5-bis(trifluoromethyl)benzenesulfonic acid anion.

[0186] As a non-nucleophilic anion, anion represented by the following formula (AN1) is also preferred.

[0187] [Chemical Formula 11]

[0188]

[0189] In general formula (AN1),

[0190] o represents an integer from 1 to 3. p represents an integer from 0 to 10. q represents an integer from 0 to 10.

[0191] Xf represents a fluorine atom or an alkyl group substituted with at least one fluorine atom. The alkyl group preferably has 1 to 10 carbon atoms, more preferably 1 to 4. Furthermore, as the alkyl group substituted with at least one fluorine atom, a perfluoroalkyl group is preferred.

[0192] Xf is preferably a fluorine atom or a perfluoroalkyl group having 1 to 4 carbon atoms, more preferably a fluorine atom or CF3. In particular, it is even more preferred that Xf in both cases is a fluorine atom.

[0193] R4 and R5 each independently represent a hydrogen atom, a fluorine atom, an alkyl group, or an alkyl group substituted with at least one fluorine atom. When multiple R4 and R5 are present, R4 and R5 can be the same or different.

[0194] The alkyl groups represented by R4 and R5 may have substituents, and the number of carbon atoms is preferably 1 to 4. R4 and R5 are preferably hydrogen atoms.

[0195] Specific examples and preferred embodiments of alkyl groups substituted with at least one fluorine atom are the same as those of Xf in general formula (AN1).

[0196] L represents a binary linker. When multiple Ls exist, they can be the same or different.

[0197] Examples of divalent linkers include -O-CO-O-, -COO-, -OCO-, -CONH-, -NHCO-, -CO-, -O-, -S-, -SO-, -SO2-, alkylene groups (preferably with 1 to 6 carbon atoms), cycloalkylene groups (preferably with 3 to 15 carbon atoms), alkenyl groups (preferably with 2 to 6 carbon atoms), and divalent linkers formed by combining multiple of these. Preferably, the alkylene compounds are -O-CO-O-, -COO-, -OCO-, -CONH-, -NHCO-, -CO-, -O-, -SO2-, -O-CO-O-alkylene-, -alkylene-O-CO-O-, -COO-alkylene-, -OCO-alkylene-, -CONH-alkylene-, or -NHCO-alkylene-, and more preferably -O-CO-O-, -O-CO-O-alkylene-, -alkylene-O-CO-O-, -COO-, -OCO-, -CONH-, -SO2-, -COO-alkylene-, or -OCO-alkylene-.

[0198] W represents an organic group containing a cyclic structure. Preferably, it is a cyclic organic group.

[0199] Examples of cyclic organic groups include alicyclic groups, aryl groups, and heterocyclic groups.

[0200] The alicyclic group can be monocyclic or polycyclic. Examples of monocyclic alicyclic groups include cyclopentyl, cyclohexyl, and cyclooctyl. Examples of polycyclic alicyclic groups include norbornyl, tricyclic decyl, tetracyclic decyl, tetracyclic dodecyl, and adamantyl. Among these, alicyclic groups with a large volume structure having 7 or more carbon atoms, such as norbornyl, tricyclic decyl, tetracyclic decyl, tetracyclic dodecyl, and adamantyl, are preferred.

[0201] The aryl group can be monocyclic or polycyclic. Examples of such aryl groups include phenyl, naphthyl, phenanthryl, and anthracene.

[0202] The heterocyclic group can be monocyclic or polycyclic. Polycyclic heterocyclic groups can better suppress acid diffusion. Furthermore, the heterocyclic group can be aromatic or non-aromatic. Examples of aromatic heterocycles include furan rings, thiophene rings, benzofuran rings, benzothiophene rings, dibenzofuran rings, dibenzothiophene rings, and pyridine rings. Examples of non-aromatic heterocycles include tetrahydropyran rings, lactone rings, sulfonyl lactone rings, and decahydroisoquinoline rings. Furan rings, thiophene rings, pyridine rings, or decahydroisoquinoline rings are particularly preferred as heterocyclic groups.

[0203] The aforementioned cyclic organic groups may have substituents. Examples of such substituents include alkyl groups (which may be linear or branched, preferably with 1 to 12 carbon atoms), cycloalkyl groups (which may be monocyclic, polycyclic, or spirocyclic, preferably with 3 to 20 carbon atoms), aryl groups (preferably with 6 to 14 carbon atoms), hydroxyl groups, alkoxy groups, ester groups, amide groups, carbamate groups, urea groups, thioether groups, sulfonamide groups, and sulfonate groups. Furthermore, the carbon atoms constituting the cyclic organic groups (the carbon atoms that contribute to ring formation) may be carbonyl carbons.

[0204] SO3 is preferred as the anion represented by the general formula (AN1). - -CF2-CH2-OCO-(L)q'-W、SO3 - -CF2-CHF-CH2-OCO-(L)q'-W、SO3 - -CF2-COO-(L)q'-W、SO3 - -CF2-CF2-CH2-CH2-(L)qW or SO3 - -CF2-CH(CF3)-OCO-(L)q'-W. Here, L, q, and W are the same as in general formula (AN1). q' represents an integer from 0 to 10.

[0205] As a non-nucleophilic anion, anion represented by the following formula (AN2) is also preferred.

[0206] [Chemical Formula 12]

[0207]

[0208] In general formula (AN2),

[0209] X B1 and X B2 Each can be represented independently as either a hydrogen atom or a monovalent organic group without a fluorine atom. X B1 and X B2 Hydrogen atoms are preferred.

[0210] X B3 and X B4 Each can independently represent a hydrogen atom or a monovalent organic group. X is preferred. B3 and X B4 At least one of them is a fluorine atom or a monovalent organic group having a fluorine atom, more preferably X B3 and X B4 Both are fluorine atoms or monovalent organic groups having fluorine atoms. X is further preferred. B3 and X B4 Both of these are alkyl groups that have been substituted with fluorine.

[0211] L, q, and W are the same as in general formula (AN1).

[0212] As a non-nucleophilic anion, the anion represented by the following formula (AN3) is preferred.

[0213] [Chemical Formula 13]

[0214]

[0215] In general formula (AN3), Xa independently represents a fluorine atom or an alkyl group substituted with at least one fluorine atom. Xb independently represents a hydrogen atom or an organic group without a fluorine atom. The definitions and preferred methods of o, p, q, R4, R5, L and W are the same as in general formula (AN1).

[0216] As a non-nucleophilic anion, anion represented by the following formula (AN4) is also preferred.

[0217] [Chemical Formula 14]

[0218]

[0219] In general formula (AN4), R 1 and R 2 Each can be used independently to represent a substituent or a hydrogen atom that is not an electron-withdrawing group.

[0220] Examples of substituents that are not electron-withdrawing groups include hydrocarbon groups, hydroxyl groups, oxyhydrocarbon groups, oxycarbonyl hydrocarbon groups, amino groups, hydrocarbon-substituted amino groups, and hydrocarbon-substituted amide groups.

[0221] Furthermore, as a substituent that is not an electron-withdrawing group, it is preferably independently -R', -OH, -OR', -OCOR', -NH2, -NR'2, -NHR', or -NHCOR'. R' is a monovalent hydrocarbon group.

[0222] Examples of monovalent hydrocarbon groups represented by R' include alkyl groups such as methyl, ethyl, propyl, and butyl; alkenyl groups such as vinyl, propynyl, and butenyl; alkynyl groups such as ethynyl, propynyl, and butynyl; cycloalkyl groups such as cyclopropyl, cyclobutyl, cyclopentyl, cyclohexyl, norbornyl, and adamantyl; cycloalkenyl groups such as cyclopropenyl, cyclobutenyl, cyclopentenyl, and norbornyl; aryl groups such as phenyl, tolyl, xylyl, mesitylelel, naphthyl, methylnaphthyl, anthracenel, and methylanthrayl; and aromatic hydrocarbon groups such as benzyl, phenethyl, phenylpropyl, naphthylmethyl, and anthracenemethyl.

[0223] Among them, R 1 and R 2 Preferably, each is independently a hydrocarbon group (preferably a cycloalkyl group) or a hydrogen atom.

[0224] In general formula (AN4), L represents a divalent linker consisting of a combination of one or more linking groups S and one or more alkylene groups that may have substituents, or a divalent linker consisting of one or more linking groups S.

[0225] The linker S is selected from * A -O-CO-O-* B 、* A -CO-* B 、* A -CO-O-* B 、* A -O-CO-* B 、* A -O-* B 、* A -S-* B and* A -SO2-* B The groups in.

[0226] Wherein, when L is a form of "a divalent linker composed of a combination of one or more linking groups S and one or more alkylene groups that may have substituents" or "a divalent linker composed of a combination of one or more linking groups S and one or more alkylene groups that do not have substituents", the linking group S is preferably selected from * A -O-CO-O-* B 、* A -CO-* B 、* A -O-CO-* B 、* A -O-* B 、* A -S-* B and* A -SO2-* B The linking group. In other words, when the alkylene groups in "a divalent linking group consisting of a combination of one or more linking groups S and one or more alkylene groups that may have substituents" are all unsubstituted alkylene groups, the linking group S is preferably selected from * A -O-CO-O-* B 、* A -CO-* B 、* A -O-CO-* B 、* A -O-* B 、* A -S-* B and* A -SO2-* B The groups in.

[0227] *A R in general formula (AN4) 3 Side bonding position, * B The -SO3 in the general formula (AN4) - The bonding position on the side.

[0228] In a divalent linker consisting of one or more linking groups S and one or more alkylene groups that may have substituents, there may be only one linking group S or there may be two or more alkylene groups that may have substituents. When there are multiple linking groups S, the multiple linking groups S may be the same or different. When there are multiple alkylene groups, the multiple alkylene groups may be the same or different.

[0229] Furthermore, the linker bases S can be continuously bonded to each other. Preferably, they are selected from * A -CO-* B 、* A -O-CO-* B and* A -O-* B The groups in the group are continuously bonded without forming "* A -O-CO-O-* B Furthermore, it is preferred to select from * A -CO-* B and* A -O-* B The groups in the group are continuously bonded and none of them form "*". A -O-CO-* B "and"* A -CO-O-* B ".

[0230] In a divalent linkage consisting of one or more linkage bases S, there can be only one linkage base S, or there can be two or more linkage bases S. When there are multiple linkage bases S, the linkage bases S can be the same or different.

[0231] At this time, it is also preferable to select from * A -CO-* B 、* A -O-CO-* B and* A -O-* B The groups in the group are continuously bonded without forming "* A -O-CO-O-* B Furthermore, it is preferred to select from * A -CO-* B and* A -O-* BThe groups in the group are continuously bonded and none of them form "*". A -O-CO-* B "and"* A -CO-O-* B ".

[0232] However, in any case, in L, relative to -SO3 - The atoms at the β position are not carbon atoms with fluorine atoms as substituents.

[0233] In addition, when the atom at the β position is a carbon atom, it is permissible for the carbon atom to be directly substituted with a fluorine atom, and the carbon atom may contain a substituent having a fluorine atom (e.g., fluoroalkyl groups such as trifluoromethyl).

[0234] Furthermore, in other words, the atom at the β position mentioned above refers to the atom corresponding to -C(R) in the general formula (AN4). 1 (R) 2 )- Atoms in L that are directly bonded.

[0235] In this case, L preferably has only one connecting base S.

[0236] That is, L preferably represents a divalent linker consisting of a combination of one linker S and one or more alkylene groups that may have substituents, or a divalent linker consisting of one linker S.

[0237] L is preferably a group represented by the following formula (AN4-2).

[0238] * a -(CR 2a 2) X -Q-(CR 2b 2) Y -* b (AN4-2)

[0239] In general formula (AN4-2), * a R in general formula (AN4) 3 The bonding positions.

[0240] *b represents -C(R) in the general formula (AN4). 1 (R) 2 The bonding position of )-.

[0241] X and Y each independently represent integers from 0 to 10, preferably integers from 0 to 3.

[0242] R 2a and R 2b Each can be used to represent a hydrogen atom or a substituent independently.

[0243] When R 2aand R 2b When there are multiple R values, there are multiple R values. 2a and R 2b They can be the same or different.

[0244] When Y is 1 or more, it corresponds to -C(R) in the general formula (AN4). 1 (R) 2 )- Directly bonded CR 2b R in 2 2b These are atoms other than fluorine atoms.

[0245] Q represents * A -O-CO-O-* B 、* A -CO-* B 、* A -CO-O-* B 、* A -O-CO-* B 、* A -O-* B 、* A -S-* B or* A -SO2-* B .

[0246] Where X+Y in general formula (AN4-2) is 1 or more and R in general formula (AN4-2) 2a and R 2b When all atoms are hydrogen atoms, Q represents * A -O-CO-O-* B 、* A -CO-* B 、* A -O-CO-* B 、* A -O-* B 、* A -S-* B or* A -SO2-* B .

[0247] * A R in general formula (AN4) 3 Side bonding position, * B The -SO3 in the general formula (AN4) - The bonding position on the side.

[0248] In general formula (AN4), R 3 It represents an organic group.

[0249] There are no restrictions on the presence of one or more carbon atoms in the aforementioned organic groups. They can be straight-chain groups (e.g., straight-chain alkyl groups), branched-chain groups (e.g., branched alkyl groups such as tert-butyl), or cyclic structures. The aforementioned organic groups may or may not have substituents. The aforementioned organic groups may or may not have heteroatoms (oxygen atoms, sulfur atoms, and / or nitrogen atoms, etc.).

[0250] Among them, R 3 Preferably, the organic group has a cyclic structure. The cyclic structure can be monocyclic, polycyclic, or have substituents. The ring in the organic group containing the cyclic structure is preferably directly bonded to L in the general formula (AN4).

[0251] The aforementioned organic groups with cyclic structures may or may not have heteroatoms (oxygen, sulfur, and / or nitrogen atoms, etc.). A heteroatom may be replaced by one or more carbon atoms forming a cyclic structure.

[0252] The organic groups having cyclic structures are preferably, for example, cyclic hydrocarbon groups, lactone cyclic groups, and sulfonyl lactone cyclic groups. Among these, the organic groups having cyclic structures are preferably cyclic hydrocarbon groups.

[0253] The hydrocarbon group in the above-mentioned cyclic structure is preferably a monocyclic or polycyclic cycloalkyl group. These groups may also have substituents.

[0254] The aforementioned cycloalkyl group can be monocyclic (such as cyclohexyl) or polycyclic (such as adamantyl), and preferably has 5 to 12 carbon atoms.

[0255] As the aforementioned lactone group and sulfonolactone group, for example, it is preferred to be a group formed by removing one hydrogen atom from the ring member atom constituting the lactone structure or sulfonolactone structure in any one of the structures represented by the general formulas (LC1-1) to (LC1-21) and (SL1-1) to (SL1-3) described below.

[0256] As a non-nucleophilic anion, it can be a benzenesulfonic acid anion, preferably a benzenesulfonic acid anion substituted with branched alkyl or cycloalkyl groups.

[0257] As a non-nucleophilic anion, an aromatic sulfonic acid anion represented by the following formula (AN5) is also preferred.

[0258] [Chemical Formula 15]

[0259]

[0260] In general formula (AN5),

[0261] Ar represents aryl (phenyl, etc.), and may also have substituents other than sulfonic acid anions and -(DB) groups. Examples of substituents that may be present include fluorine atoms and hydroxyl groups.

[0262] n represents an integer greater than or equal to 0. Preferably, n is 1 to 4, more preferably 2 to 3, and even more preferably 3.

[0263] D represents a single bond or a divalent linker. Examples of divalent linkers include ether groups, thioether groups, carbonyl groups, sulfoxide groups, sulfone groups, sulfonate groups, ester groups, and groups formed by combinations of two or more of these.

[0264] B represents a hydrocarbon group.

[0265] B is preferably an aliphatic hydrocarbon structure. B is more preferably isopropyl, cyclohexyl, or aryl (tricyclohexylphenyl, etc.) that may have further substituents.

[0266] Disulfonamide anion is preferred as a non-nucleophilic anion.

[0267] Disulfonamide anion, for example, is composed of N... - (SO2-R q )2 represents anion.

[0268] Here, R q This indicates an alkyl group that may have substituents, preferably a fluoroalkyl group, and more preferably a perfluoroalkyl group. (2 R's) q They can bond together to form a ring. Two Rs q The groups formed by bonding together are preferably alkylene groups that can have substituents, preferably fluoroalkylene groups, and more preferably perfluoroalkylene groups. The number of carbon atoms in the above-mentioned alkylene groups is preferably 2 to 4.

[0269] Furthermore, examples of anions can be given by the following formulas (d1-1) to (d1-3).

[0270] Certain compounds that have anions represented by the following formulas (d1-1) to (d1-3) as anions can also function as acid diffusion control agents, as described later.

[0271] [Chemical Formula 16]

[0272]

[0273] In general formula (d1-1), R 51 This indicates a hydrocarbon group (e.g., aryl, such as phenyl) that may have substituents (e.g., hydroxyl).

[0274] In general formula (d1-2), Z 2cThis indicates a hydrocarbon group with 1 to 30 carbon atoms that can have substituents (wherein the fluorine atom is not replaced by the carbon atom adjacent to S).

[0275] Z 2c The aforementioned hydrocarbon group can be linear or branched, and can have a cyclic structure. Furthermore, the carbon atom in the aforementioned hydrocarbon group (preferably, a carbon atom that is a ring member when the aforementioned hydrocarbon group has a cyclic structure) can be a carbonyl carbon (-CO-). Examples of such hydrocarbon groups include norbornyl groups, which can have substituents. The carbon atom forming the aforementioned norbornyl group can be a carbonyl carbon.

[0276] Furthermore, in the general formula (d1-2), "Z" 2c -SO3 - "Preferred anions are different from those represented by the formulas (AN1) to (AN5) above. For example, Z..." 2c Preferably, it contains groups other than aryl groups. And, for example, Z 2c In, relative to -SO3 - The atoms at the α and β positions are preferably atoms other than carbon atoms that have fluorine atoms as substituents. For example, Z 2c In, relative to -SO3 - The atom at the α-position and / or the atom at the β-position are preferably ring-member atoms in the cyclic group.

[0277] In general formula (d1-3), R 52 Y represents an organic group (preferably a hydrocarbon group with a fluorine atom). 3 Rf indicates a linear, branched, or cyclic alkylene, arylene, or carbonyl group, while Rf indicates a hydrocarbon group.

[0278] Organic anions can be used alone or in combination with two or more.

[0279] (Compounds represented by the general formula (S-1))

[0280] As a specific compound, it is preferred to be a compound represented by the general formula (S-1).

[0281] [Chemical Formula 17]

[0282]

[0283] In general formula (S-1), X - It represents an organic anion.

[0284] By X - The organic anions represented have the same meaning as those mentioned above.

[0285] Ar S1 ~Ar S3Each can be independently represented as an aromatic hydrocarbon cycloal group that may have substituents.

[0286] As a product of Ar S1 ~Ar S3 The aromatic hydrocarbon cyclic group represented can be, for example, aryl groups such as phenylcycloyl, naphthyl, and anthracenecycloyl. Preferably, each of the above-mentioned aromatic hydrocarbon cyclic groups is independently a phenylcycloyl group.

[0287] By Ar S1 ~Ar S3 The aromatic hydrocarbon cyclogroup represented can be an aromatic hydrocarbon cyclogroup with substituents or an unsubstituted aromatic hydrocarbon cyclogroup. Preferably, the aromatic hydrocarbon cyclogroup is an aromatic hydrocarbon cyclogroup with substituents.

[0288] Substituents in the aforementioned aromatic hydrocarbon cycloalloys can include, for example, halogen atoms, straight-chain or branched alkyl groups having halogen atoms, and alkoxy groups having halogen atoms. More specifically, they are preferably selected from at least one of fluorine atoms, iodine atoms, alkyl groups, fluoroalkyl groups, fluorool groups, and fluoroalkoxy groups, and more preferably from at least one of fluorine atoms and fluoroalkyl groups.

[0289] The aromatic hydrocarbon group is preferably an aromatic hydrocarbon group substituted with at least one selected from fluorine atoms and fluoroalkyl groups, and more preferably includes an aryl group substituted with at least one selected from fluorine atoms and fluoroalkyl groups.

[0290] The fluoroalkyl, fluorool, and fluoroalkoxy groups mentioned above only need to have one or more fluorine atoms, and all hydrogen atoms in the alkylene group can be replaced by fluorine atoms.

[0291] Furthermore, Ar S1 ~Ar S3 They can bond together to form a ring.

[0292] The number of carbon atoms in the above-mentioned alkyl, alcohol, and alkoxy groups is preferably 1 to 10, more preferably 1 to 8, and even more preferably 1 to 5.

[0293] Examples of alkyl groups mentioned above include methyl, tert-butyl, ethyl, n-propyl, isopropyl, n-butyl, sec-butyl, tert-butyl, octyl, dodecyl, nonadecanyl, cyclobutyl, cyclopentyl, cyclohexyl, methylcyclohexyl, 2-ethylpropyl, and 2-ethylhexyl.

[0294] From the viewpoint of achieving better results in this invention, the alkyl group is preferably methyl or tert-butyl.

[0295] Examples of fluoroalkyl groups include trifluoromethyl, pentafluoroethyl, heptafluoropropyl, nonafluorobutyl, 2-(perfluorobutyl)ethyl, 3-perfluorobutyl-2-hydroxypropyl, 2-(perfluorohexyl)ethyl, 3-perfluorohexyl-2-hydroxypropyl, 2-(perfluorooctyl)ethyl, 3-perfluorooctyl-2-hydroxypropyl, 2-(perfluorodecyl)ethyl, 2-(perfluoro-3-methylbutyl)ethyl, 3-(perfluoro-3-methylbutyl)-2-hydroxypropyl, 2-(perfluoro-5-methylhexyl)ethyl, 2-(perfluoro-5-methylhexyl)-2-hydroxypropyl, 2-(perfluoro-7-methyloctyl)ethyl, and 2-(perfluoro-7-methyloctyl)-2-hydroxypropyl.

[0296] From the viewpoint of achieving better results in this invention, the preferred fluoroalkyl group is trifluoromethyl, pentafluoroethyl, heptafluoropropyl, or nonafluorobutyl.

[0297] Examples of fluorool groups include -C(CF3)2OH, -CF2OH, -CH2CF2OH, -CH2CF2CF2OH, -C(CF3)2OH, -CF2CF(CF3)OH and -CH2C(CF3)2OH.

[0298] From the viewpoint of achieving better results in this invention, the fluorool group is preferably -C(CF3)2OH.

[0299] Examples of fluoroalkoxy groups include fluoromethoxy, difluoromethoxy, and trifluoromethoxy; fluoroethoxy, difluoroethoxy, trifluoroethoxy, tetrafluoroethoxy, and pentafluoroethoxy; and fluoropropoxy, difluoropropoxy, trifluoropropoxy, tetrafluoropropoxy, pentafluoropropoxy, hexafluoropropoxy, heptafluoropropoxy, and octafluoropropoxy.

[0300] From the viewpoint of achieving better results in this invention, the fluoroalkoxy group is preferably selected from at least one of fluoromethoxy, fluoroethoxy, and fluoropropoxy, and more preferably trifluoromethoxy.

[0301] Ar S1 ~Ar S3 In this context, at least one group represents a group represented by the above general formula (T-1).

[0302] By Ar 1 ~Ar 3 The aromatic hydrocarbon cyclic group represents a total of three or more fluorine atoms. Ar 1 ~Ar 3 In Ar, only one has more than three fluorine atoms, while the other may not have any fluorine atoms. 1 ~Ar 3It may have more than one fluorine atom. That is, the compound represented by the general formula (S-1) has at least three fluorine atoms. The number of fluorine atoms is preferably six or more. There is no particular upper limit, but it is preferably 30 or less, more preferably 25 or less, and even more preferably 20 or less.

[0303] As a specific compound, it is more preferably a compound represented by the general formula (S-2).

[0304] [Chemical Formula 18]

[0305]

[0306] R a This refers to a group containing an acid-degrading group. The definition of a group containing an acid-degrading group is as described above, and it is preferably a group represented by the general formula (S-3). In the general formula (S-3), *, L T1 and R T1 The definition is as described above.

[0307] [Chemical Formula 19]

[0308] *-L T1 -R T1

[0309] (S-3)

[0310] R b1 R b2 and R b3 Each can be independently represented as a fluorine atom or an organic group containing a fluorine atom. As an organic group containing a fluorine atom, it is sufficient to have a fluorine atom; for example, linear or branched alkyl groups, cycloalkyl groups, or aryl groups containing a fluorine atom can be cited.

[0311] There is no particular limitation on the number of carbon atoms in the above-mentioned alkyl and cycloalkyl groups, but the number of carbon atoms is preferably 1 to 10, more preferably 1 to 5, and even more preferably 1 to 3.

[0312] As the organic group having fluorine atoms mentioned above, it is preferably a straight-chain or branched alkyl group having fluorine atoms, more preferably a straight-chain or branched fluoroalkyl group, and even more preferably a straight-chain or branched perfluoroalkyl group.

[0313] R c1 R c2 and R c3 Unlike groups containing acid-degrading groups, each of these refers independently to an organic group that does not have a fluorine atom. Examples of such organic groups include unsubstituted alkyl groups, unsubstituted cycloalkyl groups, and unsubstituted aryl groups.

[0314] There is no particular limitation on the number of carbon atoms in the above-mentioned alkyl and cycloalkyl groups, but the number of carbon atoms is preferably 1 to 10, more preferably 1 to 5, and even more preferably 1 to 3.

[0315] b1 represents an integer from 0 to 4, b2 represents an integer from 0 to 5, and b3 represents an integer from 0 to 5.

[0316] c1 represents an integer from 0 to 4, c2 represents an integer from 0 to 5, and c3 represents an integer from 0 to 5.

[0317] The sum of b1, b2 and b3 represents an integer greater than 1.

[0318] The sum of b1 and c1 represents an integer from 0 to 4, the sum of b2 and c2 represents an integer from 0 to 5, and the sum of b3 and c3 represents an integer from 0 to 5.

[0319] R b1 The number of fluorine atoms in it, R b2 The number of fluorine atoms and R b3 The total number of fluorine atoms in the sample is 3 or more, more preferably 6 or more. There is no particular upper limit, but it is preferably 30 or less, more preferably 25 or less, and even more preferably 20 or less.

[0320] R b1 ~R b3 In this case, only one has more than three fluorine atoms, while the other may not have any fluorine atoms. Therefore, all R... b1 ~R b3 It can have more than one fluorine atom.

[0321] As a specific compound, examples include compounds having two or more cation sites and the same number of anionic sites as the aforementioned cation sites, wherein at least one of the aforementioned cation sites is a specific cation (hereinafter also simply referred to as "compound W").

[0322] A cation site is a structural site containing a positively charged atom or group of atoms. As described above, in compound W, at least one of the two or more cation sites is a specific cation. From the viewpoint of further enhancing the effects of the present invention, it is preferable that all two or more cation sites contained in compound W are specific cations.

[0323] Furthermore, in compound W, at least one of the two or more cation sites needs to be a specific cation, and it may include organic cations other than the specific cation. Examples of organic cations other than the specific cation include sulfonium cations and iodonium ions.

[0324] An anionic site is a structural site containing a negatively charged atom or group of atoms. For example, anionic functional groups that may exist in compound W can be designated as anionic sites.

[0325] Compound W preferably has an organic anion having the same number of anionic functional groups as the cation sites of compound W.

[0326] As described above, compound W has two or more (preferably two to three) cation sites and the same number of anionic sites as the cation sites.

[0327] That is, compound W has two or more (preferably two to three) anionic sites (preferably anionic functional groups).

[0328] Examples of anionic functional groups mentioned above include -SO3. - and as part of -SO3 - The group, -COO - and as part of -COO - The group, as part of which has -N - - groups, and as part of having a carboanion (-C - <) group.

[0329] Among them, the anionic site is preferably a group represented by general formula (B-1) to (B-13).

[0330] [Chemical Formula 20]

[0331]

[0332] In general formulas (B-1) to (B-13), * indicates the bonding position.

[0333] In addition, the * in general formula (B-12) is preferably a bonding position relative to a group that is neither -CO- nor -SO2-.

[0334] In general formulas (B-1) to (B-5) and (B-12), R X1 It represents an organic group.

[0335] As R X1 Preferably, it is an alkyl group (which can be straight-chain or branched, with 1 to 15 carbon atoms), a cycloalkyl group (which can be monocyclic or polycyclic, with 3 to 20 carbon atoms), or an aryl group (which can be monocyclic or polycyclic, with 6 to 20 carbon atoms).

[0336] Additionally, in general formula (B-5), R X1 In and N -The atoms that are directly bonded are preferably not either the carbon atom in -CO- or the sulfur atom in -SO2-.

[0337] R X1 The cycloalkyl group can be monocyclic or polycyclic.

[0338] As R X1 The cycloalkyl groups in the cycloalkyl group include, for example, norbornyl and adamantyl.

[0339] R X1 The cycloalkyl group may have substituents that are preferably alkyl (which may be straight-chain or branched. Preferably, it has 1 to 5 carbon atoms).

[0340] R X1 One or more carbon atoms of the cycloalkyl ring members can be replaced by carbonyl carbon atoms.

[0341] R X1 The alkyl group in the alkyl group preferably has 1 to 10 carbon atoms, more preferably 1 to 5.

[0342] R X1 The alkyl group may have substituents, preferably cycloalkyl, fluorine, or cyano groups.

[0343] Examples of cycloalkyl groups that are substituents as described above can also be found in R. X1 The cycloalkyl group is specified when it is a cycloalkyl group.

[0344] When R X1 When the alkyl group in the alkyl group has a fluorine atom as a substituent, the alkyl group can be a perfluoroalkyl group.

[0345] Furthermore, R X1 In the alkyl group, more than one -CH2- can be replaced by a carbonyl group.

[0346] R X1 The aryl group is preferably a benzene ring group.

[0347] R X1 The aryl group can preferably have substituents such as alkyl, fluorine, or cyano groups. Examples of alkyl groups as substituents include R. X1 When the alkyl group is described as cycloalkyl, it is preferably perfluoroalkyl, and more preferably perfluoromethyl.

[0348] In general formulas (B-7) and (B-11), R X2 It indicates a hydrogen atom or a substituent other than a fluorine atom and a perfluoroalkyl group.

[0349] By R X2 The fluorine atom and the substituents other than perfluoroalkyl are preferably alkyl or cycloalkyl groups other than perfluoroalkyl.

[0350] As examples of the aforementioned alkyl groups, those derived from R X1 The alkyl group is obtained by removing the perfluoroalkyl group from the alkyl group. Furthermore, the alkyl group preferably does not have a fluorine atom.

[0351] As an example of the aforementioned cycloalkyl groups, R can be cited. X1 The cycloalkyl group in the cycloalkyl group. Furthermore, the cycloalkyl group preferably does not have a fluorine atom.

[0352] In general formula (B-8), R XF1 This indicates a hydrogen atom, a fluorine atom, or a perfluoroalkyl group. Multiple R groups are included. XF1 At least one of them represents a fluorine atom or a perfluoroalkyl group.

[0353] By R XF1 The number of carbon atoms in the perfluoroalkyl group is preferably 1 to 15, more preferably 1 to 10, and even more preferably 1 to 6.

[0354] In general formula (B-10), R XF2 It indicates a fluorine atom or a perfluoroalkyl group.

[0355] By R XF2 The number of carbon atoms in the perfluoroalkyl group is preferably 1 to 15, more preferably 1 to 10, and even more preferably 1 to 6.

[0356] In general formula (B-9), n represents an integer from 0 to 4.

[0357] Compound W preferably has at least two (preferably two selected from general formulas (B-1) to (B-13)) anionic functional groups. In this case, there are no particular restrictions on the combination of anionic functional groups possessed by compound W.

[0358] For example, when compound W has a group represented by general formula (B-8) or (B-10), it may further have a group represented by general formulas (B-1) to (B-7), (B-9), or (B-11) to (B-13). Furthermore, when compound W has a group represented by general formula (B-7), it may further have a group represented by general formula (B-6). These compounds W may further have different anionic functional groups.

[0359] Among them, compound W preferably has an anionic site A. B - (Anionic functional group A) B - ) as the anion site.

[0360] Anion site A B - (Anionic functional group A) B- ) is a group represented by any one of the general formulas (BX-1) to (BX-4).

[0361] [Chemical Formula 21]

[0362]

[0363] In the general formulas (BX-1) to (BX-4), * indicates the bonding position.

[0364] In general formulas (BX-1) to (BX-4), R B It represents an organic group.

[0365] As R B Examples of organic groups in formulas (B-1) to (B-5) and (B-12) can also be cited as R. X1 Examples of organic groups.

[0366] Furthermore, compound W preferably has the anion site A mentioned above. B - (Anionic functional group A) B - In addition to ) it also has an anion site A A - (Anionic functional group A) A - ) as the anion site.

[0367] Anion site A A - (Anionic functional group A) A - ) is a group represented by any one of the general formulas (AX-1) to (AX-2).

[0368] [Chemical Formula 22]

[0369]

[0370] In the general formulas (AX-1) to (AX-2), * indicates the bonding position.

[0371] In the general formula (AX-2), R A It represents an organic group.

[0372] R A Alkyl groups are preferred.

[0373] The alkyl groups mentioned above can be straight-chain or branched.

[0374] The number of carbon atoms in the alkyl group is preferably 1 to 10, more preferably 1 to 5.

[0375] The alkyl group may preferably have fluorine atoms as a substituent.

[0376] The alkyl group described above, which has a fluorine atom as a substituent, may or may not be a perfluoroalkyl group.

[0377] Compound W, as an anionic site, in addition to having the aforementioned anionic site A, B - (Anionic functional group A) B - ) and the above-mentioned anion site A A - (Anionic functional group A) A - In addition to the above, it may or may not have further anionic sites (preferably further anionic functional groups).

[0378] As compound W, it is preferably a compound represented by the general formula (AD0).

[0379] L0-(A0 - ) nk (M0 + ) nk General formula (AD0)

[0380] In the general formula (AD0), nk represents an integer greater than 2.

[0381] The nk is preferably 2 to 10, and more preferably 2 to 3.

[0382] In the general formula (AD0), there are two nk values ​​that are the same.

[0383] In the general formula (AD0), L0 represents the linker base of the nk valence.

[0384] When nk is 2, L0 represents a single bond or a divalent linker.

[0385] Examples of divalent organic groups include -COO-, -CONH-, -CO-, -O-, alkylene groups (preferably with 1 to 6 carbon atoms, which can be straight-chain or branched), cycloalkylene groups (preferably with 3 to 15 carbon atoms), alkenyl groups (preferably with 2 to 6 carbon atoms), and divalent linking groups formed by combining multiple of these.

[0386] One or more methylene groups of the cycloalkane ring constituting the above-mentioned cycloalkyl group may be replaced by carbonyl carbon and / or heteroatoms (oxygen atoms, etc.).

[0387] These divalent linkers are also preferably further selected from -S-, -SO-, -SO2-, and -NR. N -(R N (A group consisting of a hydrogen atom or a substituent).

[0388] As a linker with an nk valence, examples include connecting single bonds and / or the aforementioned divalent linkers with -CR groups. nk A group consisting of <, -N<, >C<, a hydrocarbon cyclic group with a valence of 3 or higher, and / or a heterocyclic group with a valence of 3 or higher. R nk It represents a hydrogen atom or a substituent.

[0389] When L0 is not a single bond, the total number of atoms other than hydrogen atoms constituting L0 is preferably 1 to 100, more preferably 1 to 50.

[0390] In the general formula (AD0), A0 - This indicates an anionic functional group. For anionic functional groups, as described above, there are multiple A0 groups. - They can be the same or different.

[0391] There are multiple A0s - For example, it may have at least "a group represented by general formula (B-8) or (B-10), a group represented by general formula (B-1) to (B-7), (B-9), or (B-11) to (B-13)," or it may have at least "a group represented by general formula (B-7) and a group represented by general formula (B-6)," or it may have at least "a group represented by any one of general formula (BX-1) to (BX-4) and a group represented by any one of general formula (AX-1) to (AX-2)."

[0392] In the general formula (AD0), M0 + It indicates a cation (a specific cation or an organic cation other than a specific cation).

[0393] nk M0 + At least one (preferably all) represents a specific cation.

[0394] There are multiple M0s + They can be the same or different.

[0395] Furthermore, compound W is preferably compound (I), compound (II), or compound (III).

[0396] The following describes compounds (I) to (III).

[0397] Compound (I)

[0398] Compound (I) will be described.

[0399] Compound (I) is the following compound.

[0400] Compound (I): is a compound having one of the following structural sites X and one of the following structural sites Y, respectively, and which, upon irradiation with photochemical rays or radiation, produces an acid comprising the first acidic site derived from structural site X and the second acidic site derived from structural site Y.

[0401] Structural site X: composed of anion site A1 - and cation site M1 + It is composed of, and through irradiation by photochemical rays or radiation, forms the structural site of the first acidic region represented by HA1.

[0402] Structural region Y: composed of anion site A2 - and cation site M2 + The structure is composed of a second acidic region, represented by HA2, which has a different structure from the first acidic region formed in the aforementioned structural region X, and is formed by irradiation with photochemical rays or radiation.

[0403] Among them, the cation site M1 + and cation site M2 + At least one of them is a specific cation.

[0404] Furthermore, compound (I) satisfies the following condition I.

[0405] Condition I: In the above compound (I), the above-mentioned cation site M1 in the above-mentioned structural site X is... + and the aforementioned cation site M2 in the aforementioned structural site Y. + Replace with H + The resulting compound PI has an acid dissociation constant a1, derived from the cation M1 in the above-mentioned structural site X. + Replace with H + The acidic site represented by HA1 and the acid dissociation constant a2 are derived from the cation site M2 in the above structural site Y. + Replace with H + The acidic site represented by HA2 is formed, and the acid dissociation constant a2 is greater than the acid dissociation constant a1.

[0406] Furthermore, the acid dissociation constants a1 and a2 are obtained using the method described above. More specifically regarding the acid dissociation constants a1 and a2 of compound PI, when determining the acid dissociation constants of compound PI, compound PI (compound PI is equivalent to "a compound having HA1 and HA2") becomes "a compound having A1..." - The pKa of compounds containing HA2 is the acid dissociation constant a1. The above-mentioned compounds containing A1... - Compounds containing HA2" become "compounds with A1- and A2 - The pKa of the compound is the acid dissociation constant a2.

[0407] Furthermore, the aforementioned compound PI is equivalent to an acid produced by irradiating compound (I) with photochemical rays or radiation.

[0408] From the viewpoint of achieving better results in this invention, in the above-mentioned compound PI, the difference between the acid dissociation constant a1 and the acid dissociation constant a2 is preferably 0.10 to 20.00, more preferably 0.50 to 17.00.

[0409] Furthermore, from the viewpoint of achieving better results in this invention, in the above-mentioned compound PI, the acid dissociation constant a2 is preferably -4.00 to 15.00, more preferably -2.00 to 12.00.

[0410] Furthermore, from the viewpoint of achieving better results in this invention, in the above-mentioned compound PI, the acid dissociation constant a1 is preferably -12.00 to 1.00, more preferably -7.00 to 0.50.

[0411] ·General formula (Ia)

[0412] There are no particular limitations on what is referred to as compound (I), for example, compounds represented by the following general formula (Ia) can be cited.

[0413] M 11 + A 11 - -L1-A 12 - M 12 + (Ia)

[0414] In general formula (Ia), "M 11 + A 11 - "and "A 12 - M 12 + "These correspond to structural sites X and Y, respectively. Compound (Ia) is produced by irradiation with photochemical rays or radiation from HA." 11 -L1-A 21 H represents an acid. That is, "M" 11 + A 11 - "Formed by HA" 11 The first acidic site, "A" 12 - M 12 +"Formed by HA with a structure different from the first acidic site mentioned above" 12 The second acidic site is indicated.

[0415] In the above general formula (Ia), M will be... 11 + and M 12 + The specific cation substitution is H. + The compound formed is PIa(HA) 11 -L1-A 12 In H), it originates from A 12 The acid dissociation constant a2 of the acidic site represented by H is greater than that derived from HA. 11 The acid dissociation constant a1 represents the acidic region. Furthermore, preferred values ​​for acid dissociation constants a1 and a2 are as described above.

[0416] In general formula (Ia), M 11 + and M 12 + Each can be used to represent a cation (a specific cation or an organic cation other than a specific cation).

[0417] M 11 + and M 12 + At least one (preferably both) of them is a specific cation.

[0418] The above applies to specific cations.

[0419] For organic cations other than specific cations, the above applies.

[0420] In general formula (Ia), A 11 - and A 12 - Each of these independently represents anionic functional groups. Among them, A... 12 - Indicates the relationship with A 11 - The different structures of the anionic functional groups are represented.

[0421] For anionic functional groups, as described above.

[0422] A 11 - and A 12 - The anionic functional groups are preferably groups represented independently by general formulas (B-1) to (B-13).

[0423] As a result of A 11- and A 12 - There are no particular restrictions on the combination of anionic functional groups represented; for example, when A... 11 - When it is a group represented by the general formula (B-8) or (B-10), it is treated as a group composed of A. 12 - Examples of anionic functional groups can be those represented by general formulas (B-1) to (B-7), (B-9), or (B-11) to (B-13), when A 11 - When it is a group represented by the general formula (B-7), it is treated as a group composed of A. 12 - The anionic functional groups represented can be exemplified by groups represented by the general formula (B-6).

[0424] In general formula (Ia), L1 represents a divalent linker.

[0425] In general formula (I), the divalent linker represented by L1 is not particularly limited, and examples include -CO-, -NR-, -CO-, -O-, alkylene groups (preferably with 1 to 6 carbon atoms; can be linear or branched), cycloalkylene groups (preferably with 3 to 15 carbon atoms), alkenyl groups (preferably with 2 to 6 carbon atoms), divalent aliphatic heterocyclic groups (preferably 5 to 10-membered rings having at least one N, O, S, or Se atom in the ring structure, more preferably 5 to 7-membered rings, and even more preferably 5 to 6-membered rings), and divalent linkers formed by combining multiple of these. Examples of R include hydrogen atoms or monovalent substituents. There are no particular limitations on the monovalent substituent, but alkyl groups (preferably with 1 to 6 carbon atoms) are preferred.

[0426] These divalent linkers may also include groups selected from -S-, -SO-, and -SO2-.

[0427] Furthermore, the aforementioned alkylene group, cycloalkylene group, alkenyl group, and divalent aliphatic heterocyclic group can be substituted with substituents. Examples of substituents include halogen atoms (preferably fluorine atoms).

[0428] General formula (Ib)

[0429] Among them, the compound (I) is preferably a compound represented by the general formula (Ib).

[0430] M1 + A - -LB - M2 + (Ib)

[0431] In general formula (Ib), M1 + and M2 + Each can be used to represent a cation (a specific cation or an organic cation other than a specific cation).

[0432] M1 + and M2 + At least one (preferably both) of them represents a specific cation.

[0433] The above applies to specific cations.

[0434] The same applies to organic cations other than specific cations.

[0435] In the general formula (Ib), L represents a divalent organic group.

[0436] Examples of divalent organic groups include -COO-, -CONH-, -CO-, -O-, alkylene groups (preferably with 1 to 6 carbon atoms, which can be straight-chain or branched), cycloalkylene groups (preferably with 3 to 15 carbon atoms), alkenyl groups (preferably with 2 to 6 carbon atoms), and divalent linking groups formed by combining multiple of these.

[0437] One or more methylene groups of the cycloalkane ring constituting the above-mentioned cycloalkyl group may be replaced by carbonyl carbon and / or heteroatoms (oxygen atoms, etc.).

[0438] These divalent linkers preferably further have groups selected from -S-, -SO- and -SO2-.

[0439] Wherein, L is preferably a group represented by the following general formula (L).

[0440] *A-LA-LB-LC-LD-LE-*B (L)

[0441] In general formula (L), *A represents the expression in general formula (Ib) that is related to A. - The bonding positions.

[0442] In general formula (L), *B represents the expression with respect to B in general formula (Ib). - The bonding positions.

[0443] In the general formula (L), LA represents -(C(R) LA1 (R) LA2 )) XA -

[0444] The above XA represents an integer of 1 or more, preferably 1 to 10, and more preferably 1 to 3.

[0445] R LA1 and R LA2 Each can be used to represent a hydrogen atom or a substituent independently.

[0446] As R LA1 and R LA2 The substituents are each preferably fluorine atoms or fluoroalkyl groups, more preferably fluorine atoms or perfluoroalkyl groups, and even more preferably fluorine atoms or perfluoromethyl groups.

[0447] When XA is 2 or more, there are XA R's. LA1 They can be the same or different.

[0448] When XA is 2 or more, there are XA R's. LA2 They can be the same or different.

[0449] -(C(R LA1 (R) LA2 Preferred values ​​are -CH2-, -CHF-, -CH(CF3)-, or -CF2-.

[0450] Among them, in the general formula (Ib) and A - Directly bonded -(C(R) LA1 (R) LA2 Preferred values ​​are -CH2-, -CHF-, -CH(CF3)-, or -CF2-.

[0451] In general formula (Ib), the relationship between A and - Directly bonded -(C(R) LA1 (R) LA2 ))- other than -(C(R LA1 (R) LA2 -The preferred options are -CH2-, -CHF-, or -CF2-, respectively.

[0452] In the general formula (L), LB represents a single bond, an ester group (-COO-) or a sulfonyl group (-SO2-).

[0453] In the general formula (L), LC represents a single bond, alkylene, cycloalkylene, or a combination thereof ("-alkylene-cycloalkyl-", etc.).

[0454] The aforementioned alkylene groups can be linear or branched.

[0455] The number of carbon atoms in the aforementioned alkylene group is preferably 1 to 5, more preferably 1 to 2, and even more preferably 1.

[0456] The number of carbon atoms in the aforementioned cycloalkyl group is preferably 3 to 15, more preferably 5 to 10.

[0457] The aforementioned cycloalkyl groups can be monocyclic or polycyclic.

[0458] Examples of the aforementioned cycloalkyl groups include norbornenediyl and adamantanediyl.

[0459] The substituents that may be present as the above-mentioned cycloalkyl group are preferably alkyl groups (which may be straight-chain or branched. Preferably, they have 1 to 5 carbon atoms).

[0460] One or more methylene groups of the cycloalkane ring constituting the above-mentioned cycloalkyl group may be replaced by carbonyl carbon and / or heteroatoms (oxygen atoms, etc.).

[0461] When LC is “-alkylene-cycloalkylene-”, the alkylene portion is preferably present on the LB side.

[0462] When LB is a single bond, LC is preferably a single bond or a cycloalkylene compound.

[0463] In the general formula (L), LD represents a single bond, an ether group (-O-), a carbonyl group (-CO-), or an ester group (-COO-).

[0464] In the general formula (L), LE represents a single bond or -(C(R) LE1 (R) LE2 )) XE -

[0465] The above -(C(R) LE1 (R) LE2 )) XE In the -, XE represents an integer greater than or equal to 1, preferably 1 to 10, and more preferably 1 to 3.

[0466] R LE1 and R LE2 Each can be used to represent a hydrogen atom or a substituent independently.

[0467] When XE is 2 or more, there are XE types of R. LE1 They can be the same or different.

[0468] When XE is 2 or more, there are XE types of R. LE2 They can be the same or different.

[0469] Among them, -(C(R) LE1 (R) LE2 - Preferably -CH2- or -CF2-.

[0470] In general formula (L), when LB, LC and LD are single bonds, it is preferred that LE is also a single bond.

[0471] In general formula (Ib), A - and B - Each can be used to represent anionic functional groups independently.

[0472] For anionic functional groups, as described above.

[0473] Among them, A - Preferably, it is a group represented by any one of the general formulas (AX-1) to (AX-2).

[0474] B - Preferably, it represents a group represented by any one of the general formulas (BX-1) to (BX-4).

[0475] A - and B - Preferably, they have different structures.

[0476] Among them, A is preferred. - For groups represented by the general formula (AX-1), and B - A group or A represented by any one of the general formulas (BX-1) to (BX-4) - For groups represented by the general formula (AX-2), and B - It is a group represented by any one of the general formulas (BX-1), (BX-3), and (BX-4).

[0477] Among them, in the compound represented by general formula (Ib), M1 + and M2 + In the compounds represented by HA-L-BH, which are respectively substituted with hydrogen atoms, the pKa of the group represented by HA is lower than that of the group represented by BH.

[0478] More specifically, when determining the acid dissociation constant of a compound represented by HA-L-BH, "HA-L-BH" is changed to "A". - The pKa of "-L-BH" is set to "the pKa of the group represented by HA". Furthermore, "A" is set to... - -L-BH" becomes "A" - -LB - The pKa of the group represented by BH is set as "the pKa of the group represented by BH".

[0479] The pKa of the group represented by HA and the pKa of the group represented by BH are obtained using either software package 1 or Gaussian16.

[0480] For example, the pKa of the group represented by HA is equivalent to the acid dissociation constant a1 mentioned above, and the preferred range is also the same.

[0481] The pKa of the group represented by BH is equivalent to the acid dissociation constant a2 mentioned above, and the preferred range is also the same.

[0482] The difference between the pKa of the group represented by HB and the pKa of the group represented by HA ("pKa of the group represented by HB" - "pKa of the group represented by HA") is equivalent to the difference between the acid dissociation constant a1 and the acid dissociation constant a2 mentioned above, and the preferred range is also the same.

[0483] ·Compound (II)

[0484] Next, compound (II) will be described.

[0485] Compound (II) is the following compound.

[0486] Compound (II): is a compound having two or more of the above-described structural sites X and Y, and which, upon irradiation with photochemical rays or radiation, produces an acid comprising two or more of the first acidic sites derived from the above-described structural site X and the second acidic sites derived from the above-described structural site Y.

[0487] Among them, the cation site M1 + and cation site M2 + At least one of them is a specific cation.

[0488] Furthermore, compound (II) satisfies the following condition II.

[0489] Condition II: In the above compound (II), the above-mentioned cation site M1 in the above-mentioned structural site X is... + and the cation site M2 in the aforementioned structural site Y. + Replace with H + The resulting compound PII has an acid dissociation constant a1, derived from the cation M1 in the above-mentioned structural site X. + Replace with H + The acidic site represented by HA1 and the acid dissociation constant a2 are derived from the cation site M2 in the above structural site Y. + Replace with H + The acidic site represented by HA2 is formed, and the acid dissociation constant a2 is greater than the acid dissociation constant a1.

[0490] The acid dissociation constants a1 and a2 were determined using the method described above.

[0491] Here, the acid dissociation constants a1 and a2 of compound PII will be explained in more detail. When compound (II) is, for example, a compound that produces an acid having two of the first acidic sites derived from the above-mentioned structural site X and one of the second acidic sites derived from the above-mentioned structural site Y, compound PII is equivalent to "a compound having two HA1 and HA2". When determining the acid dissociation constant of compound PII, compound PII becomes "a compound having one A1". - The pKa of a compound containing one HA1 and one HA2 is the acid dissociation constant a1, and the pKa of a compound containing two A1s is the acid dissociation constant a1. - Compounds containing HA2 become compounds with two A1 groups. - and A2 - The pKa of the compound is the acid dissociation constant a2. That is, when the compound PII has multiple cation sites M1 derived from the above-mentioned structural site X, the pKa is the acid dissociation constant a2. + Replace with H + When the acid dissociation constant of the acidic site is represented by HA1, its minimum value is regarded as the acid dissociation constant a1.

[0492] Furthermore, the aforementioned compound PII is equivalent to an acid produced by irradiating compound (II) with photochemical rays or radiation.

[0493] In addition, compound (II) may have multiple of the above-mentioned structural sites Y.

[0494] From the viewpoint of achieving better results with the present invention, in the above-described compound PII, the difference between the acid dissociation constant a1 and the acid dissociation constant a2 is preferably 2.00 or more, more preferably 3.00 or more. Furthermore, there is no particular limitation on the upper limit of the difference between the acid dissociation constant a1 and the acid dissociation constant a2, for example, it is 15.00 or less.

[0495] Furthermore, from the viewpoint of achieving better results with the present invention, in the above-described compound PII, the acid dissociation constant a2 is preferably 2.00 or less, more preferably 1.00 or less. Additionally, as a lower limit value for the acid dissociation constant a2, it is preferably -2.00 or more.

[0496] Furthermore, from the viewpoint of achieving better results with the present invention, in the above-described compound PII, the acid dissociation constant a1 is preferably 2.00 or less, more preferably 0.50 or less, and even more preferably -0.10 or less. Additionally, as a lower limit value for the acid dissociation constant a1, it is preferably -15.00 or more.

[0497] There are no particular limitations on the compound (II), for example, compounds represented by the following general formula (IIa) can be cited.

[0498] [Chemical Formula 23]

[0499]

[0500] In general formula (IIa), "M 21 + A 21 - "and "A 22 - M 22 + "These correspond to structural sites X and Y, respectively. Compound (IIa) produces an acid represented by the following general formula (IIa-1) upon irradiation with photochemical rays or radiation. That is, "M 21 + A 21 - "Formed by HA" 21 The first acidic site, "A" 22 - M 22 + "Formed by HA with a structure different from the first acidic site mentioned above" 22 The second acidic site is indicated.

[0501] [Chemical Formula 24]

[0502]

[0503] In general formula (IIa), M 21 + and M 22 + Each can be used to represent a cation (a specific cation or an organic cation other than a specific cation).

[0504] M 21 + and M 22 + At least one (preferably both) of them represents a specific cation.

[0505] A 21 - and A 22 - Each of these independently represents anionic functional groups. Among them, A... 22 - Indicates the relationship with A 21 - The different structures of the anionic functional groups are represented.

[0506] L2 represents an organic group with a valence of (n1+n2).

[0507] n1 represents an integer greater than or equal to 2.

[0508] n2 represents an integer greater than or equal to 1.

[0509] In the above general formula (IIa), when M is... 21 + and M 22 + The cation substitution represented is H. + The resulting compound PIIa (equivalent to the compound represented by the above general formula (IIa-1)) is derived from A 22 The acid dissociation constant a2 of the acidic site represented by H is greater than that derived from HA. 21 The acid dissociation constant a1 represents the acidic region. Furthermore, preferred values ​​for acid dissociation constants a1 and a2 are as described above.

[0510] In the above general formula (IIa), M 21 + M 22 + A 21 - and A 22 - Each of the above general formulas (Ia) and M 11 + M 12 + A 11 - and A 12 - The meanings are the same, and the preferred methods are also the same.

[0511] In the above general formula (IIa), n1 M 21 + Each other, n1 A 21 + Each of them represents the same group.

[0512] In the above general formula (IIa), there is no particular limitation on the organic group with a valence of (n1+n2) represented by L2, and examples include groups represented by (A1) and (A2) below. Furthermore, in (A1) and (A2) below, at least two of the asterisks represent groups with the valence A. 21 - The bonding positions, * at least one of which indicates a bond with A 22 - The bonding positions.

[0513] [Chemical Formula 25]

[0514]

[0515] In (A1) and (A2) above, T 1 T represents a trivalent hydrocarbon cyclic group or a trivalent heterocyclic group. 2It represents a carbon atom, a tetravalent hydrocarbon cyclic group, or a tetravalent heterocyclic group.

[0516] The aforementioned hydrocarbon cyclic group can be an aromatic hydrocarbon cyclic group or an aliphatic hydrocarbon cyclic group. The number of carbon atoms contained in the aforementioned hydrocarbon cyclic group is preferably 6 to 18, more preferably 6 to 14.

[0517] The aforementioned heterocyclic group can be an aromatic heterocyclic group or an aliphatic heterocyclic group. The aforementioned heterocyclic group is preferably a 5- to 10-membered ring having at least one N atom, O atom, S atom or Se atom in the ring structure, more preferably a 5- to 7-membered ring, and even more preferably a 5- to 6-membered ring.

[0518] Furthermore, in (A1) and (A2) above, L 21 and L 22 Each can be used to independently represent a single bond or a divalent linker.

[0519] As a result of L 21 and L 22 The divalent linker represented here has the same meaning as the divalent linker represented by L1 in the above general formula (Ia), and the preferred method is also the same.

[0520] n1 represents an integer greater than or equal to 2. There is no particular upper limit; for example, it can be less than 6, preferably less than 4, and more preferably less than 3.

[0521] n² represents an integer greater than or equal to 1. There is no particular upper limit, but it can be less than 3, preferably less than 2.

[0522] Compound (III)

[0523] Next, compound (III) will be described.

[0524] Compound (III): is a compound having two or more of the above-described structural sites X and Z, and is irradiated with photochemical rays or radiation to produce an acid comprising two or more of the above-described first acidic sites derived from structural site X and structural site Z.

[0525] Structural site Z: The nonionic organic site that can neutralize the acid.

[0526] Among them, the cation site M1 + At least one of them is a specific cation.

[0527] There are no particular limitations on the nonionic organic site that can neutralize the acid in structural site Z. For example, it is preferable to have an organic site containing a functional group or an electron that can interact electrostatically with a proton.

[0528] Functional groups that have groups or electrons capable of electrostatic interaction with protons include, for example, functional groups with macrocyclic compound structures such as cyclic polyethers, or functional groups with nitrogen atoms that have unshared electron pairs that do not contribute to π-conjugation. A nitrogen atom with unshared electron pairs that do not contribute to π-conjugation is, for example, a nitrogen atom having a partial structure as shown in the following formula.

[0529] [Chemical Formula 26]

[0530] Unshared electron pairs

[0531] Examples of partial structures that have functional groups or electrons capable of electrostatic interaction with protons include crown ether structures, azacrown ether structures, primary amine structures, secondary amine structures, tertiary amine structures, pyridine structures, imidazole structures, and pyrazine structures, among which primary amine structures, secondary amine structures, and tertiary amine structures are preferred.

[0532] In the above compound (III), the above-mentioned cation M1 in the above-mentioned structural site X is... + Replace with H + From the viewpoint of having better effects than the present invention, the compound PIII derived from the above-described cation M1 in the above-described structural site X is superior. + Replace with H + The acid dissociation constant a1 of the acidic portion represented by HA1 is preferably 2.0 or less, more preferably 0.5 or less, and even more preferably -0.1 or less. Furthermore, as a lower limit value for the acid dissociation constant a1, it is preferably -15.0 or more.

[0533] Furthermore, when compound PIII has multiple cation sites M1 derived from the aforementioned structural site X, + Replace with H + When the acid dissociation constant of the acidic site is represented by HA1, its minimum value is regarded as the acid dissociation constant a1.

[0534] That is, when compound (III) is, for example, a compound that produces an acid having two acids derived from the first acidic site X and the acid derived from the first acidic site Z, compound PIII is equivalent to "a compound having two HA1 atoms". When determining the acid dissociation constant of compound PIII, compound PIII becomes "a compound having one A1 atom". - The pKa of a compound containing one HA1 is the acid dissociation constant a1. That is, when compound PIII has multiple cation sites M1 derived from the above-mentioned structural site X, the pKa is the acid dissociation constant a1. + Replace with H + When the acid dissociation constant of the acidic site is represented by HA1, its minimum value is regarded as the acid dissociation constant a1.

[0535] Furthermore, in the above compound (III), the above-mentioned cation site M1 in the above-mentioned structural site X is... + Replace with H + The compound PIII refers to, for example, when compound (III) is represented by compound (IIIa) described later, it is equivalent to HA. 31 -L3-N(R 2X )-L4-A 31 H.

[0536] There are no particular limitations on the compound (III), for example, compounds represented by the following general formula (IIIa) can be cited.

[0537] [Chemical Formula 27]

[0538]

[0539] In general formula (IIIa), "M 31 + A 31 - "Equivalent to structural site X. Compound (IIIa) is produced by irradiation with photochemical rays or radiation from HA." 31 -L3-N(R 2X )-L4-A 31 H represents an acid. That is, "M" 31 + A 31 - "Formed by HA" 31 The first acidic site is indicated.

[0540] In general formula (IIIa), M 31 + It indicates a cation (a specific cation or an organic cation other than a specific cation).

[0541] M 31 + At least one (preferably both) of them represents a specific cation.

[0542] A 31 - It represents an anionic functional group.

[0543] L3 and L4 independently represent the divalent linker bases.

[0544] R 2X This represents an organic group with a monovalent valence.

[0545] In the above general formula (IIIa), M 31 + and A31 - Each of the above general formulas (Ia) and M 11 + and A 11 - The meanings are the same, and the preferred methods are also the same.

[0546] In the above general formula (IIIa), L3 and L4 have the same meaning as L1 in the above general formula (Ia), and the preferred methods are also the same.

[0547] In the above general formula (IIIa), there are 2 M 31 + Each other, and two A's 31 - Each of them represents the same group.

[0548] In general formula (IIIa), as R 2X The monovalent organic group represented is not particularly limited. For example, -CH2- can be substituted by one or more combinations selected from -CO-, -NH-, -O-, -S-, -SO- and -SO2-, alkyl (preferably with 1 to 10 carbon atoms, which can be straight-chain or branched), cycloalkyl (preferably with 3 to 15 carbon atoms), or alkenyl (preferably with 2 to 6 carbon atoms).

[0549] Furthermore, the aforementioned alkylene group, cycloalkylene group, and alkenylene group can be substituted with substituents.

[0550] <Resin whose polarity increases through decomposition by acid (Resin (A))>

[0551] The compositions of the present invention comprise a resin whose polarity increases through decomposition by the action of an acid (hereinafter also referred to as "acid-decomposable resin" or "resin (A)").

[0552] That is, in the pattern forming method of the present invention, typically, when an alkaline developer is used as the developer, a positive pattern is preferably formed, and when an organic developer is used as the developer, a negative pattern is preferably formed.

[0553] Resin (A) typically contains groups whose polarity increases through acid decomposition (hereinafter also referred to as "acid-decomposable groups"), and preferably contains repeating units having acid-decomposable groups.

[0554] (Repeating unit with acid-degrading groups)

[0555] An acid-degradable group is a group that decomposes to produce a polar group through the action of an acid. Preferably, the acid-degradable group has a structure protected by a release group, where the polar group is released through the action of an acid. That is, the resin (A) contains repeating units containing groups that decompose to produce polar groups through the action of an acid. The resin containing these repeating units becomes more polar through the action of an acid, thereby increasing its solubility in alkaline developing solutions and decreasing its solubility in organic solvents.

[0556] As a polar group, an alkaline-soluble group is preferred. Examples include carboxyl, phenolic hydroxyl, fluorinated alcohol, sulfonic acid, phosphoric acid, sulfonamide, sulfonylimide, (alkylsulfonyl)(alkylcarbonyl)methylene, (alkylsulfonyl)(alkylcarbonyl)imide, bis(alkylcarbonyl)methylene, bis(alkylcarbonyl)imide, bis(alkylsulfonyl)methylene, bis(alkylsulfonyl)imide, tri(alkylcarbonyl)methylene and tri(alkylsulfonyl)methylene, as well as acidic groups such as alcohol hydroxyl groups.

[0557] Among them, the polar group is preferably a carboxyl group, a phenolic hydroxyl group, a fluorinated alcohol group (preferably a hexafluoroisopropanol group) or a sulfonic acid group.

[0558] As a detaching group that is released by the action of an acid, examples include groups represented by general formulas (Y1) to (Y4).

[0559] General formula (Y1): -C(Rx1)(Rx2)(Rx3)

[0560] General formula (Y2): -C(=O)OC(Rx1)(Rx2)(Rx3)

[0561] General formula (Y3): -C(R) 36 (R) 37 (OR) 38 )

[0562] General formula (Y4): -C(Rn)(H)(Ar)

[0563] In general formulas (Y1) and (Y2), Rx1 to Rx3 independently represent alkyl (straight-chain or branched) or cycloalkyl (monocyclic or polycyclic), alkenyl (straight-chain or branched) or aryl (monocyclic or polycyclic). Furthermore, when all of Rx1 to Rx3 are alkyl (straight-chain or branched), it is preferable that at least two of Rx1 to Rx3 are methyl.

[0564] Preferably, Rx1 to Rx3 represent straight-chain or branched alkyl groups, and more preferably, Rx1 to Rx3 represent straight-chain alkyl groups.

[0565] Two of Rx1 to Rx3 can also be bonded to form a single ring or multiple rings.

[0566] The alkyl groups Rx1 to Rx3 are preferably alkyl groups with 1 to 5 carbon atoms, such as methyl, ethyl, n-propyl, isopropyl, n-butyl, isobutyl, and tert-butyl.

[0567] As for the cycloalkyl groups Rx1 to Rx3, monocyclic cycloalkyl groups such as cyclopentyl and cyclohexyl, and polycyclic cycloalkyl groups such as norbornyl, tetracyclic decyl, tetracyclic dodecyl, and adamantyl are preferred.

[0568] As for the aryl group of Rx1 to Rx3, it is preferred to have 6 to 10 carbon atoms, such as phenyl, naphthyl and anthracene.

[0569] As for the alkenyl group of Rx1 to Rx3, vinyl is preferred.

[0570] The ring formed by the two bonds of Rx1 to Rx3 is preferably a cycloalkyl group. The cycloalkyl group formed by the two bonds of Rx1 to Rx3 is preferably a monocyclic cycloalkyl group such as cyclopentyl or cyclohexyl, or a polycyclic cycloalkyl group such as norbornyl, tetracyclic decyl, tetracyclic dodecyl or adamantyl, and more preferably a monocyclic cycloalkyl group with 5 to 6 carbon atoms.

[0571] In the cycloalkyl group formed by the bonding of two bonds in Rx1 to Rx3, for example, one of the methylene groups constituting the ring may be replaced by a group having a heteroatom such as an oxygen atom, a heteroatom such as a carbonyl group, or a vinylene group. Furthermore, in these cycloalkyl groups, one or more of the ethylene groups constituting the cycloalkane ring may be replaced by vinylene.

[0572] The group represented by the general formula (Y1) or (Y2) is preferably, for example, Rx1 is methyl or ethyl, and Rx2 is bonded to Rx3 to form the above-mentioned cycloalkyl group.

[0573] In general formula (Y3), R 36 ~R 38 Each can be used independently to represent a hydrogen atom or a monovalent organic group. R 37 With R 38 They can bond with each other to form rings. Examples of monovalent organic groups include alkyl, cycloalkyl, aryl, aralkyl, and alkenyl groups. R 36 Hydrogen atoms are preferred.

[0574] Furthermore, the aforementioned alkyl, cycloalkyl, aryl, and aralkyl groups may also include groups having heteroatoms such as oxygen atoms and / or heteroatoms such as carbonyl groups. For example, in the aforementioned alkyl, cycloalkyl, aryl, and aralkyl groups, one or more of the methylene groups may be substituted with groups having heteroatoms such as oxygen atoms and / or heteroatoms such as carbonyl groups.

[0575] Furthermore, R 38It can bond with another substituent in the main chain of the repeating unit to form a ring. R 38 The group formed by bonding with another substituent in the main chain of the repeating unit is preferably an alkylene group such as methylene.

[0576] As the general formula (Y3), it is preferred to be a group represented by the following formula (Y3-1).

[0577] [Chemical Formula 28]

[0578]

[0579] Here, L1 and L2 independently represent hydrogen atoms, alkyl, cycloalkyl, aryl, or groups formed by combining them (e.g., groups formed by combining alkyl and aryl).

[0580] M represents a single bond or a divalent linker.

[0581] Q represents an alkyl group that may contain heteroatoms, a cycloalkyl group that may contain heteroatoms, an aryl group, an amino group, an ammonium group, a mercapto group, a cyano group, an aldehyde group, or a combination thereof (e.g., a group composed of alkyl and cycloalkyl groups).

[0582] In alkyl and cycloalkyl groups, for example, one of the methylene groups can be substituted with a group having a heteroatom such as an oxygen atom or a heteroatom such as a carbonyl group.

[0583] In addition, it is preferred that one of L1 and L2 is a hydrogen atom and the other is an alkyl, cycloalkyl, aryl, or a group composed of alkylene and aryl groups.

[0584] At least two of Q, M and L1 can be bonded to form a ring (preferably a 5-membered ring or a 6-membered ring).

[0585] From the viewpoint of miniaturizing the pattern, L2 is preferably a secondary alkyl or tertiary alkyl group, more preferably a tertiary alkyl group. Examples of secondary alkyl groups include isopropyl, cyclohexyl, or norbornyl, while examples of tertiary alkyl groups include tert-butyl or adamantyl. In these cases, the increased Tg (glass transition temperature) and activation energy ensure film strength and suppress blurring.

[0586] In general formula (Y4), Ar represents an aromatic cycloalgyl group. Rn represents an alkyl, cycloalkyl, or aryl group. Rn and Ar can bond to each other to form a non-aromatic ring. Ar is more preferably an aryl group.

[0587] From the viewpoint of excellent acid decomposability of repeating units, it is also preferable that when the non-aromatic ring is directly bonded to the polar group (or its residue) in the detachment group of the protecting polar group, the ring member atom in the non-aromatic ring adjacent to the ring member atom directly bonded to the polar group (or its residue) does not have halogen atoms such as fluorine atoms as substituents.

[0588] In addition, the detaching group that is released by the action of acid can also be 2-cyclopentenyl with a substituent (alkyl, etc.) such as 3-methyl-2-cyclopentenyl, and cyclohexyl with a substituent (alkyl, etc.) such as 1,1,4,4-tetramethylcyclohexyl.

[0589] As a repeating unit having an acid-decomposable group, it is also preferred to be a repeating unit represented by the general formula (A).

[0590] [Chemical Formula 29]

[0591]

[0592] L1 represents a divalent linker that may have a fluorine or iodine atom; R1 represents a hydrogen atom, a fluorine atom, an iodine atom, an alkyl group that may have a fluorine or iodine atom, or an aryl group that may have a fluorine or iodine atom; and R2 represents a desorbed group that may have a fluorine or iodine atom and can be desorbed by acid. At least one of L1, R1, and R2 has a fluorine or iodine atom.

[0593] L1 represents a divalent linker that can have either a fluorine or an iodine atom. Examples of divalent linkers that can have either a fluorine or an iodine atom include -CO-, -O-, -S-, -SO-, -SO2-, hydrocarbon groups that can have either a fluorine or an iodine atom (e.g., alkylene, cycloalkylene, alkenyl, arylene, etc.), and linkers formed by linking multiple of these. Among these, -CO- or -arylene-alkylene groups having either a fluorine or an iodine atom are preferred as L1.

[0594] As an arylene group, phenylene is preferred.

[0595] The alkylene group can be linear or branched. There is no particular limitation on the number of carbon atoms in the alkylene group, but it is preferably 1 to 10, more preferably 1 to 3.

[0596] There is no particular limitation on the total number of fluorine atoms and iodine atoms contained in the alkylene group having fluorine or iodine atoms, but it is preferably 2 or more, more preferably 2 to 10, and even more preferably 3 to 6.

[0597] R1 represents a hydrogen atom, a fluorine atom, an iodine atom, an alkyl group that may have a fluorine atom or an iodine atom, or an aryl group that may have a fluorine atom or an iodine atom.

[0598] Alkyl groups can be straight-chain or branched. There is no particular limitation on the number of carbon atoms in an alkyl group, but it is preferably 1 to 10, more preferably 1 to 3.

[0599] There is no particular limitation on the total number of fluorine atoms and iodine atoms contained in the alkyl group having fluorine or iodine atoms, but it is preferably 1 or more, more preferably 1 to 5, and even more preferably 1 to 3.

[0600] The aforementioned alkyl groups may also contain heteroatoms such as oxygen atoms other than halogen atoms.

[0601] R2 represents a detached radical that is released by the action of an acid and can have either a fluorine or iodine atom.

[0602] Among them, groups represented by general formulas (Z1) to (Z4) can be cited as detaching groups.

[0603] General formula (Z1): -C(Rx) 11 (Rx) 12 (Rx) 13 )

[0604] General formula (Z2): -C(=O)OC(Rx) 11 (Rx) 12 (Rx) 13 )

[0605] General formula (Z3): -C(R) 136 (R) 137 (OR) 138 )

[0606] General formula (Z4): -C(Rn1)(H)(Ar1)

[0607] In general formulas (Z1) and (Z2), Rx 11 ~Rx 13 Each can independently represent an alkyl group (straight-chain or branched) that may have fluorine or iodine atoms, a cycloalkyl group (monocyclic or polycyclic) that may have fluorine or iodine atoms, an alkenyl group (straight-chain or branched) that may have fluorine or iodine atoms, or an aryl group (monocyclic or polycyclic) that may have fluorine or iodine atoms. Additionally, when Rx... 11 ~Rx 13 When all components are alkyl groups (linear or branched), Rx is preferred. 11 ~Rx 13 At least two of them are methyl groups.

[0608] Rx 11 ~Rx 13Except for the fact that it can have fluorine or iodine atoms, it is the same as Rx1 to Rx3 in the above general formulas (Y1) and (Y2), and is the same as the definition and preferred range of alkyl, cycloalkyl, alkenyl and aryl.

[0609] In general formula (Z3), R 136 ~R 138 Each can independently represent a hydrogen atom or a monovalent organic group that may have a fluorine or iodine atom. R 137 With R 138 They can bond with each other to form a ring. Examples of monovalent organic groups that can have fluorine or iodine atoms include alkyl groups that can have fluorine or iodine atoms, cycloalkyl groups that can have fluorine or iodine atoms, aryl groups that can have fluorine or iodine atoms, aralkyl groups that can have fluorine or iodine atoms, and groups formed by combining them (e.g., groups formed by combining alkyl and cycloalkyl groups).

[0610] In addition to fluorine and iodine atoms, the aforementioned alkyl, cycloalkyl, aryl, and aralkyl groups may also contain heteroatoms such as oxygen atoms. That is, for example, one of the aforementioned alkyl, cycloalkyl, aryl, and aralkyl groups, such as the methylene group, may be replaced by a group having heteroatoms such as oxygen atoms or carbonyl groups.

[0611] Furthermore, R 138 It can bond with another substituent in the main chain of the repeating unit to form a ring. In this case, R... 138 The group formed by bonding with another substituent in the main chain of the repeating unit is preferably an alkylene group such as methylene.

[0612] As the general formula (Z3), it is preferably a group represented by the following formula (Z3-1).

[0613] [Chemical Formula 30]

[0614]

[0615] Here, L 11 and L 12 Each of these groups can independently represent a hydrogen atom; may contain an alkyl group having a heteroatom selected from fluorine, iodine, and oxygen atoms; may contain a cycloalkyl group having a heteroatom selected from fluorine, iodine, and oxygen atoms; may contain an aryl group having a heteroatom selected from fluorine, iodine, and oxygen atoms; or a group formed by combining these groups (e.g., a group formed by combining alkyl and cycloalkyl groups having a heteroatom selected from fluorine, iodine, and oxygen atoms).

[0616] M1 represents a single bond or a divalent linker.

[0617] Q1 indicates an alkyl group that may have heteroatoms selected from fluorine, iodine, and oxygen atoms; a cycloalkyl group that may have heteroatoms selected from fluorine, iodine, and oxygen atoms; an aryl group; an amino group; an ammonium group; a mercapto group; a cyano group; an aldehyde group; or a combination thereof (e.g., a group that may have heteroatoms selected from fluorine, iodine, and oxygen atoms, and is composed of alkyl and cycloalkyl groups).

[0618] In the general formula (Z4), Ar1 represents an aromatic cyclic group that may have fluorine or iodine atoms. Rn1 represents an alkyl group that may have fluorine or iodine atoms, a cycloalkyl group that may have fluorine or iodine atoms, or an aryl group that may have fluorine or iodine atoms. Rn1 and Ar1 can bond with each other to form a non-aromatic ring.

[0619] As a repeating unit having an acid-decomposable group, it is also preferred to be a repeating unit represented by the general formula (AI).

[0620] [Chemical Formula 31]

[0621]

[0622] In the general formula (AI),

[0623] Xa1 represents a hydrogen atom or an alkyl group that may have substituents.

[0624] T represents a single bond or a divalent linker.

[0625] Rx1 to Rx3 independently represent alkyl (straight-chain or branched), cycloalkyl (monocyclic or polycyclic), alkenyl (straight-chain or branched), or aryl (monocyclic or polycyclic). Among them, when all of Rx1 to Rx3 are alkyl (straight-chain or branched), it is preferred that at least two of Rx1 to Rx3 are methyl.

[0626] Two of Rx1 to Rx3 can also be bonded to form monocyclic or polycyclic (monocyclic or polycyclic cycloalkyl groups).

[0627] As an alkyl group represented by Xa1, which can have substituents, examples include methyl groups or groups consisting of -CH2-R groups. 11 The group indicated by R. 11 The organic group representing a halogen atom (fluorine atom, etc.), a hydroxyl group, or a monovalent organic group can be exemplified by alkyl groups with 5 or fewer carbon atoms that can be substituted by a halogen atom, acyl groups with 5 or fewer carbon atoms that can be substituted by a halogen atom, and alkoxy groups with 5 or fewer carbon atoms that can be substituted by a halogen atom. Alkyl groups with 3 or fewer carbon atoms are preferred, and methyl groups are more preferred. As Xa1, hydrogen atoms, methyl groups, trifluoromethyl groups, or hydroxymethyl groups are preferred.

[0628] Examples of divalent linkers for T include alkylene groups, aromatic cycloalkanes, -COO-Rt- groups, and -O-Rt- groups. In these formulas, Rt represents an alkylene group or a cycloalkylene group.

[0629] T is preferably a single bond or a -COO-Rt- group. When T represents a -COO-Rt- group, Rt is preferably an alkylene group having 1 to 5 carbon atoms, and more preferably a -CH2- group, a -(CH2)2- group, or a -(CH2)3- group.

[0630] The alkyl groups Rx1 to Rx3 are preferably alkyl groups with 1 to 4 carbon atoms, such as methyl, ethyl, n-propyl, isopropyl, n-butyl, isobutyl, and tert-butyl.

[0631] As for the cycloalkyl groups Rx1 to Rx3, they are preferably monocyclic cycloalkyl groups such as cyclopentyl and cyclohexyl, or polycyclic cycloalkyl groups such as norbornyl, tetracyclic decyl, tetracyclic dodecyl, and adamantyl.

[0632] As for the aryl group of Rx1 to Rx3, it is preferred to have 6 to 10 carbon atoms, such as phenyl, naphthyl and anthracene.

[0633] As for the alkenyl group of Rx1 to Rx3, vinyl is preferred.

[0634] The cycloalkyl group formed by the bonding of two of Rx1 to Rx3 is preferably a monocyclic cycloalkyl group such as cyclopentyl or cyclohexyl. In addition, polycyclic cycloalkyl groups such as norbornyl, tetracyclic decyl, tetracyclic dodecyl, and adamantyl are also preferred. Among them, monocyclic cycloalkyl groups with 5 to 6 carbon atoms are preferred.

[0635] In the cycloalkyl group formed by the bonding of two bonds in Rx1 to Rx3, for example, one of the methylene groups constituting the ring may be replaced by a group having a heteroatom such as an oxygen atom, a heteroatom such as a carbonyl group, or a vinylene group. Furthermore, in these cycloalkyl groups, one or more of the ethylene groups constituting the cycloalkane ring may be replaced by vinylene.

[0636] The repeating unit represented by the general formula (AI) is preferably, for example, Rx1 is methyl or ethyl, and Rx2 is bonded to Rx3 to form the above-mentioned cycloalkyl group.

[0637] When the above groups have substituents, examples of substituents include alkyl groups (1 to 4 carbon atoms), halogen atoms, hydroxyl groups, alkoxy groups (1 to 4 carbon atoms), carboxyl groups, and alkoxycarbonyl groups (2 to 6 carbon atoms). The number of carbon atoms in the substituents is preferably 8 or less.

[0638] As the repeating unit represented by the general formula (AI), the acid-degradable tertiary alkyl methacrylate repeating unit is preferred (Xa1 represents a hydrogen atom or a methyl group, and T represents a single bond repeating unit).

[0639] The content of repeating units having acid-degradable groups is preferably 15 to 80 mol% relative to all repeating units in resin (A), more preferably 20 to 70 mol%, and even more preferably 20 to 65 mol%.

[0640] The following are specific examples of repeating units having acid-degradable groups, but the present invention is not limited thereto. Additionally, in the formula, Xa1 represents any one of H, F, CH3, CF3, and CH2OH, and Rxa and Rxb represent straight-chain or branched alkyl groups having 1 to 5 carbon atoms, respectively.

[0641] [Chemical Formula 32]

[0642]

[0643] [Chemical Formula 33]

[0644]

[0645] [Chemical Formula 34]

[0646]

[0647] [Chemical Formula 35]

[0648]

[0649] [Chemical Formula 36]

[0650]

[0651] Resin (A) may also contain repeating units other than those described above.

[0652] For example, resin (A) may also contain at least one repeating unit selected from group A and / or at least one repeating unit selected from group B.

[0653] Group A: Groups that include repeating units of (20) to (29) below.

[0654] (20) Repeating units with acid groups, as described later

[0655] (21) Repeating units with fluorine or iodine atoms, as described later.

[0656] (22) Repeating units having lactone, sulcinolone, or carbonate groups as described later

[0657] (23) The repeating unit with photoacid-generating group described later

[0658] (24) Repeating units described later by general formula (V-1) or general formula (V-2) below.

[0659] (25) The repeating unit represented by equation (A) as described later

[0660] (26) The repeating unit represented by equation (B) as described later

[0661] (27) The repeating unit represented by equation (C) as described later

[0662] (28) The repeating unit represented by equation (D) as described later

[0663] (29) The repeating unit represented by equation (E) as described later

[0664] Group B: Groups that include the repeating units of (30) to (32) below.

[0665] (30) The repeating unit described below having at least one group selected from lactone, sulcinolone, carbonate, hydroxyl, cyano and alkali-soluble groups.

[0666] (31) The repeating unit with an alicyclic hydrocarbon structure and which does not exhibit acid decomposition ability, as described later.

[0667] (32) The repeating unit described later that does not have either a hydroxyl or a cyano group and is represented by general formula (III)

[0668] When the composition of the present invention is used as a photosensitive radioactive or radiosensitive linear resin composition for EUV, the resin (A) preferably has at least one repeating unit selected from the group A above.

[0669] Furthermore, when the composition is used as a photosensitive or radiosensitive linear resin composition for EUV, the resin (A) preferably contains at least one of fluorine atoms and iodine atoms. When the resin (A) contains both fluorine atoms and iodine atoms, the resin (A) may have one repeating unit containing both fluorine atoms and iodine atoms, or the resin (A) may contain both repeating units containing fluorine atoms and repeating units containing iodine atoms.

[0670] Furthermore, when the composition is used as a photosensitive or radiosensitive linear resin composition for EUV, the resin (A) preferably contains repeating units having aromatic groups.

[0671] When the composition of the present invention is used as a photosensitive radioactive or radiosensitive linear resin composition for ArF, the resin (A) preferably has at least one repeating unit selected from group B above.

[0672] Furthermore, when the composition of the present invention is used as a photosensitive radioactive or radiosensitive linear resin composition for ArF, the resin (A) preferably does not contain either fluorine atoms or silicon atoms.

[0673] Furthermore, when the composition is used as a photosensitive or radiosensitive linear resin composition for ArF, the resin (A) preferably does not have aromatic groups.

[0674] (Repeating units with acid groups)

[0675] Resin (A) may also contain repeating units with acid groups.

[0676] As an acid group, an acid group with a pKa of 13 or less is preferred.

[0677] As an acid group, it is preferably a carboxyl group, a phenolic hydroxyl group, a fluorinated alcohol group (preferably a hexafluoroisopropanol group), a sulfonic acid group, a sulfonamide group, or an isopropanol group.

[0678] Furthermore, in the aforementioned hexafluoroisopropanol group, one or more (preferably one to two) fluorine atoms can be substituted by groups other than fluorine atoms (such as alkoxycarbonyl groups). The resulting -C(CF3)(OH)-CF2- is also preferably an acid group. Additionally, one or more fluorine atoms can be substituted by groups other than fluorine atoms to form a ring containing -C(CF3)(OH)-CF2-.

[0679] The repeating unit having an acid group is preferably a repeating unit different from the repeating units described below, including: repeating units having a structure in which a polar group is detached by the action of the acid described above and protected by a detaching group; and repeating units having a lactone group, a sulcinolone group or a carbonate group, as described later.

[0680] Repeating units with acid groups can have fluorine or iodine atoms.

[0681] As a repeating unit having an acid group, the repeating unit represented by formula (B) is preferred.

[0682] [Chemical Formula 37]

[0683]

[0684] R3 represents a hydrogen atom or an organic group that may have a 1-valent charge, such as a fluorine atom or an iodine atom.

[0685] As a monovalent organic group that can have fluorine or iodine atoms, it is preferably a group represented by -L4-R8. L4 represents a single bond or an ester group. R8 can be an alkyl group that can have fluorine or iodine atoms, a cycloalkyl group that can have fluorine or iodine atoms, an aryl group that can have fluorine or iodine atoms, or a combination thereof.

[0686] R4 and R5 represent hydrogen, fluorine, iodine, or alkyl groups that may have fluorine or iodine atoms, respectively.

[0687] L2 represents a single bond or ester group.

[0688] L3 represents an aromatic hydrocarbon cyclic group with a valence of (n+m+1) or an alicyclic hydrocarbon cyclic group with a valence of (n+m+1). Examples of aromatic hydrocarbon cyclic groups include benzene and naphthyl groups. Examples of alicyclic hydrocarbon cyclic groups include monocyclic and polycyclic groups, such as cycloalkyl groups.

[0689] R6 represents a hydroxyl group or a fluorinated alcohol group (preferably a hexafluoroisopropanol group). Additionally, when R6 is a hydroxyl group, L3 is preferably an aromatic hydrocarbon cyclic group with a (n+m+1) valence.

[0690] R7 represents a halogen atom. Examples of halogen atoms include fluorine, chlorine, bromine, and iodine.

[0691] m represents an integer greater than or equal to 1. m is preferably an integer from 1 to 3, and more preferably an integer from 1 to 2.

[0692] n represents an integer of 0 or 1 or higher. n is preferably an integer between 1 and 4.

[0693] In addition, (n+m+1) is preferably an integer from 1 to 5.

[0694] As a repeating unit having an acid group, it is also preferred to be a repeating unit represented by the following general formula (I).

[0695] [Chemical Formula 38]

[0696]

[0697] In general formula (I),

[0698] R 41 R 42 and R 43 Each of these groups independently represents a hydrogen atom, alkyl group, cycloalkyl group, halogen atom, cyano group, or alkoxycarbonyl group. Wherein, R... 42 It can bond with Ar4 to form a ring, at which point R 42 Indicates a single bond or an alkylene group.

[0699] X4 indicates a single bond, -COO-, or -CONR. 64 -, R 64 It represents a hydrogen atom or an alkyl group.

[0700] L4 indicates a single bond or alkylene group.

[0701] Ar4 represents an aromatic ring group with an (n+1) valence, when it is combined with R 42When bonded to form a ring, it represents an aromatic ring group with an (n+2) valence.

[0702] n represents an integer from 1 to 5.

[0703] R in general formula (I) 41 R 42 and R 43 The alkyl group is preferably an alkyl group with 20 or fewer carbon atoms, such as methyl, ethyl, propyl, isopropyl, n-butyl, sec-butyl, hexyl, 2-ethylhexyl, octyl, and dodecyl, more preferably an alkyl group with 8 or fewer carbon atoms, and even more preferably an alkyl group with 3 or fewer carbon atoms.

[0704] R in general formula (I) 41 R 42 and R 43 The cycloalkyl group can be monocyclic or polycyclic. Preferably, it is a monocyclic cycloalkyl group with 3 to 8 carbon atoms, such as cyclopropyl, cyclopentyl, and cyclohexyl.

[0705] R in general formula (I) 41 R 42 and R 43 The halogen atom can be fluorine, chlorine, bromine, or iodine, with fluorine being the preferred atom.

[0706] R in general formula (I) 41 R 42 and R 43 The alkyl group contained in the alkoxycarbonyl group is preferably a derivative of the above-mentioned R. 41 R 42 and R 43 The alkyl group in the text is the same as the alkyl group in the text.

[0707] Preferred substituents among the aforementioned groups include, for example, alkyl, cycloalkyl, aryl, amino, amide, urea, carbamate, hydroxyl, carboxyl, halogen, alkoxy, thioether, acyl, acyloxy, alkoxycarbonyl, cyano, and nitro groups. The substituent preferably has 8 or fewer carbon atoms.

[0708] Ar4 represents an aromatic cyclic group with an (n+1) valence. For an n of 1, a divalent aromatic cyclic group is preferably an arylene group with 6 to 18 carbon atoms, such as phenylene, tolylene group, naphthylene, or anthracene; or a divalent aromatic cyclic group containing heterocycles, such as thiophene ring, furan ring, pyrrole ring, benzothiophene ring, benzofuran ring, benzopyrrole ring, triazine ring, imidazole ring, benzimidazole ring, triazole ring, thiadiazole ring, or thiazole ring. Furthermore, the aforementioned aromatic cyclic groups may have substituents.

[0709] As a specific example of an aromatic cyclic group with a valence of (n+1) when n is an integer greater than 2, a group formed by removing (n-1) arbitrary hydrogen atoms from the above specific examples of a divalent aromatic cyclic group can be given.

[0710] (n+1) valence aromatic cyclic groups can also have substituents.

[0711] Substituents that can be present as the above-mentioned alkyl, cycloalkyl, alkoxycarbonyl, alkylene, and (n+1) valence aromatic cyclic groups include, for example, R in general formula (I). 41 R 42 and R 43 The examples listed include alkyl, methoxy, ethoxy, hydroxyethoxy, propoxy, hydroxypropoxy, and butoxy alkoxy groups; aryl groups such as phenyl groups; etc.

[0712] As represented by X4 -CONR 64 -(R 64 R in (representing hydrogen atom or alkyl group) 64 Alkyl groups, such as methyl, ethyl, propyl, isopropyl, n-butyl, sec-butyl, hexyl, 2-ethylhexyl, octyl, and dodecyl, are alkyl groups with 20 or fewer carbon atoms, and preferably alkyl groups with 8 or fewer carbon atoms.

[0713] X4 is preferably a single bond, -COO- or -CONH-, and more preferably a single bond or -COO-.

[0714] The alkylene group in L4 is preferably an alkylene group with 1 to 8 carbon atoms, such as methylene, ethylene, propylene, butylene, hexene, and octylene.

[0715] Ar4 is preferably an aromatic cyclic group with 6 to 18 carbon atoms, and more preferably a benzene cyclic group, a naphthyl cyclic group, or a biphenylene cyclic group.

[0716] The repeating unit represented by general formula (I) preferably has a hydroxystyrene structure. That is, Ar4 is preferably a benzene ring group.

[0717] As a repeating unit represented by general formula (I), it is preferred to be a repeating unit represented by the following general formula (1).

[0718] [Chemical Formula 39]

[0719]

[0720] In general formula (1),

[0721] A represents a hydrogen atom, alkyl group, cycloalkyl group, halogen atom, or cyano group.

[0722] R represents a halogen atom, alkyl, cycloalkyl, aryl, alkenyl, aralkyl, alkoxy, alkylcarbonyloxy, alkylsulfonyloxy, alkoxycarbonyl, or aryloxycarbonyl. When multiple Rs are present, they can be the same or different. When multiple Rs are present, they can collectively form a ring. Hydrogen atoms are preferred as Rs.

[0723] a represents an integer from 1 to 3.

[0724] b represents an integer from 0 to (5-a).

[0725] The following examples illustrate repeating units with acid groups. In the formula, a represents 1 or 2.

[0726] [Chemical Formula 40]

[0727]

[0728] [Chemical Formula 41]

[0729]

[0730] [Chemical Formula 42]

[0731]

[0732] Furthermore, among the repeating units described above, the repeating units specifically described below are preferred. In the formula, R represents a hydrogen atom or a methyl group, and a represents 2 or 3.

[0733] [Chemical Formula 43]

[0734]

[0735] [Chemical Formula 44]

[0736]

[0737] The content of repeating units having acid groups is preferably 10 to 70 mol% relative to all repeating units in resin (A), more preferably 10 to 60 mol%, and even more preferably 10 to 50 mol%.

[0738] (Repeating units containing fluorine or iodine atoms)

[0739] Unlike the aforementioned repeating units with acid-decomposing groups and repeating units with acid groups, resin (A) may also contain repeating units with fluorine or iodine atoms. Furthermore, the repeating units with fluorine or iodine atoms mentioned here are preferably different from other types of repeating units belonging to group A, such as repeating units with lactone, sulopentalide, or carbonate groups, and repeating units with photoacid-generating groups, as described later.

[0740] As a repeating unit having fluorine or iodine atoms, the repeating unit represented by formula (C) is preferred.

[0741] [Chemical Formula 45]

[0742]

[0743] L5 represents a single bond or ester group.

[0744] R9 represents a hydrogen atom or an alkyl group that may have a fluorine atom or an iodine atom.

[0745] R 10 It represents a hydrogen atom, an alkyl group that may have a fluorine atom or an iodine atom, a cycloalkyl group that may have a fluorine atom or an iodine atom, an aryl group that may have a fluorine atom or an iodine atom, or a group composed of these.

[0746] The following examples illustrate repeating units having fluorine or iodine atoms.

[0747] [Chemical Formula 46]

[0748]

[0749] The content of repeating units having fluorine or iodine atoms is preferably 0 to 60 mol% relative to all repeating units in resin (A), more preferably 5 to 60 mol%, and even more preferably 10 to 60 mol%.

[0750] Furthermore, as mentioned above, since the repeating units containing fluorine atoms or iodine atoms do not include <repeating units with acid-decomposing groups> and <repeating units with acid groups>, the aforementioned content of repeating units containing fluorine atoms or iodine atoms also refers to the content of repeating units containing fluorine atoms or iodine atoms other than <repeating units with acid-decomposing groups> and <repeating units with acid groups>.

[0751] The total content of repeating units containing at least one of fluorine atoms and iodine atoms in the repeating units of resin (A) is preferably 1 to 100 mol%, more preferably 5 to 80 mol%, and even more preferably 10 to 60 mol%, relative to all repeating units of resin (A).

[0752] In addition, as repeating units containing at least one of fluorine atoms and iodine atoms, examples include repeating units having fluorine atoms or iodine atoms and having acid-decomposing groups, repeating units having fluorine atoms or iodine atoms and having acid groups, and repeating units having fluorine atoms or iodine atoms.

[0753] (Repeating units with lactone, sulcinolone, or carbonate groups)

[0754] Resin (A) may contain repeating units having at least one selected from lactone, sulopentalide, and carbonate groups (hereinafter also collectively referred to as "repeating units having lactone, sulopentalide, or carbonate groups").

[0755] Repeating units having lactone, sulcinolone, or carbonate groups are preferably free of acid groups such as hexafluoropropanol groups.

[0756] As the lactone or sulfonolactone group, it is sufficient to have a lactone structure or a sulfonolactone structure. The lactone structure or sulfonolactone structure is preferably a 5- to 7-membered ring lactone structure or a 5- to 7-membered ring sulfonolactone structure. More preferably, it is a structure in which other ring structures are fused to the 5- to 7-membered ring lactone structure in the form of a bicyclic or spirocyclic structure, or a structure in which other ring structures are fused to the 5- to 7-membered ring sulfonolactone structure in the form of a bicyclic or spirocyclic structure.

[0757] The resin (A) preferably comprises repeating units having a lactone group or a sulfonolactone group, formed by removing one or more hydrogen atoms from the ring member atoms of a lactone structure represented by any one of the following general formulas (LC1-1) to (LC1-21) or a sulfonolactone structure represented by any one of the following general formulas (SL1-1) to (SL1-3).

[0758] Furthermore, lactone or sulfonyl groups can be directly bonded to the main chain. For example, the ring-membered atoms of the lactone or sulfonyl groups can form the main chain of resin (A).

[0759] [Chemical Formula 47]

[0760]

[0761] The aforementioned lactone or sulopentalide structure may have a substituent (Rb2). Preferred substituents (Rb2) include alkyl groups with 1 to 8 carbon atoms, cycloalkyl groups with 4 to 7 carbon atoms, alkoxy groups with 1 to 8 carbon atoms, alkoxycarbonyl groups with 1 to 8 carbon atoms, carboxyl groups, halogen atoms, hydroxyl groups, cyano groups, and acid-degradable groups. n2 represents an integer from 0 to 4. When n2 is 2 or more, the multiple Rb2 groups can be different, and the multiple Rb2 groups can bond together to form a ring.

[0762] As a repeating unit comprising a group having a lactone structure represented by any one of the general formulas (LC1-1) to (LC1-21) or a sulfonyl lactone structure represented by any one of the general formulas (SL1-1) to (SL1-3), for example, repeating units represented by the following general formula (AI) can be cited.

[0763] [Chemical Formula 48]

[0764]

[0765] In the general formula (AI), Rb0 represents a hydrogen atom, a halogen atom, or an alkyl group having 1 to 4 carbon atoms.

[0766] Preferred substituents that an alkyl group can have as Rb0 include hydroxyl groups and halogen atoms.

[0767] Examples of halogen atoms that can be represented by Rb0 include fluorine, chlorine, bromine, and iodine. Rb0 is preferably represented by hydrogen or methyl.

[0768] Ab represents a single bond, an alkylene group, a divalent linker having a monocyclic or polycyclic alicyclic hydrocarbon structure, an ether group, an ester group, a carbonyl group, a carboxyl group, or a divalent group composed of combinations thereof. Preferably, it is a single bond or a linker represented by -Ab1-CO2-. Ab1 is a straight-chain or branched alkylene group, or a monocyclic or polycyclic cycloalkylene group, preferably methylene, ethylene, cyclohexylene, adamantylene, or norbornylene.

[0769] V represents a group formed by removing one hydrogen atom from the ring-membered atom of a lactone structure represented by any one of the general formulas (LC1-1) to (LC1-21), or a group formed by removing one hydrogen atom from the ring-membered atom of a sulfonyl lactone structure represented by any one of the general formulas (SL1-1) to (SL1-3).

[0770] When an optical isomer exists in a repeating unit having a lactone group or a sulcinolone group, any optical isomer can be used. Furthermore, a single optical isomer can be used alone, or multiple optical isomers can be used in combination. When primarily using one optical isomer, its optical purity (ee) is preferably 90 or higher, more preferably 95 or higher.

[0771] As a carbonate group, a cyclic carbonate group is preferred.

[0772] As a repeating unit having a cyclic carbonate group, it is preferably a repeating unit represented by the following general formula (A-1).

[0773] [Chemical Formula 49]

[0774]

[0775] In general formula (A-1), R A 1 It represents a hydrogen atom, a halogen atom, or a monovalent organic group (preferably methyl).

[0776] n represents an integer greater than or equal to 0.

[0777] R A 2 This represents a substituent. When n is 2 or more, there exist multiple Rsub. A2 They can be the same or different.

[0778] A represents a single bond or a divalent linker. Preferably, the divalent linker is an alkylene group, a divalent linker having a monocyclic or polycyclic alicyclic hydrocarbon structure, an ether group, an ester group, a carbonyl group, a carboxyl group, or a divalent group formed by combining these.

[0779] Z represents a group that, together with a group represented by -O-CO-O- in the formula, forms a monocyclic or polycyclic atom.

[0780] The following examples illustrate repeating units having lactone, sulcinolone, or carbonate groups.

[0781] [Chemical Formula 50]

[0782] (in the formula ae,Rxrepresents H, CH3, CH2OH, or CF3)

[0783]

[0784] [Chemical Formula 51]

[0785] (In the formula, Rx represents H, CH3, CH2OH, or CF3.)

[0786]

[0787] [Chemical Formula 52]

[0788] (In the formula, Rx represents H, CH3, CH2OH, or CF3.)

[0789]

[0790] The content of repeating units having lactone, sulopentalide, or carbonate groups relative to all repeating units in resin (A) is preferably 1 to 70 mol%, more preferably 5 to 65 mol%, and even more preferably 5 to 60 mol%.

[0791] (Repeating unit with photoacid-generating group)

[0792] Resin (A) may also contain repeating units having groups that generate acid upon irradiation by photochemical rays or radiation (hereinafter also referred to as "photoacid-generating groups") as repeating units other than those described above.

[0793] At this point, the repeating unit having the photoacid-generating group can be considered equivalent to the compound that produces acid by irradiation with photochemical rays or radiation (hereinafter also referred to as "photoacid-generating agent").

[0794] As such a repeating unit, for example, a repeating unit represented by the following general formula (4) can be cited.

[0795] [Chemical Formula 53]

[0796]

[0797] R 41 This indicates a hydrogen atom or a methyl group. L 41 Indicates a single bond or a divalent linker. L 42 Represents a binary linker. R 40 This indicates a structural site where acid is produced in the side chain through decomposition by photochemical rays or radiation.

[0798] The following example illustrates a repeating unit with a photoacid-generating group.

[0799] [Chemical Formula 54]

[0800]

[0801]

[0802] [Chemical Formula 55]

[0803]

[0804] Furthermore, as a repeating unit represented by general formula (4), for example, the repeating unit described in paragraphs

[0094] to

[0105] of Japanese Patent Application Publication No. 2014-041327 can be cited.

[0805] The content of repeating units having photoacid-generating groups is preferably 1 to 40 mol% relative to all repeating units in resin (A), more preferably 5 to 35 mol%, and even more preferably 5 to 30 mol%.

[0806] (Repeating units represented by general formula (V-1) or (V-2))

[0807] Resin (A) may also have repeating units represented by the following general formula (V-1) or the following general formula (V-2).

[0808] The repeating unit represented by the following general formula (V-1) and the following general formula (V-2) is preferably a repeating unit that is different from the repeating unit described above.

[0809] [Chemical Formula 56]

[0810]

[0811] In the formula,

[0812] R6 and R7 independently represent a hydrogen atom, hydroxyl group, alkyl group, alkoxy group, acyloxy group, cyano group, nitro group, amino group, halogen atom, ester group (-OCOR or -COOR: R is an alkyl or fluoroalkyl group with 1 to 6 carbon atoms) or carboxyl group. As an alkyl group, a straight-chain, branched or cyclic alkyl group with 1 to 10 carbon atoms is preferred.

[0813] n3 represents an integer from 0 to 6.

[0814] n4 represents an integer from 0 to 4.

[0815] X4 represents a methylene group, an oxygen atom, or a sulfur atom.

[0816] The following examples illustrate repeating units represented by the general formula (V-1) or (V-2).

[0817] [Chemical Formula 57]

[0818]

[0819] (Repetitive units used to reduce the mobility of the main chain)

[0820] From the viewpoint of suppressing excessive diffusion of generated acid or pattern breakdown during development, resin (A) preferably has a high glass transition temperature (Tg). Tg is preferably greater than 90°C, more preferably greater than 100°C, even more preferably greater than 110°C, and particularly preferably greater than 125°C. In addition, excessively high Tg will lead to a decrease in the dissolution rate in the developer, so Tg is preferably below 400°C, more preferably below 350°C.

[0821] In addition, in this specification, the glass transition temperature (Tg) of polymers such as resin (A) is calculated by the following method. First, the Tg of the homopolymer composed only of each repeating unit contained in the polymer is calculated separately using the Bicerano method. Then, the calculated Tg is referred to as the "repeating unit Tg". Next, the mass ratio (%) of each repeating unit relative to all repeating units in the polymer is calculated. Then, the Tg of each mass ratio is calculated using the Fox formula (described in Materials Letters 62 (2008) 3152 et al.), and their sum is set as the Tg (°C) of the polymer.

[0822] The Bicerano method is documented in *Prediction of polymer properties*, Marcel Dekker Inc., New York (1993), etc. Furthermore, the Tg calculation performed using the Bicerano method can be performed using the polymer property estimation software MDL Polymer (MDL Information Systems, Inc.).

[0823] In order to increase the Tg of resin (A) (preferably exceeding 90°C), it is preferable to reduce the mobility of the main chain of resin (A). Methods for reducing the mobility of the main chain of resin (A) include the following methods (a) to (e).

[0824] (a) Introducing bulk substituents into the main chain

[0825] (b) Introducing multiple substituents into the main chain

[0826] (c) Introduce substituents that initiate interactions between resins (A) near the main chain.

[0827] (d) Formation of the main chain in the ring structure

[0828] (e) Connect the ring structure to the main chain

[0829] In addition, resin (A) preferably has repeating units with a Tg of 130°C or higher in homopolymers.

[0830] Furthermore, there are no particular restrictions on the types of repeating units with a Tg of 130°C or higher in the homopolymer, as long as the repeating unit has a Tg of 130°C or higher as calculated by the Bicerano method. Additionally, the types of functional groups in the repeating units represented by equations (A) to (E) described later correspond to repeating units with a Tg of 130°C or higher in the homopolymer.

[0831] (Repeating unit represented by equation (A))

[0832] As an example of a specific implementation of (a) above, a method of introducing the repeating unit represented by formula (A) into resin (A) can be given.

[0833] [Chemical Formula 58]

[0834]

[0835] In formula (A), R A This indicates a group with a polycyclic structure. R x This indicates a hydrogen atom, methyl, or ethyl group. A polycyclic group is a group with multiple ring structures; these ring structures may or may not be fused.

[0836] As a specific example of a repeating unit represented by equation (A), the following repeating unit can be given.

[0837] [Chemical Formula 59]

[0838]

[0839] [Chemical Formula 60]

[0840]

[0841] [Chemical Formula 61]

[0842]

[0843] In the above formula, R represents a hydrogen atom, a methyl group, or an ethyl group.

[0844] Ra represents a hydrogen atom, alkyl, cycloalkyl, aryl, aralkyl, alkenyl, hydroxyl, alkoxy, acyloxy, cyano, nitro, amino, halogen atom, ester group (-OCOR"' or -COOR"': R"' is an alkyl or fluoroalkyl group with 1 to 20 carbon atoms), or carboxyl group. Furthermore, the aforementioned alkyl, cycloalkyl, aryl, aralkyl, and alkenyl groups may each have substituents. Additionally, the hydrogen atom bonded to the carbon atom in the group represented by Ra may be replaced by a fluorine atom or an iodine atom.

[0845] Furthermore, R' and R” independently represent alkyl, cycloalkyl, aryl, aralkyl, alkenyl, hydroxyl, alkoxy, acyloxy, cyano, nitro, amino, halogen atom, ester group (-OCOR”' or -COOR”': R”' is an alkyl or fluoroalkyl group with 1 to 20 carbon atoms) or carboxyl group. Additionally, the aforementioned alkyl, cycloalkyl, aryl, aralkyl, and alkenyl groups may each have substituents. Furthermore, the hydrogen atoms bonded to the carbon atoms in the groups represented by R' and R” may be replaced by fluorine or iodine atoms.

[0846] L represents a single bond or a divalent linker. Examples of divalent linkers include -COO-, -CO-, -O-, -S-, -SO-, -SO2-, alkylene, cycloalkylene, alkenyl, and linkers formed by the linkage of multiple of these.

[0847] m and n each independently represent integers greater than or equal to 0. There is no particular upper limit to m and n, but they are usually below 2, and more often below 1.

[0848] (Repeating unit represented by equation (B))

[0849] As an example of a specific implementation of (b) above, a method of introducing the repeating unit represented by formula (B) into resin (A) can be given.

[0850] [Chemical Formula 62]

[0851]

[0852] In equation (B), R b1 ~R b4 Each can independently represent a hydrogen atom or an organic group, Rb1 ~R b4 At least two of them represent organic groups.

[0853] Furthermore, when at least one of the organic groups is a ring structure directly attached to the main chain of the repeating unit, there are no particular restrictions on the types of other organic groups.

[0854] Furthermore, when none of the organic groups are directly attached to the main chain of the repeating unit by a ring structure, at least two of the organic groups are substituents with a number of three or more constituent atoms other than hydrogen atoms.

[0855] As a specific example of a repeating unit represented by equation (B), the following repeating unit can be given.

[0856] [Chemical Formula 63]

[0857]

[0858] In the above formula, R independently represents a hydrogen atom or an organic group. Examples of organic groups include alkyl, cycloalkyl, aryl, aralkyl, and alkenyl groups, which can have substituents.

[0859] R' can independently represent alkyl, cycloalkyl, aryl, aralkyl, alkenyl, hydroxyl, alkoxy, acyloxy, cyano, nitro, amino, halogen atom, ester group (-OCOR" or -COOR": R" is an alkyl or fluoroalkyl group with 1 to 20 carbon atoms) or carboxyl group. Furthermore, the aforementioned alkyl, cycloalkyl, aryl, aralkyl, and alkenyl groups may each have substituents. Additionally, the hydrogen atoms bonded to the carbon atoms in the group represented by R' can be replaced by fluorine or iodine atoms.

[0860] m represents an integer greater than or equal to 0. There is no specific upper limit to m, but it is usually below 2, and more often below 1.

[0861] (Repeating unit represented by equation (C))

[0862] As an example of a specific implementation of (c) above, a method of introducing the repeating unit represented by formula (C) into resin (A) can be given.

[0863] [Chemical Formula 64]

[0864]

[0865] In equation (C), R c1 ~R c4 Each can independently represent a hydrogen atom or an organic group, R c1 ~R c4At least one of them is a group having hydrogen atoms with hydrogen bonding capacity of 3 or less from the main chain carbon. Preferably, it has hydrogen atoms with hydrogen bonding capacity of 2 or less (closer to the main chain side) on the basis of causing the interaction between the main chains of resin (A).

[0866] As a specific example of a repeating unit represented by equation (C), the following repeating units can be cited.

[0867] [Chemical Formula 65]

[0868]

[0869] In the above formula, R represents an organic group. Examples of organic groups include alkyl, cycloalkyl, aryl, aralkyl, alkenyl, and ester groups (-OCOR or -COOR: R is an alkyl or fluoroalkyl group with 1 to 20 carbon atoms).

[0870] R' represents a hydrogen atom or an organic group. Examples of organic groups include alkyl, cycloalkyl, aryl, aralkyl, and alkenyl groups. Additionally, the hydrogen atom in an organic group can be replaced by a fluorine or iodine atom.

[0871] (Repeating unit represented by equation (D))

[0872] As an example of a specific implementation of (d) above, a method of introducing the repeating unit represented by formula (D) into resin (A) can be given.

[0873] [Chemical Formula 66]

[0874]

[0875] In formula (D), "Cyclic" represents a group whose main chain is formed by a ring structure. There is no particular restriction on the number of atoms constituting the ring.

[0876] As a specific example of a repeating unit represented by equation (D), the following repeating unit can be given.

[0877] [Chemical Formula 67]

[0878]

[0879] In the above formulas, R independently represents a hydrogen atom, alkyl, cycloalkyl, aryl, aralkyl, alkenyl, hydroxyl, alkoxy, acyloxy, cyano, nitro, amino, halogen atom, ester group (-OCOR” or -COOR”: R” is an alkyl or fluoroalkyl group with 1 to 20 carbon atoms), or carboxyl group. Furthermore, the aforementioned alkyl, cycloalkyl, aryl, aralkyl, and alkenyl groups may each have substituents. Additionally, the hydrogen atom bonded to the carbon atom in the group represented by R may be replaced by a fluorine atom or an iodine atom.

[0880] In the above formulas, R' independently represents an alkyl, cycloalkyl, aryl, aralkyl, alkenyl, hydroxyl, alkoxy, acyloxy, cyano, nitro, amino, halogen atom, ester group (-OCOR" or -COOR": R" is an alkyl or fluoroalkyl group with 1 to 20 carbon atoms), or carboxyl group. Furthermore, the aforementioned alkyl, cycloalkyl, aryl, aralkyl, and alkenyl groups may each have substituents. Additionally, the hydrogen atoms bonded to the carbon atoms in the group represented by R' may be replaced by fluorine or iodine atoms.

[0881] m represents an integer greater than or equal to 0. There is no specific upper limit to m, but it is usually below 2, and more often below 1.

[0882] (Repeating unit represented by equation (E))

[0883] As an example of a specific implementation of (e) above, a method of introducing the repeating unit represented by formula (E) into resin (A) can be given.

[0884] [Chemical Formula 68]

[0885]

[0886] In formula (E), Re independently represents either a hydrogen atom or an organic group. Examples of organic groups that can have substituents include alkyl, cycloalkyl, aryl, aralkyl, and alkenyl groups.

[0887] "Cyclic" is a cyclic group containing carbon atoms in its main chain. There is no particular limitation on the number of atoms contained in a cyclic group.

[0888] As a specific example of a repeating unit represented by equation (E), the following repeating unit can be given.

[0889] [Chemical Formula 69]

[0890]

[0891] [Chemical Formula 70]

[0892]

[0893] In the above formulas, R independently represents a hydrogen atom, alkyl, cycloalkyl, aryl, aralkyl, alkenyl, hydroxyl, alkoxy, acyloxy, cyano, nitro, amino, halogen atom, ester group (-OCOR” or -COOR”: R” is an alkyl or fluoroalkyl group with 1 to 20 carbon atoms), or carboxyl group. Furthermore, the aforementioned alkyl, cycloalkyl, aryl, aralkyl, and alkenyl groups may each have substituents. Additionally, the hydrogen atom bonded to the carbon atom in the group represented by R may be replaced by a fluorine atom or an iodine atom.

[0894] R' can independently represent a hydrogen atom, alkyl, cycloalkyl, aryl, aralkyl, alkenyl, hydroxyl, alkoxy, acyloxy, cyano, nitro, amino, halogen atom, ester (-OCOR" or -COOR": R" is an alkyl or fluoroalkyl group with 1 to 20 carbon atoms), or carboxyl. Furthermore, the aforementioned alkyl, cycloalkyl, aryl, aralkyl, and alkenyl groups may each have substituents. Additionally, the hydrogen atom bonded to the carbon atom in the group represented by R' can be replaced by a fluorine or iodine atom.

[0895] m represents an integer greater than or equal to 0. There is no specific upper limit to m, but it is usually below 2, and more often below 1.

[0896] Furthermore, two R atoms bonded to the same carbon atom can bond with each other to form a ring.

[0897] In equations (E-2), (E-4), (E-6), and (E-8), two Rs can together form “=O”.

[0898] The content of the repeating unit represented by formula (E) relative to all repeating units in resin (A) is preferably 5 mol% or more, more preferably 10 mol% or more. Furthermore, as an upper limit, it is preferably 60 mol% or less, more preferably 55 mol% or less.

[0899] (A repeating unit having at least one group selected from lactone, sulcinolone, carbonate, hydroxyl, cyano, and alkali-soluble groups)

[0900] Resin (A) may contain repeating units having at least one group selected from lactone, sulcinolone, carbonate, hydroxyl, cyano and alkali-soluble groups.

[0901] As for the repeating units having lactone, sulfonyl, or carbonate groups in resin (A), examples of repeating units described in the above-described section on "Repeating Units Having Lactone, Sulfolactone, or Carbonate Groups" can be cited. The preferred content is also as described in the above-described section on "Repeating Units Having Lactone, Sulfolactone, or Carbonate Groups".

[0902] Resin (A) may also contain repeating units having hydroxyl or cyano groups. This improves substrate adhesion and developer affinity.

[0903] The repeating unit having a hydroxyl or cyano group is preferably a repeating unit having an alicyclic hydrocarbon structure substituted with a hydroxyl or cyano group.

[0904] Repeating units having hydroxyl or cyano groups preferably do not have acid-degradable groups.

[0905] As repeating units having hydroxyl or cyano groups, examples of repeating units represented by the following general formulas (AIIa) to (AIId) can be cited.

[0906] [Chemical Formula 71]

[0907]

[0908] In general formulas (AIIa) to (AIId),

[0909] R 1c It represents a hydrogen atom, methyl, trifluoromethyl, or hydroxymethyl.

[0910] R 2c ~R 4c Each can independently represent a hydrogen atom, a hydroxyl group, or a cyano group. Wherein, R... 2c ~R 4c At least one of them represents a hydroxyl or cyano group. R is preferred. 2c ~R 4c One or two of them are hydroxyl groups, and the rest are hydrogen atoms. More preferably, R... 2c ~R 4c Two of them are hydroxyl groups, and the rest are hydrogen atoms.

[0911] The content of repeating units having hydroxyl or cyano groups relative to all repeating units in resin (A) is preferably 5 mol% or more, more preferably 10 mol% or more. Furthermore, as an upper limit, it is preferably 60 mol% or less, more preferably 55 mol% or less, and even more preferably 50 mol% or less.

[0912] The following are specific examples of repeating units having hydroxyl or cyano groups, but the invention is not limited to these.

[0913] [Chemical Formula 72]

[0914]

[0915] Resin (A) may also contain repeating units with alkali-soluble groups.

[0916] Examples of alkali-soluble groups include carboxyl groups, sulfonamide groups, sulfonylimide groups, bissulfonylimide groups, and aliphatic alcohol groups substituted at the α-position with an electron-withdrawing group (e.g., hexafluoroisopropanol groups), with carboxyl groups being preferred. By including repeating units having alkali-soluble groups in the resin (A), the resolution in contact hole applications is improved.

[0917] Examples of repeating units with alkali-soluble groups include repeating units formed from acrylic acid and methacrylic acid where the alkali-soluble groups are directly bonded to the resin backbone, or repeating units where the alkali-soluble groups are bonded to the resin backbone via linkers. Furthermore, the linkers can have monocyclic or polycyclic cyclic hydrocarbon structures.

[0918] As a repeating unit having an alkali-soluble group, it is preferably a repeating unit formed of acrylic acid or methacrylic acid.

[0919] The content of repeating units having alkali-soluble groups is preferably 0 mol% or more, more preferably 3 mol% or more, and even more preferably 5 mol% or more, relative to all repeating units in resin (A). As an upper limit, it is preferably 20 mol% or less, more preferably 15 mol% or less, and even more preferably 10 mol% or less.

[0920] The following are specific examples of repeating units having alkali-soluble groups, but the invention is not limited thereto. In the specific examples, Rx represents H, CH3, CH2OH, or CF3.

[0921] [Chemical Formula 73]

[0922]

[0923] As a repeating unit having at least one group selected from lactone, hydroxyl, cyano and alkali-soluble groups, it is preferably a repeating unit having at least two groups selected from lactone, hydroxyl, cyano and alkali-soluble groups, more preferably a repeating unit having cyano and lactone groups, and even more preferably a repeating unit having a cyano-substituted structure in the lactone structure represented by general formula (LC1-4).

[0924] (Repeating unit with an alicyclic hydrocarbon structure and not exhibiting acid decomposition properties)

[0925] Resin (A) may also contain repeating units with an alicyclic hydrocarbon structure that do not exhibit acid decomposition properties. This reduces the leaching of low-molecular-weight components from the resist film into the immersion solution during immersion exposure. Examples of such repeating units include those derived from 1-adamantane (meth)acrylate, diadamantane (meth)acrylate, tricyclodecane (meth)acrylate, or cyclohexyl (meth)acrylate.

[0926] (A repeating unit that does not have either a hydroxyl or a cyano group and is represented by general formula (III))

[0927] Resin (A) may also contain repeating units that do not have either hydroxyl or cyano groups and are represented by general formula (III).

[0928] [Chemical Formula 74]

[0929]

[0930] In general formula (III), R5 represents a hydrocarbon group having at least one cyclic structure and not having either a hydroxyl or a cyano group.

[0931] Ra represents a hydrogen atom, an alkyl group, or a -CH2-O-Ra2 group. In the formula, Ra2 represents a hydrogen atom, an alkyl group, or an acyl group.

[0932] The cyclic structure of R5 includes monocyclic hydrocarbon groups and polycyclic hydrocarbon groups. Examples of monocyclic hydrocarbon groups include cycloalkyl groups with 3 to 12 carbon atoms (more preferably 3 to 7 carbon atoms) or cycloalkenyl groups with 3 to 12 carbon atoms.

[0933] Examples of polycyclic hydrocarbon groups include cyclic aggregate hydrocarbon groups and cross-linked cyclic hydrocarbon groups. Examples of cross-linked cyclic hydrocarbon rings include 2-cyclic hydrocarbon rings, 3-cyclic hydrocarbon rings, and 4-cyclic hydrocarbon rings. Furthermore, cross-linked cyclic hydrocarbon rings may also include fused rings with multiple 5- to 8-membered cycloalkane rings.

[0934] As a crosslinked cyclic hydrocarbon group, norbornyl, adamantyl, bicyclooctyl, or tricyclo[5, 2, 1, 0] are preferred. 2,6 ] Decyl, more preferably norbornyl or adamantyl.

[0935] Alicyclic hydrocarbon groups can have substituents. Examples of substituents include halogen atoms, alkyl groups, hydroxyl groups protected by a protecting group, and amino groups protected by a protecting group.

[0936] The preferred halogen atom is a bromine atom, a chlorine atom, or a fluorine atom.

[0937] The preferred alkyl group is methyl, ethyl, butyl, or tert-butyl. The alkyl group may also have substituents, such as halogen atoms, alkyl groups, hydroxyl groups protected by a protecting group, or amino groups protected by a protecting group.

[0938] Examples of protecting groups include alkyl, cycloalkyl, aralkyl, substituted methyl, substituted ethyl, alkoxycarbonyl, and aralkoxycarbonyl.

[0939] As an alkyl group, an alkyl group having 1 to 4 carbon atoms is preferred.

[0940] The preferred substituted methyl group is methoxymethyl, methoxythiomethyl, benzyloxymethyl, tert-butoxymethyl, or 2-methoxyethoxymethyl.

[0941] As the substituted ethyl group, 1-ethoxyethyl or 1-methyl-1-methoxyethyl is preferred.

[0942] As an acyl group, it is preferably an aliphatic acyl group with 1 to 6 carbon atoms, such as formyl, acetyl, propionyl, butyryl, isobutyryl, valeryl, and neovaleryl.

[0943] As an alkoxycarbonyl group, an alkoxycarbonyl group having 1 to 4 carbon atoms is preferred.

[0944] The content of repeating units that do not have either a hydroxyl or a cyano group and are represented by general formula (III) relative to all repeating units in resin (A) is preferably 0 to 40 mol%, more preferably 0 to 20 mol%.

[0945] The following are specific examples of repeating units represented by general formula (III), but the invention is not limited to these. In the specific examples, Ra represents H, CH3, CH2OH, or CF3.

[0946] [Chemical Formula 75]

[0947]

[0948] (Other repeating units)

[0949] Resin (A) may also contain repeating units other than those described above.

[0950] For example, resin (A) may contain repeating units selected from repeating units having an oxathiane ring group, repeating units having an oxazorone ring group, repeating units having a dioxane ring group, and repeating units having a hydantoin ring group.

[0951] The following is an example of such repeating units.

[0952] [Chemical Formula 76]

[0953]

[0954] In addition to the repeating structural units mentioned above, resin (A) may also have various repeating structural units for purposes such as adjusting dry etching resistance, compatibility with standard developer, substrate adhesion, resist profile, resolution, heat resistance, and sensitivity.

[0955] As resin (A), (especially when the composition is used as a photosensitive or radiosensitive linear resin composition for ArF) it is also preferred that all repeating units are composed of (meth)acrylate repeating units. In this case, any one of the following repeating units can be used: repeating units in which all repeating units are methacrylate repeating units, repeating units in which all repeating units are acrylate repeating units, or repeating units in which all repeating units are formed from methacrylate repeating units and acrylate repeating units, wherein the acrylate repeating units are preferably 50 mol% or less of all repeating units.

[0956] Resin (A) can be synthesized using conventional methods (e.g., free radical polymerization).

[0957] As a conversion value for polystyrene based on the GPC method, the weight-average molecular weight of resin (A) is preferably 1,000 to 200,000, more preferably 3,000 to 20,000, and even more preferably 5,000 to 15,000. By setting the weight-average molecular weight of resin (A) to 1,000 to 200,000, the deterioration of heat resistance and dry etching resistance can be further suppressed. Furthermore, the deterioration of film-forming properties caused by deterioration of developability and increased viscosity can be further suppressed.

[0958] The dispersion (molecular weight distribution) of resin (A) is typically 1 to 5, preferably 1 to 3, more preferably 1.20 to 3.00, and even more preferably 1.20 to 2.00. The smaller the dispersion, the better the resolution and resist shape, and the smoother the sidewalls of the resist pattern, and the better the roughness.

[0959] In the composition of the present invention, the content of resin (A) is preferably 50 to 99.9% by mass, more preferably 60 to 99.0% by mass, relative to the total solid content of the composition.

[0960] In addition, solid components refer to components other than solvents in the composition. Any component other than solvents, even liquid components, are considered solid components.

[0961] Furthermore, one type of resin (A) may be used, or multiple types may be used together.

[0962] <Other photoacid generators>

[0963] The resist composition may contain other photoacid generators (compounds that generate acid by exposure to photochemical rays or radiation, which are not equivalent to a specific compound). Other photoacid generators are compounds that generate acid by exposure (preferably EUV light and / or ArF exposure).

[0964] Other photoacid-generating agents can be in the form of low-molecular-weight compounds or in the form of compounds embedded in a polymer. Furthermore, both low-molecular-weight compound forms and forms embedded in a polymer can be used in combination.

[0965] When other photoacid-generating agents are in the form of low molecular weight compounds, the molecular weight is preferably 3000 or less, more preferably 2000 or less, and even more preferably 1000 or less.

[0966] When other photoacid generators are in the form of being embedded in a part of a polymer, they can be embedded in a part of resin (A) or in a resin different from resin (A).

[0967] In this invention, the photoacid generator is preferably in the form of a low molecular weight compound.

[0968] Other photoacid-generating agents are not particularly limited, but compounds that generate organic acids are preferred. As for the organic acids mentioned above, examples of organic acids that can be generated by specific compounds can also be given.

[0969] Other photoacid-producing agents include, for example, those derived from "M" + X - The compound indicated by "" is a bismuth salt.

[0970] In the case of “M” + X - In the compound represented by "X", - It represents an organic anion.

[0971] “M + X - X in " - The same method can be used to describe the general formula (1) in a specific compound by X. - The organic anion is represented.

[0972] In the case of “M” + X - In the compounds represented by "", M + It represents an organic cation.

[0973] The aforementioned organic cations are preferably cations represented by the general formula (ZaI) (cation (ZaI)) or cations represented by the general formula (ZaII) (cation (ZaII)).

[0974] The cation represented by the general formula (ZaI) is different from the specific cation in a particular compound.

[0975] [Chemical Formula 77]

[0976]

[0977] R 204 -| + —R 205 (ZaII)

[0978] In the above general formula (ZaI),

[0979] R 201 R 202 and R 203 Each organic group can be represented independently.

[0980] As R 201 R 202 and R 203 The number of carbon atoms in the organic group is typically 1 to 30, preferably 1 to 20. Furthermore, R... 201 ~R 203 The two atoms in the ring can bond together to form a ring structure, or the ring can contain oxygen atoms, sulfur atoms, ester groups, amide groups, or carbonyl groups. As R 201 ~R 203 Two groups formed by bonding can be alkylene groups (e.g., butylene, pentylene, etc.) and -CH2-CH2-O-CH2-CH2-.

[0981] Examples of cations in the general formula (ZaI) include, for example, the cation described later (ZaI-1).

[0982] The cation (ZaI-1) is R in the above general formula (ZaI). 201 ~R 203 At least one of them is an aryl arbutin cation of aryl.

[0983] In arylsulfonium cations, R can be 201 ~R 203 All are aryl, or can be R 201 ~R 203 One part of it is aryl, and the rest is alkyl or cycloalkyl.

[0984] Furthermore, R 201 ~R 203 One of them is aryl, R 201 ~R 203 The remaining two atoms can bond together to form a ring structure, or the ring can contain oxygen atoms, sulfur atoms, ester groups, amide groups, or carbonyl groups. As R 201 ~R 203 Two groups formed by bonding in the group, for example, one or more methylene groups can be substituted by an oxygen atom, a sulfur atom, an ester group, an amide group and / or a carbonyl group (e.g., butylene, pentylene or -CH2-CH2-O-CH2-CH2-).

[0985] Examples of arylsulfonium cations include triarylsulfonium cations, diarylalkylsulfonium cations, aryldialkylsulfonium cations, diarylcycloalkylsulfonium cations, and aryldicycloalkylsulfonium cations.

[0986] The aryl group contained in the aryl sulfonium cation is preferably phenyl or naphthyl, more preferably phenyl. The aryl group can be an aryl group containing a heterocyclic structure having an oxygen atom, nitrogen atom, or sulfur atom. Examples of heterocyclic structures include pyrrole residues, furan residues, thiophene residues, indole residues, benzofuran residues, and benzothiophene residues. When the aryl sulfonium cation has two or more aryl groups, the two or more aryl groups can be the same or different.

[0987] The alkyl or cycloalkyl group of the arylsulfonium cation is preferably a straight-chain alkyl group with 1 to 15 carbon atoms, a branched alkyl group with 3 to 15 carbon atoms, or a cycloalkyl group with 3 to 15 carbon atoms. Examples include methyl, ethyl, propyl, n-butyl, sec-butyl, tert-butyl, cyclopropyl, cyclobutyl, and cyclohexyl.

[0988] R 201 ~R 203 The aryl, alkyl, and cycloalkyl groups may have substituents that are preferably alkyl (e.g., 1 to 15 carbon atoms), cycloalkyl (e.g., 3 to 15 carbon atoms), aryl (e.g., 6 to 14 carbon atoms), alkoxy (e.g., 1 to 15 carbon atoms), cycloalkylalkoxy (e.g., 1 to 15 carbon atoms), halogen atom, hydroxyl or phenylthio group.

[0989] The above-mentioned substituents may also have substituents where possible. For example, the above-mentioned alkyl group may have a halogen atom as a substituent to become a trifluoromethyl or other haloalkyl group.

[0990] Other photoacid-generating agents include, for example, the following compounds.

[0991] [Chemical Formula 78]

[0992]

[0993]

[0994]

[0995] When the resist composition contains other photoacid-generating agents, their content is not particularly limited. However, from the viewpoint of achieving better results in this invention, the content is preferably 0.5% by mass or more, more preferably 1% by mass or more, and even more preferably 2% by mass or more, relative to the total solid content of the composition. Furthermore, the above-mentioned content is preferably 40% by mass or less, more preferably 35% by mass or less, and even more preferably 30% by mass or less.

[0996] One type of photoacid generator can be used alone, or two or more types can be used.

[0997] <Solvent>

[0998] The resist composition may also contain a solvent.

[0999] The solvent preferably contains at least one of (M1) propylene glycol monoalkyl ether carboxylic acid ester and (M2), wherein (M2) is selected from at least one of propylene glycol monoalkyl ether, lactate, acetate, alkoxypropionate, chain ketone, cyclic ketone, lactone, and alkylene carbonate. Additionally, the solvent may contain components other than (M1) and (M2).

[1000] The inventors have discovered that by combining this solvent with the aforementioned resin, the coatability of the composition is improved, and patterns with fewer development defects can be formed. Although the reason is not yet clear, the inventors believe that the reason is that, due to the good balance of solubility, boiling point, and viscosity of these solvents in the aforementioned resin, uneven film thickness of the composition film and the generation of precipitates during spin coating can be suppressed.

[1001] The component (M1) is preferably selected from at least one of propylene glycol monomethyl ether acetate (PGMEA), propylene glycol monomethyl ether propionate and propylene glycol monoethyl ether acetate, more preferably propylene glycol monomethyl ether acetate (PGMEA).

[1002] The preferred solvent for component (M2) is as follows.

[1003] The preferred propylene glycol monoalkyl ethers are propylene glycol monomethyl ether (PGME) and propylene glycol monoethyl ether (PGEE).

[1004] The lactate is preferably ethyl lactate, butyl lactate or propyl lactate.

[1005] The preferred acetates are methyl acetate, ethyl acetate, butyl acetate, isobutyl acetate, propyl acetate, isoamyl acetate, methyl formate, ethyl formate, butyl formate, propyl formate, or 3-methoxybutyl acetate.

[1006] Furthermore, butyl butyrate is preferred.

[1007] The preferred alkoxypropionate is methyl 3-methoxypropionate (MMP) or ethyl 3-ethoxypropionate (EEP).

[1008] The preferred chain ketones are 1-octanone, 2-octanone, 1-nonanone, 2-nonanone, acetone, 2-heptanone, 4-heptanone, 1-hexanone, 2-hexanone, diisobutyl ketone, phenylacetone, methyl ethyl ketone, methyl isobutyl ketone, acetylacetone, acetone-based acetone, ionone, diacetonyl alcohol, acetoethanol, acetophenone, methyl naphthyl ketone, or methyl pentyl ketone.

[1009] Cyclic ketones are preferably methylcyclohexanone, isophorone, cyclopentanone, or cyclohexanone.

[1010] The preferred lactone is γ-butyrolactone.

[1011] Alkyl carbonate is preferably propylene carbonate.

[1012] The component (M2) is more preferably propylene glycol monomethyl ether (PGME), ethyl lactate, ethyl 3-ethoxypropionate, methyl pentyl ketone, cyclohexanone, butyl acetate, pentyl acetate, γ-butyrolactone, or propylene carbonate.

[1013] In addition to the above-mentioned components, it is preferable to use an ester solvent with 7 or more carbon atoms (preferably 7 to 14, more preferably 7 to 12, and even more preferably 7 to 10) and 2 or fewer heteroatoms.

[1014] Examples of ester solvents having 7 or more carbon atoms and 2 or fewer heteroatoms include amyl acetate, 2-methylbutyl acetate, 1-methylbutyl acetate, hexyl acetate, amyl propionate, hexyl propionate, butyl propionate, isobutyl isobutyrate, heptyl propionate, and butyl butyrate, with isoamyl acetate being preferred.

[1015] The component (M2) is preferably a solvent with a flash point (hereinafter also referred to as "fp") of 37°C or higher. This component (M2) is preferably propylene glycol monomethyl ether (fp: 47°C), ethyl lactate (fp: 53°C), ethyl 3-ethoxypropionate (fp: 49°C), methyl pentyl ketone (fp: 42°C), cyclohexanone (fp: 44°C), amyl acetate (fp: 45°C), methyl 2-hydroxyisobutyrate (fp: 45°C), γ-butyrolactone (fp: 101°C), or propylene carbonate (fp: 132°C). More preferably, it is propylene glycol monoethyl ether, ethyl lactate, amyl acetate, or cyclohexanone; even more preferably, it is propylene glycol monoethyl ether or ethyl lactate.

[1016] Additionally, here, "flash point" refers to the value listed in the reagent product catalog of Tokyo Chemical Industry Co., Ltd. or Sigma-Aldrich.

[1017] The solvent preferably contains component (M1). More preferably, the solvent consists of component (M1) alone or is a mixture of component (M1) and other components. In the latter case, the solvent further preferably contains both component (M1) and component (M2).

[1018] The mass ratio (M1 / M2) of component (M1) to component (M2) is preferably “100 / 0” to “0 / 10”, more preferably “100 / 0” to “15 / 85”, even more preferably “100 / 0” to “40 / 60”, and especially preferably “100 / 0” to “60 / 40”.

[1019] That is, when the solvent contains both component (M1) and component (M2), the mass ratio of component (M1) to component (M2) is preferably 15 / 85 or more, more preferably 40 / 60 or more, and even more preferably 60 / 40 or more. Using this configuration further reduces the number of development defects.

[1020] In addition, when the solvent contains both component (M1) and component (M2), the mass ratio of component (M1) to component (M2) is set to, for example, 99 / 1 or less.

[1021] As described above, the solvent may also contain components other than (M1) and (M2). In this case, the content of components other than (M1) and (M2) is preferably 5 to 30% by mass relative to the total amount of solvent.

[1022] The solvent content in the resist composition is preferably set to a solid component concentration of 0.5 to 30% by mass, more preferably 1 to 20% by mass. This can further improve the coatability of the resist composition.

[1023] In addition, solid components refer to all components except the solvent.

[1024] <Acid diffusion control agent>

[1025] The resist composition may further contain an acid diffusion control agent. The acid diffusion control agent acts as a quencher to capture acid generated by the photoacid generator and plays a role in controlling the diffusion of acid in the resist film.

[1026] Acid diffusion control agents can be, for example, basic compounds.

[1027] The basic compound is preferably a compound having a structure represented by the following general formulas (A) to (E).

[1028] [Chemical Formula 79]

[1029]

[1030] In general formulas (A) and (E), R 200 R 201 and R 202 These can be the same or different, representing hydrogen atoms, alkyl groups (preferably 1 to 20 carbon atoms), cycloalkyl groups (preferably 3 to 20 carbon atoms), or aryl groups (preferably 6 to 20 carbon atoms). Here, R... 201 and R 202 They can bond together to form a ring.

[1031] Regarding the aforementioned alkyl group, the alkyl group having a substituent is preferably an aminoalkyl group having 1 to 20 carbon atoms, a hydroxyalkyl group having 1 to 20 carbon atoms, or a cyanoalkyl group having 1 to 20 carbon atoms.

[1032] R 203 R 204 R 205 and R 206 They can be the same or different, and they represent alkyl groups with 1 to 20 carbon atoms.

[1033] The alkyl groups in these general formulas (A) and (E) are more preferably unsubstituted.

[1034] As basic compounds, guanidine, aminopyrrolidine, pyrazole, pyrazoline, piperazine, aminomorpholine, aminoalkylmorpholine (the alkyl portion can be straight-chain or branched, and may be partially substituted with ether and / or ester groups. The total number of atoms other than hydrogen atoms in the alkyl portion is preferably 1 to 17) or piperidine, etc. More preferably are compounds having an imidazole structure, a diazabicyclic structure, an ononium hydroxide structure, an ononium carboxylate structure, a trialkylamine structure, an aniline structure, or a pyridine structure, alkylamine derivatives having hydroxyl and / or ether bonds, or aniline derivatives having hydroxyl and / or ether bonds, etc.

[1035] Examples of compounds having an imidazole structure include imidazole, 2,4,5-triphenylimidazolium, and benzimidazole. Examples of compounds having a diazabicyclic structure include 1,4-diazabicyclic[2,2,2]octane, 1,5-diazabicyclic[4,3,0]non-5-ene, and 1,8-diazabicyclic[5,4,0]undecane-7-ene. Examples of compounds having a onium hydroxide structure include triarylsulfonium hydroxide, benzoylsulfonium hydroxide, and sulfonium hydroxide having a 2-oxoalkyl group. Specifically, examples include triphenylsulfonium hydroxide, tris(tert-butylphenyl)sulfonium hydroxide, bis(tert-butylphenyl)sulfonium hydroxide, benzoylthiophene hydroxide, and 2-oxopropylthiophene hydroxide. Compounds having a carboxylic acid onium structure are compounds in which the anionic portion of a compound having a hydroxide onium structure is converted into a carboxylic acid ester, such as acetate esters, adamantane-1-carboxylic acid esters, and perfluoroalkyl carboxylic acid esters. Compounds having a trialkylamine structure include, for example, tri(n-butyl)amine and tri(n-octyl)amine. Aniline compounds include, for example, 2,6-diisopropylaniline, N,N-dimethylaniline, N,N-dibutylaniline, and N,N-dihexylaniline. Alkylamine derivatives having a hydroxyl group and / or an ether bond include, for example, ethanolamine, diethanolamine, triethanolamine, tri(methoxyethoxyethyl)amine, and "(HO-C2H4-O-C2H4)2N(-C3H6-O-CH3)". Aniline derivatives having a hydroxyl group and / or an ether bond include, for example, N,N-bis(hydroxyethyl)aniline.

[1036] As basic compounds, amine compounds having a phenoxy group and ammonium salt compounds having a phenoxy group are preferred examples.

[1037] As amine compounds, primary, secondary, and tertiary amine compounds can be used, with amine compounds having at least one alkyl group bonded to a nitrogen atom being preferred. Tertiary amine compounds are more preferred. In amine compounds, as long as at least one alkyl group (preferably having 1 to 20 carbon atoms) is bonded to a nitrogen atom, cycloalkyl groups (preferably having 3 to 20 carbon atoms) or aryl groups (preferably having 6 to 12 carbon atoms) may also be bonded to a nitrogen atom in addition to alkyl groups.

[1038] Furthermore, the amine compound preferably has an oxidized alkenyl group. The number of oxidized alkenyl groups within the molecule is preferably 1 or more, more preferably 3 to 9, and even more preferably 4 to 6.

[1039] Among the oxidized alkenyl groups, oxyvinyl (-CH2CH2O-) or oxypropylene (-CH(CH3)CH2O- or CH2CH2CH2O-) is preferred, and oxyvinyl is more preferred.

[1040] Examples of ammonium salt compounds include primary, secondary, tertiary, and quaternary ammonium salt compounds, with at least one alkyl group bonded to a nitrogen atom being preferred. In ammonium salt compounds, if at least one alkyl group (preferably with 1 to 20 carbon atoms) is bonded to a nitrogen atom, then in addition to the alkyl group, cycloalkyl groups (preferably with 3 to 20 carbon atoms) or aryl groups (preferably with 6 to 12 carbon atoms) may also be bonded to the nitrogen atom.

[1041] The ammonium salt compound preferably has an oxidized alkenyl group. The number of oxidized alkenyl groups in the molecule is preferably 1 or more, more preferably 3 to 9, and even more preferably 4 to 6. Among the oxidized alkenyl groups, oxyvinyl (-CH2CH2O-) or oxypropylene (-CH(CH3)CH2O- or CH2CH2CH2O-) is preferred, and oxyvinyl is even more preferred.

[1042] Examples of anions that can be used as anions in ammonium salt compounds include halogen atoms, sulfonates, borates, and phosphates, with halogen atoms or sulfonates being preferred. Halogen atoms are preferably chlorine, bromine, or iodine atoms.

[1043] The sulfonate is preferably an organic sulfonate having 1 to 20 carbon atoms. Examples of organic sulfonates include alkyl sulfonates and aryl sulfonates having 1 to 20 carbon atoms. The alkyl group of the alkyl sulfonate may have substituents, such as fluorine, chlorine, bromine, alkoxy, acyl, and aromatic cyclic groups. Examples of alkyl sulfonates include methane sulfonates, ethane sulfonates, butane sulfonates, hexane sulfonates, octane sulfonates, benzyl sulfonates, trifluoromethane sulfonates, pentafluoroethane sulfonates, and nonafluorobutane sulfonates. Examples of aryl sulfonates include phenylcycloyl, naphthyl, and anthracene cycloyl groups. The substituents that the phenylcycloyl, naphthyl, and anthracene cycloyl groups may have are preferably straight-chain or branched alkyl groups having 1 to 6 carbon atoms or cycloalkyl groups having 3 to 6 carbon atoms. Examples of linear or branched alkyl and cycloalkyl groups include methyl, ethyl, n-propyl, isopropyl, n-butyl, isobutyl, tert-butyl, n-hexyl, and cyclohexyl. Other substituents include alkoxy groups, halogen atoms, cyano, nitro, acyl, and acyloxy groups having 1 to 6 carbon atoms.

[1044] Amine compounds with phenoxy groups and ammonium salt compounds with phenoxy groups refer to compounds in which a phenoxy group is located at the end of the alkyl group opposite to the nitrogen atom.

[1045] Examples of substituents for phenoxy groups include alkyl, alkoxy, halogen, cyano, nitro, carboxylic acid, carboxylic acid ester, sulfonate, aryl, aralkyl, acyloxy, and aryloxy groups. The substituent position can be any one of the 2 to 6 positions. The number of substituents can be any one of the 1 to 5.

[1046] Preferably, at least one oxidized alkenyl group is present between the phenoxy group and the nitrogen atom. The number of oxidized alkenyl groups in the molecule is preferably 1 or more, more preferably 3 to 9, and even more preferably 4 to 6. Among the oxidized alkenyl groups, oxyvinyl (-CH2CH2O-) or oxypropylene (-CH(CH3)CH2O- or CH2CH2CH2O-) is preferred, and oxyvinyl is even more preferred.

[1047] Amine compounds having a phenoxy group are obtained by heating a primary or secondary amine having a phenoxy group and a haloalkyl ether to react, then adding an aqueous solution of a strong base (e.g., sodium hydroxide, potassium hydroxide, and tetraalkylammonium) to the reaction system, and further extracting the reaction product using an organic solvent (e.g., ethyl acetate and chloroform). Alternatively, they are obtained by heating a primary or secondary amine and a haloalkyl ether having a terminal phenoxy group to react, then adding an aqueous solution of a strong base to the reaction system, and further extracting the reaction product using an organic solvent.

[1048] (A compound (PA) is produced that has a proton acceptor functional group and is decomposed by photochemical rays or radiation, thereby reducing, eliminating, or changing from a proton acceptor to an acidic state.)

[1049] The resist composition, as an acid diffusion control agent, may contain a compound (hereinafter also referred to as "compound (PA)") that produces a proton acceptor functional group and decomposes upon irradiation with photochemical rays or radiation, thereby reducing or eliminating proton acceptor properties or transforming from proton acceptor properties to acidic properties.

[1050] A proton acceptor functional group is a functional group that has a group or electrons capable of electrostatically interacting with a proton. For example, it represents a functional group having the structure of a macrocyclic compound such as a cyclic polyether, or a functional group having a nitrogen atom with an unshared electron pair that does not contribute to π-conjugation. A nitrogen atom with an unshared electron pair that does not contribute to π-conjugation is, for example, a nitrogen atom having a partial structure shown in the following general formula.

[1051] [Chemical Formula 80]

[1052] Unshared electron pairs

[1053] Preferred partial structures for proton acceptor functional groups include, for example, crown ether structures, azacrown ether structures, primary amine structures, secondary amine structures, tertiary amine structures, pyridine structures, imidazole structures, and pyrazine structures.

[1054] Compound (PA) can decompose upon exposure to photochemical rays or radiation, thereby reducing or eliminating its proton acceptor property, or transforming it from proton acceptor to acidic. Here, the reduction or elimination of proton acceptor property, or the change from proton acceptor to acidic, is due to the change in proton acceptor property caused by the addition of a proton to a proton acceptor functional group. Specifically, this refers to the decrease in the equilibrium constant of the chemical equilibrium when a compound (PA) with a proton acceptor functional group forms a proton adduct.

[1055] As compounds (PA), for example, those described in paragraphs

[0421] to

[0428] of Japanese Patent Application Publication No. 2014-41328 and paragraphs

[0108] to

[0116] of Japanese Patent Application Publication No. 2014-134686 are included in this specification.

[1056] Low-molecular-weight compounds having a nitrogen atom and a group that can be removed by the action of an acid can also be used as acid diffusion control agents. Preferably, these low-molecular-weight compounds are amine derivatives having a group on the nitrogen atom that can be removed by the action of an acid.

[1057] The groups that are removed by the action of acid are preferably acetal, carbonate, carbamate, tertiary ester, tertiary hydroxyl, or hemiacetal ether, more preferably carbamate or hemiacetal ether.

[1058] The molecular weight of the low molecular weight compound is preferably 100 to 1000, more preferably 100 to 700, and even more preferably 100 to 500.

[1059] Low molecular weight compounds can also have urethane groups with a protecting group on the nitrogen atom.

[1060] The following are specific examples of acid diffusion control agents, but the present invention is not limited thereto.

[1061] [Chemical Formula 81]

[1062]

[1063] [Chemical Formula 82]

[1064]

[1065] [Chemical Formula 83]

[1066]

[1067] [Chemical Formula 84]

[1068]

[1069] [Chemical Formula 85]

[1070]

[1071] When the resist composition contains an acid diffusion control agent, the content of the acid diffusion control agent is preferably 0.001 to 15% by mass, more preferably 0.01 to 8% by mass, relative to the total solid content of the resist composition.

[1072] Acid diffusion control agents can be used alone or in combination with two or more.

[1073] Furthermore, when the resist composition contains a specific compound having an anion represented by any one of formulas (d1-1) to (d1-3) and / or other photoacid generators having an anion represented by any one of formulas (d1-1) to (d1-3) (hereinafter, they are also collectively referred to as "d1-type photoacid generators"), the d1-type photoacid generators can also function as acid diffusion control agents. When the resist composition contains a d1-type photoacid generator, it is also preferable that the resist composition does not actually contain an acid diffusion control agent. Here, "does not actually contain an acid diffusion control agent" means that the content of the acid diffusion control agent is 5% by mass or less relative to the total content of the d1-type photoacid generators.

[1074] Furthermore, when the resist composition contains both a d1-type photoacid generator and an acid diffusion control agent, their combined content is preferably 1 to 30% by mass, more preferably 3 to 20% by mass.

[1075] The preferred ratio of photoacid generator to acid diffusion control agent in the resist composition is 2.0 to 300 (molar ratio). From the viewpoint of sensitivity and resolution, a molar ratio of 2.0 or higher is preferred; from the viewpoint of suppressing the reduction in resolution caused by the coarsening of the resist pattern over time from exposure to heat treatment, a molar ratio of 300 or lower is preferred. A more preferred molar ratio is 2.0 to 200, and even more preferred is 2.0 to 150.

[1076] As acid diffusion control agents, examples include compounds described in paragraphs

[0140] to

[0144] of Japanese Patent Application Publication No. 2013-011833 (amine compounds, amide-containing compounds, urea compounds, and nitrogen-containing heterocyclic compounds, etc.).

[1077] <Hydrophobic resin>

[1078] In addition to the resin (A) described above, the resist composition may also contain a hydrophobic resin different from resin (A).

[1079] Hydrophobic resins are preferably designed to be biased towards the surface of the resist film, but unlike surfactants, they do not necessarily need to have hydrophilic groups in the molecule, nor do they need to contribute to the uniform mixing of polar and non-polar substances.

[1080] As an example of the effects of adding hydrophobic resin, the control of the static and dynamic contact angle of the resist film surface with respect to water and the suppression of outgassing can be cited.

[1081] From the viewpoint of favoring the surface layer of the film, the hydrophobic resin preferably has one or more of the following: "fluorine atoms", "silicon atoms", and "CH3 moiety contained in the side chain portion of the resin", more preferably two or more. Furthermore, the hydrophobic resin preferably has a hydrocarbon group with five or more carbon atoms. These groups may be present in the main chain of the resin or may be substituted by the side chain.

[1082] When a hydrophobic resin contains fluorine atoms and / or silicon atoms, the aforementioned fluorine atoms and / or silicon atoms in the hydrophobic resin may be contained in the main chain of the resin or in the side chain.

[1083] When the hydrophobic resin contains fluorine atoms, the fluorine-containing portion of the structure is preferably an alkyl group, a cycloalkyl group, or an aryl group.

[1084] The alkyl group having fluorine atoms (preferably having 1 to 10 carbon atoms, more preferably having 1 to 4 carbon atoms) is a straight-chain or branched alkyl group in which at least one hydrogen atom is replaced by a fluorine atom, and may also have substituents other than fluorine atoms.

[1085] A cycloalkyl group having a fluorine atom is a monocyclic or polycyclic cycloalkyl group in which at least one hydrogen atom is replaced by a fluorine atom, and may also have substituents other than a fluorine atom.

[1086] As an aryl group having a fluorine atom, examples include aryl groups such as phenyl and naphthyl in which at least one hydrogen atom is replaced by a fluorine atom, and it may also have substituents other than a fluorine atom.

[1087] As a repeating unit having fluorine or silicon atoms, for example, the repeating unit illustrated in paragraph

[0519] of US2012 / 0251948A1 can be cited.

[1088] Furthermore, as described above, it is preferable that the hydrophobic resin contains a CH3 moiety in the side chain portion.

[1089] Here, the CH3 moiety structure of the side chain portion in the hydrophobic resin includes the CH3 moiety structure of ethyl and propyl groups.

[1090] On the other hand, methyl groups (e.g., α-methyl groups with repeating units of methacrylic acid structure) that are directly bonded to the main chain of the hydrophobic resin contribute little to the surface segregation of the hydrophobic resin due to the influence of the main chain, and are therefore not included in the CH3 part structure of this invention.

[1091] Hydrophobic resins may also contain repeating units with acid-degradable groups.

[1092] Regarding hydrophobic resins, please refer to paragraphs

[0348] to

[0415] of Japanese Patent Application Publication No. 2014-010245, which are included in this application specification.

[1093] In addition, the hydrophobic resin may preferably be the resin described in Japanese Patent Application Publication No. 2011-248019, Japanese Patent Application Publication No. 2010-175859 and Japanese Patent Application Publication No. 2012-032544.

[1094] The following shows preferred examples of monomers that correspond to the repeating units constituting the hydrophobic resin.

[1095] [Chemical Formula 86]

[1096]

[1097] [Chemical Formula 87]

[1098]

[1099] When the resist composition contains a hydrophobic resin, the content of the hydrophobic resin is preferably 0.01 to 20% by mass, more preferably 0.1 to 15% by mass, relative to the total solid content of the resist composition.

[1100] <surfactants>

[1101] The resist composition may also contain surfactants. If surfactants are present, patterns with better adhesion and fewer development defects can be formed.

[1102] The surfactant is preferably a fluorinated and / or silicone surfactant.

[1103] As fluorinated and / or silicone surfactants, examples include those described in paragraph

[0276] of U.S. Patent Application Publication No. 2008 / 0248425. Furthermore, it can use Eftop EF301 or EF303 (manufactured by Shin-Akita Kasei Co., Ltd.); Fluorad FC430, 431, and 4430 (manufactured by Sumitomo 3MLimited); Megaface F171, F173, F176, F189, F113, F110, F177, F120, and R08 (manufactured by DICCORPORATION); Surflon S-382, SC101, 102, 103, 104, 105, or 106 (manufactured by ASAHI GLASS CO.,LTD.); TroySol S-366 (manufactured by Troy Chemical Industries Inc.); GF-300 or GF-150 (manufactured by Toagosei Chemical Co., Ltd.); and Surflon S-393 (manufactured by SEIMI). (Manufactured by CHEMICALCO.,LTD.); Eftop EF121, EF122A, EF122B, RF122C, EF125M, EF135M, EF351, EF352, EF801, EF802 or EF601 (manufactured by Gemco Co.,Ltd.); PF636, PF656, PF6320 and PF6520 (manufactured by OMNOVA Solutions Inc.); KH-20 (manufactured by Asahi Kasei Corporation); FTX-204G, 208G, 218G, 230G, 204D, 208D, 212D, 218D and 222D (manufactured by Neos Corporation). Additionally, as a silicone surfactant, the polysiloxane polymer KP-341 (manufactured by Shin-Etsu Chemical Co.,Ltd.) can also be used.

[1104] Furthermore, in addition to the known surfactants described above, surfactants can also be synthesized using fluorinated aliphatic compounds manufactured by telomerization (also known as short-chain polymer telomerization) or oligomerization (also known as oligomerization). Specifically, polymers possessing fluorinated aliphatic groups derived from the fluorinated aliphatic compound can be used as surfactants. These fluorinated aliphatic compounds can be synthesized using, for example, the method described in Japanese Patent Application Publication No. 2002-090991.

[1105] Furthermore, surfactants other than those of fluorine and / or silicon as described in paragraph

[0280] of U.S. Patent Application Publication No. 2008 / 0248425 may also be used.

[1106] These surfactants can be used alone or in combination with two or more.

[1107] When the resist composition contains a surfactant, the surfactant content is preferably 0.0001 to 2% by mass, more preferably 0.0005 to 1% by mass, relative to the total solid content of the composition.

[1108] <Other Additives>

[1109] The resist composition may further comprise a dissolution-inhibiting compound, a dye, a plasticizer, a photosensitizer, a light absorber, and / or a compound that promotes solubility in the developer (e.g., a phenolic compound with a molecular weight of less than 1000 or an alicyclic or aliphatic compound containing a carboxylic acid group).

[1110] The resist composition may further include a dissolution-inhibiting compound. Here, "dissolution-inhibiting compound" refers to a compound with a molecular weight of less than 3000 that decomposes under the action of acid and has reduced solubility in organic developers.

[1111] [Resist film and pattern formation method]

[1112] The steps of the pattern forming method using the above-described resist composition are not particularly limited, but the following steps are preferred.

[1113] Step 1: A step of forming a resist film on a substrate using a resist composition.

[1114] Step 2: The process of exposing the resist film.

[1115] Step 3: The process of developing the exposed resist film with a developing solution to form a pattern.

[1116] The steps of each of the above processes will be explained in detail below.

[1117] <Process 1: Resist Film Formation Process>

[1118] Step 1 is a step of forming a resist film on a substrate using a resist composition.

[1119] The definition of the resist composition is as described above.

[1120] As a method for forming a resist film on a substrate using a resist composition, one example is the method of coating the resist composition onto the substrate.

[1121] Furthermore, it is preferable to filter the resist composition as needed before coating. The pore size of the filter is preferably 0.1 μm or less, more preferably 0.05 μm or less, and even more preferably 0.03 μm or less. The filter is preferably made of polytetrafluoroethylene, polyethylene, or nylon.

[1122] The photoresist composition can be applied to substrates (e.g., silicon, silicon dioxide coatings) used in the manufacture of integrated circuit components using a suitable coating method such as a spin coater or a coating machine. Spin coating using a spin coater is preferred. The rotation speed when performing spin coating using a spin coater is preferably 1000–3000 rpm.

[1123] A resist film can be formed by drying the substrate after coating the resist composition. Additionally, various substrate films (inorganic films, organic films, anti-reflective films) can be formed under the resist film as needed.

[1124] As a drying method, drying by heating can be cited as an example. Heating can be carried out using devices found in general exposure machines and / or developing machines, or by using hot plates or the like. The heating temperature is preferably 80 to 150°C, more preferably 80 to 140°C, and even more preferably 80 to 130°C. The heating time is preferably 30 to 1000 seconds, more preferably 60 to 800 seconds, and even more preferably 60 to 600 seconds.

[1125] There is no particular limitation on the thickness of the resist film, but from the viewpoint of being able to form finer patterns with higher precision, it is preferably 10 to 65 nm, and more preferably 15 to 50 nm.

[1126] Alternatively, a topcoat composition can be used to form a topcoat layer on top of the resist film.

[1127] The preferred topcoat composition can be applied more evenly to the top layer of the resist film without mixing with it.

[1128] Topcoat compositions may include, for example, resins, additives, and solvents.

[1129] As the resin described above, the same resin as the hydrophobic resin described above can be used. The resin content is preferably 50 to 99.9% by mass, more preferably 60 to 99.7% by mass, relative to the total solids content of the topcoat composition.

[1130] As the aforementioned additives, the acid diffusion control agent and d1-type photoacid generator can be used. Furthermore, compounds having radical scavenging groups, such as those containing N-oxygen radicals, can also be used. Examples of such compounds include [4-(benzoyloxy)-2,2,6,6-tetramethylpiperidinoxy] radical. The additive content is preferably 0.01 to 20% by mass, more preferably 0.1 to 15% by mass, relative to the total solids content of the topcoat composition.

[1131] The solvents mentioned above preferably do not dissolve the resist film. Examples include alcohol solvents (4-methyl-2-pentanol, etc.), ether solvents (diisopentyl ether, etc.), ester solvents, fluorine solvents, and hydrocarbon solvents (n-decane, etc.).

[1132] The solvent content in the topcoat composition is preferably set to a solid component concentration of 0.5 to 30% by mass, more preferably 1 to 20% by mass.

[1133] Furthermore, in addition to the additives mentioned above, the topcoat composition may also contain a surfactant. The surfactant can be any surfactant that can be included in the composition of the present invention. The surfactant content is preferably 0.0001 to 2% by mass, more preferably 0.0005 to 1% by mass, relative to the total solids content of the topcoat composition.

[1134] Furthermore, there are no particular limitations on the top coating, and conventional top coatings can be formed by conventionally known methods. For example, the top coating can be formed based on the content described in paragraphs

[0072] to

[0082] of Japanese Patent Application Publication No. 2014-059543.

[1135] For example, it is preferable to form a top coating containing an alkaline compound, such as that described in Japanese Patent Application Publication No. 2013-061648, on the resist film. Specific examples of alkaline compounds that the top coating may contain include alkaline compounds that the resist composition may contain.

[1136] Furthermore, the top coating preferably contains a compound that includes at least one group or bond selected from ether bonds, thioether bonds, hydroxyl groups, thiols, carbonyl bonds, and ester bonds.

[1137] <Process 2: Exposure Process>

[1138] Step 2 is the process of exposing the resist film.

[1139] As an example of exposure method, one could irradiate the formed resist film with EUV light through a prescribed mask.

[1140] It is preferable to bake (heat) the exposed area after exposure and before development. Baking promotes the reaction of the exposed part, and the sensitivity and pattern shape become better.

[1141] The heating temperature is preferably 80-150°C, more preferably 80-140°C, and even more preferably 80-130°C.

[1142] The heating time is preferably 10 to 1000 seconds, more preferably 10 to 180 seconds, and even more preferably 30 to 120 seconds.

[1143] Heating can be achieved using devices found in general exposure machines and / or developing machines, or by using hot plates or the like.

[1144] This process is also known as post-exposure baking.

[1145] <Process 3: Development Process>

[1146] Step 3 is the process of developing the exposed resist film with a developing solution to form a pattern.

[1147] The developer can be an alkaline developer or a developer containing organic solvents (hereinafter also referred to as "organic developer").

[1148] Examples of development methods include: immersing the substrate in a tank filled with developer for a certain time (dip method); developing the substrate by causing the developer to bulge on the substrate surface through surface tension and then allowing it to stand for a certain time (puddle method); spraying developer onto the substrate surface (spray method); and continuously dispensing developer onto a substrate rotating at a certain speed while scanning the developer nozzle at a certain speed (dynamic dispense method).

[1149] Furthermore, after the developing process, a process can be implemented where the developing process is stopped while the solvent is being replaced with another solvent.

[1150] There are no particular limitations as long as the development time is the time it takes for the resin in the unexposed area to fully dissolve. It is preferably 10 to 300 seconds, and more preferably 20 to 120 seconds.

[1151] The temperature of the developer is preferably 0–50°C, and more preferably 15–35°C.

[1152] Alkaline developers preferably use aqueous solutions containing alkali. There are no particular limitations on the type of alkaline solution; examples include aqueous solutions containing quaternary ammonium salts (e.g., tetramethylammonium hydroxide), inorganic bases, primary amines, secondary amines, tertiary amines, alkanolamines, or cyclic amines. Among these, aqueous solutions containing quaternary ammonium salts, such as tetramethylammonium hydroxide (TMAH), are preferred. Appropriate amounts of alcohols and surfactants may be added to the alkaline developer. The alkali concentration of the alkaline developer is typically 0.1–20% by mass. Furthermore, the pH of the alkaline developer is typically 10.0–15.0.

[1153] Organic developer solutions are preferably developer solutions containing at least one organic solvent selected from ketone solvents, ester solvents, alcohol solvents, amide solvents, ether solvents and hydrocarbon solvents.

[1154] Examples of ketone solvents include 1-octanone, 2-octanone, 1-nonanone, 2-nonanone, acetone, 2-heptanone (methyl pentyl ketone), 4-heptanone, 1-hexanone, 2-hexanone, diisobutyl ketone, cyclohexanone, methyl cyclohexanone, phenyl acetone, methyl ethyl ketone, methyl isobutyl ketone, acetylacetone, acetone-based acetone, ionone, diacetonyl alcohol, acetyl alcohol, acetoethyl alcohol, acetophenone, methyl naphthyl ketone, isophorone, and propylene carbonate.

[1155] Examples of ester solvents include methyl acetate, butyl acetate, ethyl acetate, isopropyl acetate, amyl 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 butanoate, methyl 2-hydroxyisobutyrate, isobutyl isobutyrate, and butyl propionate.

[1156] As an alcohol solvent, amide solvent, ether solvent, and hydrocarbon solvent, the solvents disclosed in paragraphs

[0715] to

[0718] of the specification published in U.S. Patent Application Publication No. 2016 / 0070167A1 can be used, for example.

[1157] It can be mixed with various of the above-mentioned solvents, or with solvents other than those mentioned above, or with water. The water content of the developer as a whole is preferably less than 50% by mass, more preferably less than 20% by mass, even more preferably less than 10% by mass, and especially preferably virtually free of water.

[1158] Relative to the total amount of developer, the content of organic solvent in organic developer is preferably 50% by mass or more and 100% by mass or less, more preferably 80% by mass or more and 100% by mass or less, even more preferably 90% by mass or more and 100% by mass or less, and particularly preferably 95% by mass or more and 100% by mass or less.

[1159] <Other Processes>

[1160] The above pattern forming method preferably includes a cleaning step using a rinsing solution after step 3.

[1161] As a rinsing solution used in the rinsing process following the development process using an alkaline developer, pure water can be an example. Additionally, an appropriate amount of surfactant can be added to the pure water.

[1162] An appropriate amount of surfactant can be added to the rinsing solution.

[1163] In the rinsing process following the developing step using an organic developer, there are no particular restrictions on the rinsing solution used, as long as it does not dissolve the pattern; solutions containing common organic solvents can be used. Preferably, the rinsing solution contains at least one organic solvent selected from hydrocarbon solvents, ketone solvents, ester solvents, alcohol solvents, amide solvents, and ether solvents.

[1164] Examples of hydrocarbon solvents, ketone solvents, ester solvents, alcohol solvents, amide solvents, and ether solvents include solvents that are the same as those described in the developing solution containing organic solvents.

[1165] There are no particular limitations on the rinsing process. For example, methods such as continuously spraying rinsing liquid onto a substrate rotating at a certain speed (spin coating), immersing the substrate in a tank filled with rinsing liquid for a certain time (immersion method), and spraying rinsing liquid onto the substrate surface (spraying method) can be used.

[1166] Furthermore, the pattern forming method of the present invention may include a post-bake step after the rinsing step. This step removes the developer and rinsing solution remaining between and inside the pattern after baking. This step also smooths the resist pattern and improves the surface roughness of the pattern. The post-rinsing step is typically performed at 40–250°C (preferably 90–200°C) for 10 seconds to 3 minutes (preferably 30 to 120 seconds).

[1167] Furthermore, the formed pattern can be used as a mask to perform etching on the substrate. That is, the pattern formed in step 3 can also be used as a mask to form a pattern on the substrate by processing the substrate (or the lower film and the substrate).

[1168] The processing method of the substrate (or the lower film and substrate) is not particularly limited. Preferred method is to form a pattern on the substrate by using the pattern formed in step 3 as a mask and performing dry etching on the substrate (or the lower film and substrate).

[1169] Dry etching can be a single-stage etching process or an etching process consisting of multiple stages. When etching consists of multiple stages, the etching processes in each stage can be the same or different.

[1170] Etching can be performed using any known method, with various conditions appropriately determined according to the type or application of the substrate. For example, etching can also be performed according to the minutes of the International Society for Optical Engineering (SPIE) Proc. 6924, 692420 (2008) and Japanese Patent Application Publication No. 2009-267112. Furthermore, the method described in Chapter 4, Etching, of the "Semiconductor Process Textbook 4th Edition, 2007, Publisher: SEMI Japan" can also be used.

[1171] Dry etching is preferably oxygen plasma etching.

[1172] The various materials used in the resist composition and the pattern forming method of the present invention (e.g., solvents, developers, rinsing solutions, antireflective film forming compositions, topcoat forming compositions, etc.) preferably do not contain impurities such as metals. The content of impurities contained in these materials is preferably 1 ppm by mass or less, more preferably 10 ppb by mass or less, further preferably 100 ppt by mass or less, particularly preferably 10 ppt by mass or less, and most preferably 1 ppt by mass or less. Examples of metallic impurities include, for instance, Na, K, Ca, Fe, Cu, Mg, Al, Li, Cr, Ni, Sn, Ag, As, Au, Ba, Cd, Co, Pb, Ti, V, W, and Zn.

[1173] As a method for removing impurities such as metals from various materials, filtration using a filter can be cited as an example. The filter pore size is preferably less than 100 nm, more preferably less than 10 nm, and even more preferably less than 5 nm. The filter is preferably made of polytetrafluoroethylene, polyethylene, or nylon. The filter can be constructed from a composite material combining the aforementioned filter raw materials and ion exchange media. The filter can be a filter that has been pre-cleaned with an organic solvent. In the filter filtration process, multiple filters can be connected in series or in parallel. When using multiple filters, filters with different pore sizes and / or materials can be used in combination. Furthermore, various materials can be filtered multiple times; the multiple filtration process can be a circulating filtration process.

[1174] In the manufacture of the photoresist composition, it is preferable to dissolve various components such as the resin and photoacid generator in a solvent, and then perform circulating filtration using multiple filters made from different raw materials. For example, it is preferable to sequentially connect a polyethylene filter with a pore size of 50 nm, a nylon filter with a pore size of 10 nm, and a polyethylene filter with a pore size of 3 nm, and perform circulating filtration more than 10 times. The smaller the pressure difference between the filters, the better; typically it is 0.1 MPa or less, preferably 0.05 MPa or less, and more preferably 0.01 MPa or less. The smaller the pressure difference between the filter and the filling nozzle, the better; typically it is 0.5 MPa or less, preferably 0.2 MPa or less, and more preferably 0.1 MPa or less.

[1175] Preferably, the interior of the apparatus for manufacturing the resist composition is purged with an inert gas such as nitrogen. This prevents reactive gases such as oxygen from dissolving into the resist composition.

[1176] The resist composition is filtered and then filled into a clean container. Preferably, the resist composition filled in the container is refrigerated. This suppresses performance degradation over time. The shorter the time from the completion of filling the container to the start of refrigeration, the better, typically within 24 hours, preferably within 16 hours, more preferably within 12 hours, and even more preferably within 10 hours. The storage temperature is preferably 0–15°C, more preferably 0–10°C, and even more preferably 0–5°C.

[1177] Furthermore, as methods to reduce impurities such as metals contained in various materials, examples include selecting raw materials with low metal content as the constituent materials, filtering the raw materials that constitute the various materials, and distilling under conditions that suppress contamination as much as possible by lining the device with Teflon (registered trademark).

[1178] Besides filtration, impurities can be removed by adsorption materials, and filtration and adsorption materials can be used in combination. Known adsorption materials can be used, such as inorganic adsorption materials like silica gel and zeolite, and organic adsorption materials like activated carbon. To reduce impurities such as metals contained in these materials, it is necessary to prevent the introduction of metal impurities during the manufacturing process. Whether metal impurities have been adequately removed from the manufacturing apparatus can be confirmed by measuring the metal content in the cleaning solution used during cleaning of the manufacturing apparatus. The metal content in the used cleaning solution is preferably 100 parts per trillion (ppt), more preferably 10 ppt, and even more preferably 1 ppt.

[1179] To prevent malfunctions in the chemical solution piping and various components (filters, O-rings, hoses, etc.) caused by static electricity and subsequent electrostatic discharge, conductive compounds can be added to organic processing solutions such as rinsing solutions. There are no particular limitations on the conductive compounds; methanol is an example. The amount added is not particularly limited, but from the viewpoint of maintaining preferred developing or rinsing characteristics, it is preferably 10% by mass or less, more preferably 5% by mass or less.

[1180] For pharmaceutical piping, various pipes coated with antistatic-treated polyethylene, polypropylene, or fluoropolymers (such as polytetrafluoroethylene or perfluoroalkoxy resins) can be used. Similarly, filters and O-rings can also be made of antistatic-treated polyethylene, polypropylene, or fluoropolymers (such as polytetrafluoroethylene or perfluoroalkoxy resins).

[1181] The method for improving the surface roughness of a pattern formed by the method of the present invention can also be applied. For example, the method disclosed in International Patent Publication No. 2014 / 002808, which involves processing the pattern with plasma containing hydrogen gas, can be cited. In addition, known methods such as those described in Japanese Patent Application Publication No. 2004-235468, U.S. Patent Application Publication No. 2010 / 0020297, Japanese Patent Application Publication No. 2008-083384, and Proc. of SPIE Vol. 8328 83280N-1 “EUV Resist Curing Technique for LWR Reduction and Etch Selectivity Enhancement” can also be cited.

[1182] When the formed pattern is linear, the aspect ratio obtained by dividing the pattern height by the line width is preferably 2.5 or less, more preferably 2.1 or less, and even more preferably 1.7 or less.

[1183] When the formed pattern is a groove pattern or a contact hole pattern, the aspect ratio obtained by dividing the pattern height by the groove width or hole diameter is preferably 4.0 or less, more preferably 3.5 or less, and even more preferably 3.0 or less.

[1184] The patterning method of the present invention can also be used for guided patterning in DSA (Directed Self-Assembly) (e.g., see ACS Nano Vol.4 No.8 4815-4823).

[1185] Furthermore, the pattern formed by the above method can be used as the core material in the spacer process disclosed in, for example, Japanese Patent Application Publication No. 3-270227 and Japanese Patent Application Publication No. 2013-164509.

[1186] Furthermore, the present invention relates to a method for manufacturing an electronic device including the above-described pattern forming method, and to an electronic device manufactured by the same method.

[1187] The electronic device of the present invention is an electronic device that is suitably mounted on electrical and electronic equipment (home appliances, OA (Office Automation), media-related equipment, optical equipment, and communication equipment, etc.).

[1188] Example

[1189] The present invention will now be described in further detail with reference to embodiments. The materials, amounts, proportions, processing contents, and processing steps shown in the following embodiments can be appropriately modified without departing from the spirit of the invention. Therefore, the scope of the present invention should not be construed as limited to the embodiments shown below.

[1190] [Preparation of photosensitive or radiosensitive linear resin compositions]

[1191] The following shows the components and manufacturing steps of the photosensitive radioactive or radiosensitive linear resin composition (hereinafter also referred to as "resist composition") used in the examples or comparative examples.

[1192] <Photo-acid generators (specific compounds and comparative compounds)>

[1193] (Synthesis of a specific compound X-1)

[1194] The specific compound X-1 was synthesized according to the following scheme.

[1195] [Chemical Formula 88]

[1196]

[1197] Magnesium (18.0 g) was added to tetrahydrofuran (500 mL) to obtain a mixture. 4-Bromotrifluorotoluene (151.5 g) was added dropwise to the obtained mixture. The mixture was then stirred for 1 hour to prepare Grignard reagent X-1-1. Thionyl chloride (37.7 g) was added to tetrahydrofuran (500 mL) to obtain a mixture. The obtained mixture was cooled to 0 °C, and the previously prepared Grignard reagent X-1-1 was added dropwise to the mixture. After stirring the mixture for 1 hour, 1 N hydrochloric acid (600 mL) was added to the mixture while maintaining the temperature at 0 °C. The reaction product generated in the mixture was extracted with ethyl acetate (600 mL). The obtained organic phase was washed with a saturated aqueous sodium bicarbonate solution (500 mL) and water (500 mL), and then the solvent was removed by distillation from the organic phase. The concentrate was washed with hexane (300 mL) and filtered to obtain X-1-A (60 g) (yield 56%).

[1198] [Chemical Formula 89]

[1199]

[1200] X-1-A (30.0 g) was added to a mixture of phosphorus pentoxide (6.8 g) and methanesulfonic acid (90.8 g). After cooling the resulting mixture to 10 °C, 2,6-dimethylphenol (11.9 g) was added and the mixture was stirred at 20 °C for 30 minutes. The resulting mixture was heated to 50 °C and stirred further for 3 hours, after which water (300 mL) was added dropwise below 20 °C. Extraction was performed with dichloromethane (300 mL), the organic phase was washed with water (300 mL), and the solvent was removed by distillation. The concentrate was crystallized with ethyl acetate (300 mL), and X-1-B (35 g) was obtained by filtration (yield 73%).

[1201] [Chemical Formula 90]

[1202]

[1203] 7.9 g of tert-butyl-2-bromoacetate, 18.2 g of cesium carbonate, and 174 g of dimethylacetamide were added to X-1-B (20.0 g), and the mixture was stirred at 40 °C for 2 hours. The resulting mixture was cooled to room temperature, filtered, and then 150 g of dichloromethane was added. The mixture was washed twice with 1 N hydrochloric acid (100 mL). The organic phase was then washed twice with water (100 mL), and the solvent was removed by distillation. The concentrate was crystallized with diisopropyl ether (200 mL) and filtered to obtain X-1-C (19 g) (78% yield).

[1204] [Chemical Formula 91]

[1205]

[1206] After mixing dichloromethane (100 mL) and water (100 mL), X-1-2 (5.0 g) and X-1-C (8.0 g) were added. After stirring for 1 hour, the aqueous layer was removed, and the organic phase was washed with 1% potassium carbonate aqueous solution (100 mL), 0.1 N hydrochloric acid (100 mL), and water (100 mL). X-1 (10.3 g) was obtained by removing the solvent by distillation (yield 95%).

[1207] Following the synthetic method described above, specific compounds X-2 to X-29 of the examples were synthesized. They are shown below.

[1208] [Chemical Formula 92]

[1209]

[1210] [Chemical Formula 93]

[1211]

[1212] [Chemical Formula 94]

[1213]

[1214]

[1215] [Chemical Formula 95]

[1216]

[1217] [Chemical Formula 96]

[1218]

[1219] The following are comparative compounds Z-1 to Z-3.

[1220] [Chemical Formula 97]

[1221]

[1222] <Acid-degradable resin (resin (A))>

[1223] The following shows the acid-degradable resin (resin (A)) used in the manufacture of the resist composition. * indicates a bonding site.

[1224] [Chemical Formula 98]

[1225]

[1226] [Chemical Formula 99]

[1227]

[1228]

[1229] [Chemical Formula 100]

[1230]

[1231]

[1232] [Chemical Formula 101]

[1233]

[1234]

[1235] The molar ratios of the repeating units constituting each of the resins shown above (corresponding to A, B, C, and D from left to right), the weight-average molecular weight (Mw), and the dispersion (Mw / Mn) of each resin are shown in Table 1 below.

[1236] [Table 1]

[1237]

[1238]

[1239] The following shows photoacid-producing agents.

[1240] [Chemical Formula 102]

[1241]

[1242]

[1243]

[1244] <Acid diffusion control agent>

[1245] When the resist composition contains an acid diffusion control agent, the following acid diffusion control agent is used.

[1246] [Chemical Formula 103]

[1247]

[1248] <Hydrophobic resin>

[1249] When the resist composition contains a hydrophobic resin, a hydrophobic resin having repeating units based on the monomers described below is used.

[1250] [Chemical Formula 104]

[1251]

[1252] The molar ratio of repeating units of each monomer, the weight-average molecular weight (Mw), and the dispersion (Mw / Mn) of each resin in the hydrophobic resin used in the composition are shown in the table below.

[1253] [Table 2]

[1254]

[1255] <Preparation of the resist composition>

[1256] (Preparation of resist compositions for EUV exposure testing (Re-1~Re-32, Re-53~Re-55, Re-59~Re-71))

[1257] The components shown in the table below were mixed to a solid concentration of 2% by mass. The resulting mixture was then filtered in the following order: first through a polyethylene filter with a pore size of 50 nm, then through a nylon filter with a pore size of 10 nm, and finally through a polyethylene filter with a pore size of 5 nm, thereby preparing a resist composition for EUV-based exposure testing.

[1258] Furthermore, in the resist composition, solid components refer to all components other than the solvent. The obtained resist compositions were used in the examples and comparative examples.

[1259] In addition, in the table below, the content (mass%) of each component refers to the content relative to the total solids content.

[1260] (Preparation of resist compositions for ArF exposure testing (Re-33~Re-52, Re-56~Re-58))

[1261] The components shown in the table below were mixed to a solid concentration of 4% by mass. The resulting mixture was then filtered in the following order: first through a polyethylene filter with a pore size of 50 nm, then through a nylon filter with a pore size of 10 nm, and finally through a polyethylene filter with a pore size of 5 nm, thereby preparing a resist composition for ArF-based exposure testing.

[1262] The following shows the proportions of each resist composition.

[1263] [Table 3]

[1264]

[1265] [Table 4]

[1266]

[1267] <surfactants>

[1268] When the resist composition contains a surfactant, the following surfactant is used.

[1269] E-1: Megaface F176 (manufactured by DIC CORPORATION, a fluorinated surfactant)

[1270] E-2: Megaface R08 (manufactured by DIC CORPORATION, fluorine and silicone surfactant)

[1271] E-3: PF656 (manufactured by OMNOVA Solutions Inc., a fluorinated surfactant)

[1272] <Solvent>

[1273] The following shows the solvents contained in the resist composition.

[1274] F-1: Propylene glycol monomethyl ether acetate (PGMEA)

[1275] F-2: Propylene glycol monomethyl ether (PGME)

[1276] F-3: Propylene glycol monoethyl ether (PGEE)

[1277] F-4: Cyclohexanone

[1278] F-5: Cyclopentanone

[1279] F-6: 2-Heptanone

[1280] F-7: Ethyl lactate

[1281] F-8: γ-Butyrolactone

[1282] F-9: Propylene carbonate

[1283] [Preparation of the topcoat composition]

[1284] In this embodiment, when using the above-described resist composition to prepare the resist film, a top coating layer is further prepared on the resist film as needed.

[1285] The following shows the components and manufacturing steps used in the topcoat composition for forming the topcoat.

[1286] <Resin>

[1287] The mole fraction of repeating units based on each monomer, the weight-average molecular weight (Mw), and the dispersion (Mw / Mn) of each resin used in the topcoat composition are shown in the table below.

[1288] Additionally, the structures of the monomers corresponding to the repeating units shown in the table can be referenced to the monomers described in the above description of <Hydrophobic Resins>.

[1289] [Table 5]

[1290]

[1291] <Preparation of Top Coating Composition>

[1292] The components were dissolved in a solvent to meet the formulation requirements listed in the table below, and the concentration of the solid components was 3.8% by mass, thereby preparing a solution.

[1293] Next, the resulting solution was filtered using a polyethylene filter with a pore size of 0.1 μm to prepare the top coating compositions TC-1 to TC-3.

[1294] [Table 6]

[1295]

[1296] <Additives>

[1297] The following shows the additives contained in the topcoat composition.

[1298] [Chemical Formula 105]

[1299]

[1300] <Solvent>

[1301] The following shows the solvents contained in the topcoat composition.

[1302] FT-1: 4-Methyl-2-pentanol (MIBC)

[1303] FT-2: n-Decane

[1304] FT-3: Diisopentyl ether

[1305] 〔test〕

[1306] The LWR of patterns developed under the conditions shown below was evaluated using the resist composition prepared as described above.

[1307] <EUV exposure, organic solvent development>

[1308] (Pattern Formation)

[1309] A substrate film with a thickness of 20 nm was formed by coating a base film with the underlying film formation composition AL412 (manufactured by Brewer Science) onto a silicon wafer and baking it at 205°C for 60 seconds. A resist composition as shown in Table 6 was then coated onto the substrate and baked at 100°C for 60 seconds to form a resist film with a thickness of 30 nm.

[1310] The silicon wafer with the obtained resist film was patterned using an EUV exposure apparatus (manufactured by Exitech Corporation, Micro Exposure Tool, NA 0.3, Quadruple, outer sigma 0.68, inner sigma 0.36). Additionally, a mask with a line size of 20 nm and a line-to-space ratio of 1:1 was used as the reticle.

[1311] After the exposed resist film is baked at 90°C for 60 seconds, it is developed with n-butyl acetate for 30 seconds and then rotated to dry, thus obtaining a negative pattern.

[1312] (evaluate)

[1313] A 20nm (1:1) line and spatial pattern, analyzed for optimal exposure when resolving line patterns with an average linewidth of 20nm, was observed from the top of the pattern using a length-measuring scanning electron microscope (SEM, S-9380II manufactured by Hitachi, Ltd.). The linewidth of the pattern was observed at any point (100), and its measurement deviation was evaluated by 3σ and set as LWR. The smaller the LWR value, the better the LWR performance. When using the resist composition of the present invention, the LWR (nm) is 4.6nm or less, preferably 4.2nm or less, more preferably 3.9nm or less, and even more preferably 3.7nm or less.

[1314] [Table 7]

[1315]

[1316] (result)

[1317] As shown in Table 7, it was confirmed that when EUV exposure is performed and the pattern is obtained by developing with an organic solvent, the resist composition of the present invention can form a pattern with excellent LWR performance.

[1318] Comparisons of Examples 1-1 to 1-45 confirm that the effects of the present invention are more superior when the sulfonium cation has an acid-degrading group represented by general formula (a-1) or (a-2). Furthermore, similar comparisons confirm that the effects of the present invention are further superior when the sulfonium cation has an acid-degrading group represented by general formula (a-1).

[1319] The comparison of Examples 1-1 to 1-45 confirms that the present invention is more effective when the sulfonium cation has one acid-decomposing group.

[1320] The comparison of Examples 1-1 to 1-45 confirms that the present invention is more effective when a specific compound containing a sulfonium cation represented by the general formula (S-1) is used.

[1321] <EUV exposure, alkaline development>

[1322] (Pattern Formation)

[1323] A substrate film with a thickness of 20 nm was formed by coating a silicon wafer with an underlying film forming composition AL412 (manufactured by Brewer Science) and baking it at 205°C for 60 seconds. A resist composition as shown in Table 7 was then coated onto the substrate and baked at 100°C for 60 seconds to form a resist film with a thickness of 30 nm.

[1324] The silicon wafer with the obtained resist film was patterned using an EUV exposure apparatus (manufactured by Exitech Corporation, Micro Exposure Tool, NA 0.3, Quadruple, outer sigma 0.68, inner sigma 0.36). Additionally, a mask with a line size of 20 nm and a line-to-space ratio of 1:1 was used as the reticle.

[1325] After the exposed resist film was baked at 90°C for 60 seconds, it was developed with a tetramethylammonium hydroxide aqueous solution (2.38% by mass) for 30 seconds, followed by rinsing with pure water for 30 seconds. Then, it was rotated to dry, thus obtaining a positive pattern.

[1326] (evaluate)

[1327] The obtained pattern was evaluated using the same method as that used to evaluate the LWR of the pattern in <EUV exposure, organic solvent development>.

[1328] [Table 8]

[1329]

[1330] (result)

[1331] As shown in Table 8, it was confirmed that when EUV exposure is performed and patterns are obtained by alkaline development, the resist composition of the present invention can form patterns with excellent LWR performance.

[1332] Comparisons of Examples 2-1 to 2-45 confirm that the effects of the present invention are more superior when the sulfonium cation has an acid-degrading group represented by general formula (a-1) or (a-2). Furthermore, similar comparisons confirm that the effects of the present invention are further superior when the sulfonium cation has an acid-degrading group represented by general formula (a-1).

[1333] The comparison of Examples 2-1 to 2-45 confirms that the present invention is more effective when the sulfonium cation has one acid-decomposing group.

[1334] The comparison of Examples 2-1 to 2-45 confirms that the present invention is more effective when a specific compound containing a sulfonium cation represented by the general formula (S-1) is used.

[1335] <ArF immersion exposure, organic solvent development>

[1336] (Pattern Formation)

[1337] An organic antireflective film forming composition ARC29SR (manufactured by Brewer Science) was coated onto a silicon wafer and baked at 205°C for 60 seconds to form an antireflective film with a thickness of 98 nm. The resist composition shown in Table 8 was then coated onto the wafer and baked at 100°C for 60 seconds to form a resist film (photosensitive or radiosensitive linear film) with a thickness of 90 nm.

[1338] In addition, for Examples 3-18 to 3-20, a topcoat film was formed on top of the resist film (the types of topcoat compositions used are shown in Table 8). The thickness of the topcoat film was set to 100 nm in all cases.

[1339] For the resist film, an ArF excimer laser immersion scanner (manufactured by ASML; XT1700i, NA 1.20, Dipole, outer sigma 0.950, inner sigma 0.850, Y-deflection) was used for exposure via a 6% halftone mask with a 1:1 line-space pattern and a linewidth of 45 nm. Ultrapure water was used as the immersion solution.

[1340] After the exposed resist film was baked at 90°C for 60 seconds, it was developed with n-butyl acetate for 30 seconds, followed by rinsing with 4-methyl-2-pentanol for 30 seconds. Then, it was rotated to dry, thus obtaining a negative pattern.

[1341] (evaluate)

[1342] A 45nm (1:1) line and spatial pattern, analyzed for optimal exposure when resolving line patterns with an average linewidth of 45nm, was observed from the top of the pattern using a length-measuring scanning electron microscope (SEM, S-9380II manufactured by Hitachi, Ltd.). The linewidth of the pattern was observed at any point (100), and its measurement deviation was evaluated by 3σ and set as LWR. The smaller the LWR value, the better the LWR performance. When using the resist composition of the present invention, the LWR (nm) is 3.8nm or less, preferably 3.2nm or less, more preferably 2.9nm or less, further preferably 2.7nm or less, and especially preferably 2.5nm or less.

[1343] [Table 9]

[1344]

[1345] (result)

[1346] As shown in Table 9, it was confirmed that when ArF exposure is performed and the pattern is obtained by developing with an organic solvent, the resist composition of the present invention can form a pattern with excellent LWR performance.

[1347] The comparison of Examples 3-1 to 3-20 confirms that the effects of the present invention are even better when the sulfonium cation has an acid-decomposing group represented by general formula (a-1).

[1348] The comparison of Examples 3-1 to 3-20 confirms that the present invention is more effective when the sulfonium cation has one acid-decomposing group.

[1349] The comparison of Examples 3-1 to 3-20 confirms that the present invention is more effective when a specific compound containing a sulfonium cation represented by the general formula (S-1) is used.

[1350] <ArF immersion exposure, alkaline development>

[1351] (Pattern Formation)

[1352] An organic antireflective film forming composition ARC29SR (manufactured by Brewer Science) was coated onto a silicon wafer and baked at 205°C for 60 seconds to form an antireflective film with a thickness of 98 nm. The resist composition shown in Table 9 was then coated onto the wafer and baked at 100°C for 60 seconds to form a resist film with a thickness of 90 nm.

[1353] In addition, for Examples 4-18 to 4-20, a topcoat film was formed on top of the resist film (the types of topcoat compositions used are shown in Table 9). The thickness of the topcoat film was set to 100 nm in all cases.

[1354] For the resist film, an ArF excimer laser immersion scanner (manufactured by ASML; XT1700i, NA 1.20, Dipole, outer sigma 0.950, inner sigma 0.890, Y-deflection) was used for exposure via a 6% halftone mask with a 1:1 line-space pattern and a linewidth of 45 nm. Ultrapure water was used as the immersion solution.

[1355] After the exposed resist film was baked at 90°C for 60 seconds, it was developed with a tetramethylammonium hydroxide aqueous solution (2.38% by mass) for 30 seconds, followed by rinsing with pure water for 30 seconds. Then, it was rotated to dry, thus obtaining a positive pattern.

[1356] (evaluate)

[1357] The obtained pattern was evaluated using the same method as that used to evaluate the LWR of the pattern in <ArF immersion exposure, organic solvent development>.

[1358] [Table 10]

[1359]

[1360] (result)

[1361] As shown in Table 10, it was confirmed that when ArF exposure is performed and a pattern is obtained by alkaline development, the resist composition of the present invention can form a pattern with excellent LWR performance.

[1362] The comparison of Examples 4-1 to 4-20 confirms that the effects of the present invention are even better when the sulfonium cation has an acid-decomposing group represented by general formula (a-1).

[1363] The comparison of Examples 4-1 to 4-20 confirms that the present invention is more effective when the sulfonium cation has one acid-decomposing group.

[1364] The comparison of Examples 4-1 to 4-20 confirms that the present invention is more effective when a specific compound containing a sulfonium cation represented by the general formula (S-1) is used.

Claims

1. A radiation-sensitive or radio-sensitive resin composition comprising: a compound represented by the following general formula (S-2); and a resin which increases in polarity by decomposition by the action of an acid, In General Formula (S-2), R a represents a group represented by General Formula (S-3) below, R b1 , R b2 , and R b3 each independently represents a fluorine atom or an organic group having a fluorine atom, R c1 , R c2 , and R c3 each independently represents an organic group different from the group containing an acid-decomposable group and not having a fluorine atom, the acid-decomposable group meaning a group that generates a polar group by the action of an acid, X - represents an organic anion, b1 represents an integer of 0 to 4, b2 represents an integer of 0 to 5, b3 represents an integer of 0 to 5, c1 represents an integer of 0 to 4, c2 represents an integer of 0 to 5, c3 represents an integer of 0 to 5, the total of b1, b2, and b3 represents an integer of 1 or more and 3 or less, the total of b1 and c1 represents an integer of 0 to 4, the total of b2 and c2 represents an integer of 0 to 5, and the total of b3 and c3 represents an integer of 0 to 5, R b1 The number of fluorine atoms in it, R b2 The number of fluorine atoms and R b3 The total number of fluorine atoms in it is 3 or more. in General Formula (S-3), represents a bonding position, L T1 represents a single bond, -O-, -CO-, -CS-, -COO-, an alkylene group, or a linking group formed by multiple connections of these, R T1 represents a group that does not contain a fluorine atom and that increases in polarity by the action of an acid, the group which does not contain a fluorine atom and increases in polarity by decomposition by the action of an acid is a group represented by general formula (a-1) or (a-2), In General Formula (a-1), R a1 represents a linear or branched alkyl group optionally having a substituent not containing a fluorine atom, or a cycloalkyl group optionally having a substituent not containing a fluorine atom, represents a bonding position, In General Formula (a-2), R a2 represents a linear or branched alkyl group optionally having a substituent other than a fluorine atom, or a cycloalkyl group optionally having a substituent other than a fluorine atom, R a3 represents a hydrogen atom, a linear or branched alkyl group optionally having a substituent other than a fluorine atom, or a cycloalkyl group optionally having a substituent other than a fluorine atom, R a2 and R a3 are optionally linked to each other to form a ring, represents a bonding position.

2. The radiation-sensitive or radio-sensitive resin composition according to claim 1, wherein R b1 The number of fluorine atoms in it, R b2 The number of fluorine atoms and R b3 The total number of fluorine atoms in it is more than 6.

3. The radiation-sensitive or radio-sensitive resin composition according to claim 1, wherein the organic group having a fluorine atom is a linear or branched alkyl group having a fluorine atom, a cyclic alkyl group having a fluorine atom, or an aryl group having a fluorine atom.

4. The radiation-sensitive or radio-sensitive resin composition according to claim 1, wherein the resin which increases in polarity by decomposition by the action of an acid has a repeating unit represented by the following general formula (I), In General Formula (I), R 41 , R 42 , and R 43 each independently represent a hydrogen atom, an alkyl group, a cycloalkyl group, a halogen atom, a cyano group, or an alkoxycarbonyl group, wherein R 42 is optionally bonded to Ar4to form a ring, R 42 represents a single bond or an alkylene group, X4represents a single bond, -COO- or -CONR 64 -, R 64 represents a hydrogen atom or an alkyl group, L4represents a single bond or an alkylene group, Ar4represents an (n+1) valent aromatic ring group, when it forms a ring by bonding with R 42 , represents an (n+2) valent aromatic ring group, and n represents an integer of 1 to 5.

5. The radiation-sensitive or radio-sensitive resin composition according to claim 4, wherein the repeating unit represented by the general formula (I) is a repeating unit represented by the following general formula (1), in general formula (1), A represents a hydrogen atom, an alkyl group, a cyclic alkyl group, a halogen atom, or a cyano group, R represents a halogen atom, an alkyl group, a cyclic alkyl group, an aryl group, an alkenyl group, an aralkyl group, an alkoxy group, an alkylcarbonyloxy group, an alkylsulfonyloxy group, an alkoxycarbonyl group, or an aryloxycarbonyl group, in the case where a plurality of R is present, the plurality of R is optionally the same or different, and the plurality of R is optionally collectively forms a ring with each other, a represents an integer of 1 to 3, and b represents an integer of 0 to (5-a).

6. The radiation-sensitive or radio-sensitive resin composition according to claim 1, wherein the group which does not contain a fluorine atom and increases in polarity by decomposition by the action of an acid is a group represented by the general formula (a-1).

7. The radiation-sensitive or radio-sensitive resin composition according to any one of claims 1 to 6, wherein R b1 , R b2 , and R b3 each independently represent a fluorine atom, or a linear or branched fluoroalkyl group.

8. A resist film formed using the radiation-sensitive or radio-sensitive resin composition according to any one of claims 1 to 7.

9. A pattern forming method having the following steps: a step of forming a resist film on a substrate using the radiation-sensitive or radio-sensitive resin composition according to any one of claims 1 to 7; a step of exposing the resist film to light; and a step of developing the exposed resist film using a developing solution and forming a pattern.

10. A method for manufacturing an electronic device, which includes the pattern forming method according to claim 9.

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