Method for producing a photosensitive or radiation-sensitive resin composition, a method for forming a pattern, and a method for producing an electronic device.

Abstract

To provide a method for producing an active-ray- or radiation-sensitive resin composition which contains an onium salt containing anion having a pKa of a conjugate acid of 2.0 or more and is excellent in LWR performance after etching, a pattern formation method and a method for manufacturing an electronic device using the production method, and a method for producing the onium salt.SOLUTION: There are provided a method for producing an active-ray- or radiation-sensitive resin composition including the steps of passing a solution containing an acid compound having a pKa of 2.0 or more through a column filled with an ion exchange resin, producing an onium salt using an acid compound after having passed through the column, and mixing the onium salt with a resin whose polarity increases due to action of an acid; a pattern formation method and a method for manufacturing an electronic device using the production method; and a method for producing the onium salt.SELECTED DRAWING: None

Description

[Technical Field]

[0001] The present invention relates to a method for producing a photosensitive or radiation-sensitive resin composition, a pattern forming method, a method for producing an electronic device, and a method for producing an onium salt. More specifically, the present invention relates to a method for producing a photosensitive or radiation-sensitive resin composition, a pattern forming method, a method for producing an electronic device, and a method for producing an onium salt, which are suitably used in ultramicrolithography processes applicable to the manufacturing processes of ultra-large-scale integrations (ULSIs) and high-capacity microchips, nanoimprint mold creation processes, and high-density information recording media, as well as other photofabrication processes. [Background technology]

[0002] Traditionally, in the manufacturing process of semiconductor devices such as ICs (Integrated Circuits) and LSIs, microfabrication has been performed using lithography with photoresist compositions. In recent years, with the increasing integration of integrated circuits, there has been a growing demand for the formation of ultrafine patterns in the submicron or quarter-micron region. Accordingly, there has been a trend toward shorter exposure wavelengths, from the g-line to the i-line, and further to KrF excimer laser light. Currently, exposure machines using ArF excimer lasers with a wavelength of 193 nm as the light source have been developed. Furthermore, as a technique to further improve resolution, development of the so-called immersion method has been progressing, in which a high refractive index liquid (hereinafter also called "immersion liquid") is filled between the projection lens and the sample.

[0003] Furthermore, in addition to excimer laser light, lithography using electron beams (EB), X-rays, and extreme ultraviolet (EUV) light is currently under development. Accordingly, chemically amplified resist compositions that are highly sensitive to various types of radiation and exhibit excellent sensitivity and resolution are being developed.

[0004] Onium salts are often used in photosensitive or radiation-sensitive resin compositions, such as resist compositions. For example, Patent Document 1 describes a resist composition containing a resin having an aproton-type onium salt. Patent Document 1 describes a method for producing an aproton-type onium salt compound having a hydroxyl group anion by passing an aqueous solution of an aproton-type onium salt compound having an acetate anion through an anion exchange resin to exchange the acetate anion for a hydroxyl group anion. [Prior art documents] [Patent Documents]

[0005] [Patent Document 1] International Publication No. 99 / 54788 [Overview of the project] [Problems that the invention aims to solve]

[0006] Our investigations have shown that, among onium salts, when an onium salt containing a conjugate acid with a pKa of 2.0 or higher is used in a resist composition, the line width roughness (LWR) of the resist pattern after etching is likely to be large when a resist pattern is formed on a workpiece such as a silicon wafer. Therefore, a resist composition is needed that contains an onium salt with a conjugate acid pKa of 2.0 or higher, and exhibits excellent LWR performance after etching. LWR performance refers to the ability to reduce the LWR of the pattern.

[0007] The present invention aims to provide a method for producing a photosensitive or radiation-sensitive resin composition that contains an onium salt with a conjugate acid pKa of 2.0 or higher, and exhibits excellent LWR performance after etching. The present invention also aims to provide a pattern forming method and a method for producing an electronic device using the above method for producing a photosensitive or radiation-sensitive resin composition, as well as a method for producing the above onium salt.

Means for Solving the Problem

[0008] In the process of studying the above problems, the inventors of the present invention found that when purifying an onium salt containing an anion with a pKa of the conjugate acid of 2.0 or higher, passing it through an ion exchange resin or performing acid washing would result in protonation during purification, leading to a decrease in the LWR performance after etching. Then, by passing a solution containing an acid compound with a pKa of 2.0 or higher through a column filled with an ion exchange resin and producing an onium salt using the acid compound after passing through the column, it was found that purification could be enabled while suppressing protonation, thus solving the above problems.

[0009] The inventors of the present invention found that the above problems can be achieved by the following configuration. <1> (1) A step in which a solution containing an acid compound (CA) with a pKa of 2.0 or higher is passed through a column packed with ion exchange resin. (2) A step to produce an onium salt (C) using the acid compound (CA) after passing it through the column, and A method for producing a photosensitive or radiation-sensitive resin composition, comprising the step (3) of mixing the above-mentioned onium salt (C) with a resin (A) whose polarity increases by the action of an acid, A method for producing a photosensitive or radiation-sensitive resin composition, wherein the resin (A) has at least one selected from the group consisting of repeating units represented by the following general formula (A1), repeating units represented by the following general formula (A2), and repeating units represented by the following general formula (A3).

Chemical Formula

[0010] [1] (1) A step in which a solution containing an acid compound (CA) with a pKa of 2.0 or higher is passed through a column packed with ion exchange resin. (2) A step to produce an onium salt (C) using the acid compound (CA) after passing it through the column, and A method for producing a photosensitive or radiation-sensitive resin composition, comprising the step (3) of mixing the above-mentioned onium salt (C) with a resin (A) whose polarity increases by the action of an acid. [2] A method for producing the photosensitive or radiation-sensitive resin composition according to [1], wherein the ion exchange resin has a strongly acidic cation exchange group as an ion exchange group. [3] A method for producing the photosensitive or radiation-sensitive resin composition according to [2], wherein the above-mentioned strongly acidic cation exchange group is a sulfonic acid group. [4] A method for producing a photosensitive or radiation-sensitive resin composition according to any one of [1] to [3], wherein the pKa of the above-mentioned acid compound (CA) is 3.0 or higher. [5] A method for producing a photosensitive or radiation-sensitive resin composition according to any one of [1] to [4], wherein the above-mentioned acid compound (CA) is a carboxylic acid or a phenol. [6] A method for producing a photosensitive or radiation-sensitive resin composition according to any one of [1] to [4], wherein the above-mentioned acid compound (CA) is a compound represented by the following general formula (CA1) or (CA2).

[0011] [ka]

[0012] In the general formula (CA1), j represents either 0 or 1. Q C1 represents a substituent. m1 and m2 each independently represent either 0 or 1. m3 represents an integer greater than or equal to 0 and less than or equal to (6 + 2j - m1 - m2). However, the sum of m1 and m2 is either 1 or 2. *Each of these symbols represents a bond that attaches to an aromatic hydrocarbon listed in the general formula (CA1).

[0013] [ka]

[0014] In general formula (CA2), Q C2 represents an alkyl group or cycloalkyl group. [7] A method for producing a photosensitive or radiation-sensitive resin composition according to any one of [1] to [6], wherein the value obtained by subtracting the pKa of the ion exchange group of the ion exchange resin from the pKa of the acid compound (CA) is 3.0 or greater. [8] A method for producing a photosensitive or radiation-sensitive resin composition according to any one of [1] to [7], wherein the degree of crosslinking of the ion exchange resin is 10% or less. [9] A method for producing the above-mentioned photosensitive or radiation-sensitive resin composition according to any one of [1] to [8], wherein the above-mentioned photosensitive or radiation-sensitive resin composition contains 10% by mass or more of the above-mentioned onium salt (C) based on the total solid content.

[10] The above-mentioned photosensitive or radiation-sensitive resin composition further contains a compound (B) that generates acid upon irradiation with active light or radiation, The mass-based content of the onium salt (C) in the above-mentioned photosensitive or radiation-sensitive resin composition is A C The mass-based content of the above compound (B) is set to A B In that case, A C :A B A method for producing a photosensitive or radiation-sensitive resin composition according to any one of [1] to [9], wherein the ratio is 1:4 to 4:1.

[11] A method for producing a photosensitive or radiation-sensitive resin composition according to any one of [1] to

[10] , wherein the resin (A) comprises at least one selected from the group consisting of repeating units represented by the following general formula (A1), repeating units represented by the following general formula (A2), and repeating units represented by the following general formula (A3).

[0015] [ka]

[0016] In general formula (A1), R a1 , R a2 and R a3 Each of these independently represents a hydrogen atom, an alkyl group, a cycloalkyl group, a halogen atom, a cyano group, or an alkoxycarbonyl group. a1 Ar represents a single bond or a divalent linking group. a1 R represents an aromatic ring group. a4 R represents a hydrogen atom, alkyl group, cycloalkyl group, aryl group, aralkyl group, or alkenyl group. a5 and R a6 Each of these independently represents an alkyl group, a cycloalkyl group, an aryl group, an aralkyl group, or an alkenyl group. a4 and R a5 They may combine with each other to form a ring. a1 is R a3 or R a4 It may also combine with other elements to form a ring. In general formula (A2), R a7 , R a8 and R a9 Each of these independently represents a hydrogen atom, an alkyl group, a cycloalkyl group, a halogen atom, a cyano group, or an alkoxycarbonyl group. a2 Ar represents a single bond or a divalent linking group. a2 R represents an aromatic ring group. a10 , R a11 and R a12 Each of these independently represents an alkyl group, a cycloalkyl group, an aryl group, an aralkyl group, or an alkenyl group. a10 , R a11 and R a12 Two of them may be joined together to form a ring. In general formula (A3), R a13 , R a14 and R a15 Each of these independently represents a hydrogen atom, an alkyl group, a cycloalkyl group, a halogen atom, a cyano group, or an alkoxycarbonyl group. a3 Ar represents a single bond or a divalent linking group. a3 R represents an aromatic ring group. a16 , R a17 and R a18Each of these independently represents an alkyl group, a cycloalkyl group, an aryl group, an aralkyl group, or an alkenyl group. a16 , R a17 and R a18 Two of them may be joined together to form a ring.

[12] A method for producing a photosensitive or radiation-sensitive resin composition according to any one of [1] to

[11] , wherein the resin (A) has repeating units having groups that generate acid upon irradiation with active light or radiation.

[13] A pattern forming method comprising the steps of: forming a resist film on a substrate using a photosensitive or radiation-sensitive resin composition produced by a method for producing a photosensitive or radiation-sensitive resin composition described in any one of [1] to

[11] ; exposing the resist film; and developing the exposed resist film using a developer.

[14] A method for manufacturing an electronic device, including the pattern formation method described in

[13] .

[15] (1) A step of passing a solution containing an acid compound (CA) with a pKa of 2.0 or higher through a column packed with ion exchange resin, and A method for producing an onium salt, comprising step (2) of producing an onium salt (C) using the acid compound (CA) after passing it through the column described above. [Effects of the Invention]

[0017] The present invention provides a method for producing a photosensitive or radiation-sensitive resin composition containing an onium salt with a conjugate acid pKa of 2.0 or higher, which exhibits excellent LWR performance after etching. Furthermore, the present invention provides a pattern forming method and an electronic device manufacturing method using the above method for producing the photosensitive or radiation-sensitive resin composition, as well as a method for producing the above onium salt. [Modes for carrying out the invention]

[0018] The present invention will be described in detail below. The following description of the constituent elements may be based on typical embodiments of the present invention, but the present invention is not limited to such embodiments. In this specification, regarding the notation of groups (atomic groups), unless contrary to the spirit of the present invention, notations that do not specify substituted or unsubstituted include both unsubstituted and substituted groups. For example, "alkyl group" includes not only unsubstituted alkyl groups but also substituted alkyl groups. Furthermore, in this specification, "organic group" means a group containing at least one carbon atom. Unless otherwise specified, monovalent substituents are preferred.

[0019] In this specification, the type of substituent, the position of the substituent, and the number of substituents are not particularly limited when we say "may have substituents." The number of substituents may be, for example, one, two, three, or more. Examples of substituents include monovalent nonmetallic groups excluding hydrogen atoms, and for example, substituents T can be selected from the following:

[0020] (substituent T) Substituents T include halogen atoms such as fluorine, chlorine, bromine, and iodine; alkoxy groups such as methoxy, ethoxy, and tert-butoxy; aryloxy groups such as phenoxy and p-tolyloxy; alkoxycarbonyl groups such as methoxycarbonyl, butoxycarbonyl, and phenoxycarbonyl; acyloxy groups such as acetoxy, propionyloxy, and benzoyloxy; acyl groups such as acetyl, benzoyl, isobutyryl, acryloyl, methacryloyl, and methoxalyl; methylsulfanyl and tert-butylsulfanyl Examples include alkylsulfanyl groups such as phenyl groups; arylsulfanyl groups such as phenylsulfanyl groups and p-tolylsulfanyl groups; alkyl groups (e.g., 1 to 10 carbon atoms); cycloalkyl groups (e.g., 3 to 20 carbon atoms); aryl groups (e.g., 6 to 20 carbon atoms); heteroaryl groups; hydroxyl groups; carboxyl groups; formyl groups; sulfo groups; cyano groups; alkylaminocarbonyl groups; arylaminocarbonyl groups; sulfonamide groups; silyl groups; amino groups; monoalkylamino groups; dialkylamino groups; arylamino groups, nitro groups; formyl groups; and combinations thereof.

[0021] In this specification, "active light" or "radiation" means, for example, the emission 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 specification, "light" means active light or radiation. In this specification, unless otherwise specified, "exposure" includes not only exposure using emission line spectra from mercury lamps, far ultraviolet light represented by excimer lasers, extreme ultraviolet (EUV) light, and X-rays, but also drawing using particle beams such as electron beams and ion beams. In this specification, "~" is used to mean that the numbers before and after it are included as the lower and upper limits, respectively.

[0022] In this specification, the bonding direction of the divalent linking group is not limited unless otherwise specified. For example, in a compound represented by the formula "XYZ", if Y is -COO-, Y may also be -CO-O- or -O-CO-. The above compound may also be "X-CO-OZ" or "XO-CO-Z".

[0023] In this specification, (meth)acrylate refers to acrylate and methacrylate, and (meth)acrylic refers to acrylic and methacrylic. In this specification, weight-average molecular weight (Mw), number-average molecular weight (Mn), and degree of dispersion (hereinafter also referred to as "molecular weight distribution") (Mw / Mn) are determined by GPC (Gel Permeation Chromatography) measurement using a GPC (Tosoh Corporation HLC-8120GPC) instrument (solvent: tetrahydrofuran, flow rate (sample injection volume): 10 μL, column: Tosoh Corporation TSK gel Multipore HXL-M, column temperature: 40°C, flow rate: 1.0 mL / min, detector: differential refractive index detector (Refractive Index) It is defined as a polystyrene equivalent value by Detector.

[0024] In this specification, the acid dissociation constant (pKa) refers to the pKa in aqueous solution, and specifically, it is a value calculated using the software package 1 described below, based on a database of Hammett substituent constants and known literature values. Software Package 1: Advanced Chemistry Development (ACD / Labs) Software V8.14 for Solaris (1994-2007 ACD / Labs).

[0025] pKa can also be determined by molecular orbital calculations. Specifically, based on the thermodynamic cycle, H in aqueous solution + One method is to calculate it by calculating the dissociation free energy. +The dissociation free energy can be calculated using, for example, DFT (Density Functional Theory), but various other methods have been reported in the literature and are not limited to this. Several software programs exist that can perform DFT; for example, Gaussian16 is one such program.

[0026] In this specification, pKa refers to a value calculated using software package 1, based on a database of Hammett substituent constants and publicly available literature values, as described above. However, if pKa cannot be calculated using this method, the value obtained by Gaussian16 based on DFT (Density Functional Theory) shall be adopted. In this specification, pKa refers to "pKa in aqueous solution" as described above, but if pKa in aqueous solution cannot be calculated, "pKa in dimethyl sulfoxide (DMSO) solution" shall be used. "Solid content" refers to components that form photosensitive or radiation-sensitive films (typically resist films), and does not include solvents. Furthermore, any component that forms a photosensitive or radiation-sensitive film is considered solid content, even if its state is liquid.

[0027] The present invention will be described in detail below.

[0028] <Method for producing a photosensitive or radiation-sensitive resin composition> The method for producing the photosensitive or radiation-sensitive resin composition of the present invention is as follows: (1) A step in which a solution containing an acid compound (CA) with a pKa of 2.0 or higher is passed through a column packed with ion exchange resin. (2) A step to produce an onium salt (C) using the acid compound (CA) after passing it through the column, and The process includes a step (3) of mixing an onium salt (C) with a resin (A) whose polarity increases due to the action of an acid.

[0029] The photosensitive or radiation-sensitive resin composition in the present invention is typically a resist composition, and may be either a positive-type resist composition or a negative-type resist composition. The resist composition may be a resist composition for alkaline development or a resist composition for organic solvent development. The resist composition may be a chemically amplified resist composition or a non-chemically amplified resist composition. Typically, the resist composition is a chemically amplified resist composition. The photosensitive or radiation-sensitive resin composition in this invention may also be referred to as a "resist composition."

[0030] ·Process (1) Step (1) is a step in which a solution containing an acid compound (CA) with a pKa of 2.0 or higher is passed through a column packed with ion exchange resin.

[0031] (Acid compounds (CA) with a pKa of 2.0 or higher) This section explains acid compounds (CA) with a pKa of 2.0 or higher (also called "acid compounds (CA)"). The pKa of the acid compound (CA) is preferably 2.0 or higher, more preferably 2.5 or higher, and more preferably 3.0 or higher. Furthermore, the pKa of the acid compound (CA) is preferably 8.0 or lower, more preferably 6.0 or lower, and even more preferably 5.0 or lower. The pKa of an acid compound (CA) can be determined by the method described above.

[0032] If an acid compound (CA) has two or more acid groups, two or more pKa values ​​will be calculated, but in that case, the smallest pKa value must be 2.0 or higher. For example, the compound CH-2 below has two acid groups, and the pKa of the dissociation reaction between CH-2 and CH-2a (the first-step acid dissociation constant, called "pKa1") and the pKa of the dissociation reaction between CH-2a and CH-2b (the second-step acid dissociation constant, called "pKa2") can be determined, but 2.0 ≤ pKa1 <pKa2である。

[0033] [ka]

[0034] The molecular weight of the acid compound (CA) is preferably 50 to 500, more preferably 50 to 300, and even more preferably 50 to 200.

[0035] The acid compound (CA) is preferably a carboxylic acid (a compound having a carboxyl group) or a phenol (a compound having a phenolic hydroxyl group).

[0036] The acid compound (CA) is preferably a compound represented by the following general formula (CA1).

[0037] [ka]

[0038] In the general formula (CA1), j represents either 0 or 1. Q C1 represents a substituent. m1 and m2 each independently represent either 0 or 1. m3 represents an integer greater than or equal to 0 and less than or equal to (6 + 2j - m1 - m2). However, the sum of m1 and m2 is either 1 or 2. *Each of these symbols represents a bond that attaches to an aromatic hydrocarbon listed in the general formula (CA1).

[0039] When j in general formula (CA1) represents 0, the aromatic hydrocarbon listed in general formula (CA1) represents benzene. When j in general formula (CA1) represents 1, the aromatic hydrocarbon listed in general formula (CA1) represents naphthalene.

[0040] Q in the general formula (CA1) C1 represents a substituent. Q C1The substituent represented by [is not particularly limited, but a halogen atom, an alkyl group, a cycloalkyl group, an alkenyl group, an aryl group, a heterocyclic group, a cyano group or a nitro group is preferred.

[0041] Q C1 When [represents a halogen atom, the halogen atom is preferably a fluorine atom, a chlorine atom, a bromine atom or an iodine atom, and particularly preferably a fluorine atom.

[0042] Q C1 When [represents an alkyl group, the alkyl group may be linear or branched. As the above alkyl group, an alkyl group having 1 to 10 carbon atoms such as a methyl group, an ethyl group, an n-propyl group, an isopropyl group, an n-butyl group, an isobutyl group, a t-butyl group, etc. is preferred, and an alkyl group having 1 to 6 carbon atoms is more preferred. Further, the above alkyl group may have a substituent, and examples of the alkyl group having a substituent include a fluorinated alkyl group such as a trifluoromethyl group.

[0043] Q C1 When [represents a cycloalkyl group, the cycloalkyl group may be a monocyclic cycloalkyl group or a polycyclic cycloalkyl group. The number of carbon atoms of the above cycloalkyl group is preferably 3 to 20, more preferably 4 to 15, and still more preferably 5 to 10. Further, the above cycloalkyl group may have a substituent. An oxo group (=O) may be substituted on the carbon atom contained as a ring member in the above cycloalkyl group. As the above cycloalkyl group, monocyclic cycloalkyl groups such as a cyclopentyl group, a cyclohexyl group, etc., and polycyclic cycloalkyl groups such as a norbornyl group, a tetracyclodecanyl group, a tetracyclododecanyl group, an adamantyl group, etc. are preferred.

[0044] Q C1The aryl group represented by aryl may be a monocyclic aryl group or a polycyclic aryl group. Furthermore, the aryl group may have substituents. The aryl group is preferably an aryl group having 6 to 20 carbon atoms, more preferably an aryl group having 6 to 10 carbon atoms, and examples include a phenyl group, a naphthyl group, and an anthyl group.

[0045] Q C1 When represents an alkenyl group, the alkenyl group may be linear or branched. Furthermore, the alkenyl group may have substituents. The alkenyl group is preferably a C2-C10 alkenyl group such as a vinyl group, and more preferably a C2-C6 alkenyl group.

[0046] Q C1 When represents a heterocyclic group, it is preferable that the heterocyclic group be an aromatic heterocyclic group or a non-aromatic heterocyclic group.

[0047] Q C1 When representing an aromatic heterocyclic group (heteroaryl group), the preferred aromatic heterocyclic group is one that contains at least one heteroatom selected from the group consisting of nitrogen, sulfur, and oxygen atoms. The above aromatic heterocyclic group may have substituents. The carbon atoms included as ring members in the above aromatic heterocyclic group may be substituted with oxo groups (=O).

[0048] Q C1 When represents a non-aromatic heterocyclic group (aliphatic heterocyclic group), a non-aromatic heterocyclic group containing at least one heteroatom selected from the group consisting of nitrogen, sulfur, and oxygen atoms is preferred. The above non-aromatic heterocyclic group may have substituents. The carbon atoms included as ring members in the above non-aromatic heterocyclic group may be substituted with oxo groups (=O).

[0049] When m1 represents 0 and m2 represents 1, m3 preferably represents an integer of 1 or more, and at least one Q C1 preferably represents a fluorine atom or a fluoroalkyl group.

[0050] The acid compound (CA) is also preferably a compound represented by the following general formula (CA2).

[0051]

Chemical formula

[0052] In the general formula (CA2), Q C2 represents an alkyl group or a cycloalkyl group.

[0053] Q C2 When Q represents an alkyl group, the alkyl group may be linear or branched. Examples of the alkyl group include alkyl groups having 1 to 10 carbon atoms such as methyl group, ethyl group, n-propyl group, isopropyl group, n-butyl group, isobutyl group, t-butyl group, etc., and alkyl groups having 1 to 6 carbon atoms are more preferable. Further, the above alkyl group may have a substituent, and examples of the alkyl group having a substituent include fluoroalkyl groups such as trifluoromethyl group.

[0054] Q C2 When Q represents a cycloalkyl group, the cycloalkyl group may be a monocyclic cycloalkyl group or a polycyclic cycloalkyl group. The number of carbon atoms of the above cycloalkyl group is preferably 3 to 20, more preferably 4 to 15, and still more preferably 5 to 10. Further, the above cycloalkyl group may have a substituent. An oxo group (=O) may be substituted on the carbon atom contained as a ring member in the above cycloalkyl group. Examples of the above cycloalkyl group include monocyclic cycloalkyl groups such as cyclopentyl group and cyclohexyl group, and polycyclic cycloalkyl groups such as norbornyl group, tetracyclodecanyl group, tetracyclododecanyl group, and adamantyl group.

[0055] Specific examples of acid compounds (CA) are shown below, but the present invention is not limited to these. Me represents a methyl group.

[0056] [ka]

[0057] Acid compounds (CAs) can be synthesized using conventionally known methods, or commercially available products can be used.

[0058] (solvent) The solution containing the acid compound (CA) used in step (1) can be obtained by mixing the acid compound (CA) with a solvent. The solvent is not particularly limited; it may be an organic solvent or water. Examples of solvents include methylene chloride, chloroform, methanol, ethanol, acetonitrile, tetrahydrofuran, and water.

[0059] (Ion exchange resin) The ion exchange resin used in step (1) is preferably one that has a cation exchange group as an ion exchange group. Examples of cation exchange groups include sulfonic acid groups and carboxylic acid groups. The ion exchange resin is preferably one that has a strongly acidic cation exchange group as an ion exchange group, and more preferably one that has a sulfonic acid group. A strongly acidic cation exchange group is an ion exchange group with a pKa of 1.0 or less.

[0060] The value obtained by subtracting the pKa (X2) of the ion exchange group of the ion exchange resin from the pKa (X1) of the acid compound (CA) (X1) (X1-X2) is preferably 1.0 or higher, more preferably 2.0 or higher, and even more preferably 3.0 or higher. Furthermore, X1-X2 is preferably 8.0 or lower, more preferably 7.0 or lower, and even more preferably 6.0 or lower.

[0061] Specifically, the pKa of the ion exchange group in the ion exchange resin is the pKa obtained by the method described above for the monomer (M) of the structure corresponding to the repeating unit (T) to which the ion exchange group is bonded in the ion exchange resin. For example, if the repeating unit to which the ion exchange group is attached is represented by the following formula (T1), then the pKa of the compound represented by the following formula (M1), which is a monomer with a structure corresponding to the repeating unit represented by formula (T1), is taken as the pKa of the ion exchange group in the ion exchange resin.

[0062] [ka]

[0063] The degree of crosslinking of the ion exchange resin is preferably 12% or less, and more preferably 10% or less. When an ion exchange resin has a structure in which an ion exchange group is bonded to a substrate that is a copolymer of a main monomer (e.g., styrene or (meth)acrylic acid) and a crosslinking agent (e.g., divinylbenzene), the degree of crosslinking is defined as the mass percentage of the crosslinking agent in the substrate. For example, if the ion exchange resin is based on a copolymer of styrene and divinylbenzene (crosslinking agent), the degree of crosslinking is defined as the mass percentage of divinylbenzene in the base.

[0064] Commercially available ion exchange resins can be used. Examples of ion exchange resins include DIAION SK1BH, DIAION SK112L, Diaion WK10, DIAION SK104H, DIAION SK110, DIAION SK110L, DIAION SK112, DIAION SK1B, DIAION SK1BL, DIAION SK1BLH, DIAION SKL10, DIAION SKT10L, DIAION SKT110, DIAION SKT110L, DIAION SKT20L, DIAION PK208, DIAION PK208L, DIAION PK208LH, DIAION PK212L, DIAION PK212LH, DIAION PK216, DIAION PK216L, DIAION PK216H, and DIAION PK216L, all manufactured by Mitsubishi Chemical Corporation. PK216LH, DIAION PK218, DIAION PK218L, DIAION PK220, DIAION PK220L, DIAION PK228, DIAION PK228L, DIAION PK228LH, DIAION RCP145H, DIAION RCP160M, DIAION RCP200, DIAION RCP400, DIAION RCP610, DIAION UBK04, DIAION UBK08, DIAION UBK08H, DIAION UBK08HUP, DIAION UBK10, DIAION UBK10H, DIAION UBK10HUP, DIAION UBK12, DIAION UBK16, DIAION UBKN1U, DIAION UBKN1UMB, DIAION UBK522M, DIAION Examples include UBK530, DIAION UBK530J, DIAION UBK530K, DIAION UBK535, DIAION UBK535J, DIAION UBK535K, DIAION UBK535L, DIAION UBK550, DIAION UBK555, DIAION JC600, and DIAION JC603.

[0065] (column) The column used in step (1) is not particularly limited as long as it can be packed with ion exchange resin. For example, a glass column can be used.

[0066] In step (1), the temperature and pressure used when passing the solution containing the acid compound (CA) through the column packed with ion exchange resin are not particularly limited. For example, it can be carried out at 5 to 40°C and atmospheric pressure.

[0067] ·Process (2) Step (2) is a step in which an onium salt (C) is produced using the acid compound (CA) that has been passed through the column in step (1).

[0068] (Onium salt (C)) The onium salt (C) produced by step (2) is an onium salt containing an anion with a conjugate acid pKa of 2.0 or higher.

[0069] The onium salt (C) is preferably a compound that generates an acid compound (CA) upon irradiation with active light or radiation. The pKa of the acid generated from the photoacid generator (B), described later, is preferably smaller than the pKa of the acid compound (CA). In photosensitive or radiation-sensitive resin compositions, the onium salt (C) preferably functions as an acid diffusion control agent. When a photosensitive or radiation-sensitive resin composition contains a photoacid generator (B) as described later, the onium salt (C) can act as a quencher to trap the acid generated from the photoacid generator (B) during exposure and suppress the reaction of the acid-degradable resin in the unexposed areas due to excess generated acid. More specifically, if the onium salt (C) is an onium salt that generates an acid that is relatively weaker than the acid generated from the photoacid generator (B), when the acid generated from the photoacid generator (B) by irradiation with active light or radiation collides with the onium salt (C) which has an unreacted weak acid anion, salt exchange occurs, releasing the weak acid and producing an onium salt with a strong acid anion. In this process, the strong acid is exchanged for a weaker acid with lower catalytic activity, so the acid is seemingly deactivated and acid diffusion can be controlled.

[0070] Onium salt (C) is "M + X - It is preferable that the compound is represented by ". "M + X - In the compound represented by ", X - This is an anion formed when an acid compound (CA) is deprotonated.

[0071] Anion (X) contained in onium salt (C) - ) is preferably an anion represented by the following general formula (CA1a-1).

[0072] [ka]

[0073] In the general formula (CA1a-1), j represents either 0 or 1. Q C1 represents a substituent. m2 represents either 0 or 1. m3 represents an integer greater than or equal to 0 and less than or equal to (5 + 2j - m2). *Each of these symbols represents a bond that attaches to the aromatic hydrocarbon listed in the general formula (CA1a-1).

[0074] j and Q in the general formula (CA1a-1) C1 The explanation, specific examples, and preferred ranges are given by j and Q in general formula (CA1), respectively. C1 This is similar to what was described earlier.

[0075] When m2 in general formula (CA1a-1) represents 1, the anion represented by general formula (CA1a-1) may also become the anion represented by the following general formula (CA1a-1b) through the second-step dissociation reaction.

[0076] [ka]

[0077] In the general formula (CA1a-1b), j represents either 0 or 1. Q C1 represents a substituent. m3 represents an integer greater than or equal to 0 and less than or equal to (4+2j). *Each of these symbols represents a bond that attaches to the aromatic hydrocarbon listed in the general formula (CA1a-1b).

[0078] j and Q in the general formula (CA1a-1b) C1 The explanation, specific examples, and preferred ranges are given by j and Q in general formula (CA1), respectively. C1 This is similar to what was described earlier.

[0079] Anion (X) contained in onium salt (C) - ) is also preferably an anion represented by the following general formula (CA1a-2).

[0080] [ka]

[0081] In the general formula (CA1a-2), j represents either 0 or 1. Q C1 represents a substituent. m3 represents an integer greater than or equal to 0 and less than or equal to (5 + 2j - m2). *Each of these symbols represents a bond that attaches to the aromatic hydrocarbon listed in the general formula (CA1a-1).

[0082] j and Q in the general formula (CA1a-2) C1 The explanation, specific examples, and preferred ranges are given by j and Q in general formula (CA1), respectively. C1 This is similar to what was described earlier. In the general formula (CA1a-2), m3 preferably represents an integer greater than or equal to 1, and at least one Q C1 Preferably, represents a fluorine atom or an alkyl fluoride.

[0083] Anion (X) contained in onium salt (C)- ) is also preferably an anion represented by the following general formula (CA2a).

[0084] [ka]

[0085] In the general formula (CA2a), Q C2 represents an alkyl group or cycloalkyl group.

[0086] Q in the general formula (CA2a) C2 The explanation, specific examples, and preferred range of Q in general formula (CA2) C2 This is similar to what was described earlier.

[0087] Anion (X) contained in onium salt (C) - Specific examples of ) are shown below, but the present invention is not limited to these. Me represents a methyl group.

[0088] [ka]

[0089] "M + X - In the compound represented by ", M + This represents an organic cation. The organic cation is not particularly limited. The valency of the organic cation may be 1 or 2 or more. In particular, among the above organic cations, the cation represented by formula (ZaI) (hereinafter also referred to as "cation (ZaI)") or the cation represented by formula (ZaII) (hereinafter also referred to as "cation (ZaII)") is preferred.

[0090] [ka]

[0091] In the above equation (ZaI), R 201 , R 202, and R 203 Each of these independently represents an organic group. R 201 , R 202 , and R 203 The number of carbon atoms in the organic group is preferably 1 to 30, and more preferably 1 to 20. 201 ~R 203 Two of these may bond together to form a ring structure, and the ring may contain an oxygen atom, a sulfur atom, an ester group, an amide group, or a carbonyl group. 201 ~R 203 Examples of groups formed by the bonding of two of these include alkylene groups (e.g., butylene and pentylene groups) and -CH2-CH2-O-CH2-CH2-.

[0092] Preferred embodiments of the organic cation in formula (ZaI) include cation (ZaI-1), cation (ZaI-2), cation (ZaI-3b), and cation (ZaI-4b), which will be described later.

[0093] First, let's explain the cation (ZaI-1). The cation (ZaI-1) is R in the above formula (ZaI). 201 ~R 203 It is an arylsulfonium cation in which at least one of the groups is an aryl group. Aryl sulfonium cations are R 201 ~R 203 All of them may be aryl groups, or R 201 ~R 203 A portion of the group may be an aryl group, and the remainder may be an alkyl group or a cycloalkyl group. R 201 ~R 203 One of them is an aryl group, R 201 ~R 203 The remaining two of these may bond to form a ring structure, which may contain an oxygen atom, a sulfur atom, an ester group, an amide group, or a carbonyl group. 201 ~R 203Examples of groups formed by the bonding of two of these include alkylene groups (e.g., butylene group, pentylene group, and -CH2-CH2-O-CH2-CH2-) in which one or more methylene groups may be substituted with an oxygen atom, a sulfur atom, an ester group, an amide group, and / or a carbonyl group. Examples of arylsulfonium cations include triarylsulfonium cations, diarylalkylsulfonium cations, aryldialkylsulfonium cations, diarylcycloalkylsulfonium cations, and aryldicycloalkylsulfonium cations.

[0094] The aryl group contained in the arylsulfonium cation is preferably a phenyl group or a naphthyl group, with the phenyl group being more preferred. The aryl group may be an aryl group having a heterocyclic structure containing an oxygen atom, a nitrogen atom, or a sulfur atom, etc. Examples of heterocyclic structures include pyrrole residues, furan residues, thiophene residues, indole residues, benzofuran residues, and benzothiophene residues. When the arylsulfonium cation has two or more aryl groups, the two or more aryl groups may be the same or different. The alkyl or cycloalkyl group that the arylsulfonium cation may optionally have is preferably a linear alkyl group having 1 to 15 carbon atoms, a branched alkyl group having 3 to 15 carbon atoms, or a cycloalkyl group having 3 to 15 carbon atoms, and more preferably a methyl group, ethyl group, propyl group, n-butyl group, sec-butyl group, t-butyl group, cyclopropyl group, cyclobutyl group, or cyclohexyl group.

[0095] R 201 ~R 203Preferred substituents that the aryl group, alkyl group, and cycloalkyl group may have are alkyl groups (e.g., C1-C15), cycloalkyl groups (e.g., C3-C15), aryl groups (e.g., C6-C14), alkoxy groups (e.g., C1-C15), cycloalkylalkoxy groups (e.g., C1-C15), halogen atoms (e.g., fluorine and iodine), hydroxyl groups, carboxyl groups, ester groups, sulfinyl groups, sulfonyl groups, alkylthio groups, or phenylthio groups. The above substituents may have further substituents if possible, and it is also preferable that the alkyl group has a halogen atom as a substituent, forming a halogenated alkyl group such as a trifluoromethyl group. The above substituents may also preferably form an acid-degradable group in any combination. Furthermore, an acid-degradable group is defined as a group that decomposes upon the action of an acid to produce a polar group, and it is preferable that the polar group is protected by a group that is eliminated by the action of an acid. The polar group and leaving group are the same as those in resin (A) described later.

[0096] Next, we will explain the cation (ZaI-2). The cation (ZaI-2) is R in formula (ZaI). 201 ~R 203 However, each of these independently represents a cation that is an organic group without an aromatic ring. The term "aromatic ring" also includes aromatic rings that contain heteroatoms. R 201 ~R 203 The number of carbon atoms in the organic group that does not have an aromatic ring is preferably 1 to 30, and more preferably 1 to 20. R 201 ~R 203 The preferred members are, independently, alkyl groups, cycloalkyl groups, allyl groups, or vinyl groups, more preferably linear or branched 2-oxoalkyl groups, 2-oxocycloalkyl groups, or alkoxycarbonylmethyl groups, and even more preferably linear or branched 2-oxoalkyl groups.

[0097] R 201 ~R 203Examples of alkyl and cycloalkyl groups include linear alkyl groups having 1 to 10 carbon atoms or branched alkyl groups having 3 to 10 carbon atoms (e.g., methyl group, ethyl group, propyl group, butyl group, and pentyl group), and cycloalkyl groups having 3 to 10 carbon atoms (e.g., cyclopentyl group, cyclohexyl group, and norbornyl group). R 201 ~R 203 This may be further substituted with a halogen atom, an alkoxy group (e.g., having 1 to 5 carbon atoms), a hydroxyl group, a cyano group, or a nitro group. R 201 ~R 203 It is also preferable that each substituent independently forms an acid-degradable group in any combination of substituents.

[0098] Next, we will explain the cation (ZaI-3b). The cation (ZaI-3b) is a cation represented by the following formula (ZaI-3b).

[0099] [ka]

[0100] In formula (ZaI-3b), R 1c ~R 5c Each of these independently represents a hydrogen atom, an alkyl group, a cycloalkyl group, an aryl group, an alkoxy group, an aryloxy group, an alkoxycarbonyl group, an alkylcarbonyloxy group, a cycloalkylcarbonyloxy group, a halogen atom, a hydroxyl group, a nitro group, an alkylthio group, or an arylthio group. R 6c and R 7c Each of these independently represents a hydrogen atom, an alkyl group (e.g., a t-butyl group), a cycloalkyl group, a halogen atom, a cyano group, or an aryl group. R x and R y Each of these independently represents an alkyl group, a cycloalkyl group, a 2-oxoalkyl group, a 2-oxocycloalkyl group, an alkoxycarbonylalkyl group, an allyl group, or a vinyl group. R 1c ~R 7c , and R x and R y It is also preferable that each substituent independently forms an acid-degradable group in any combination of substituents.

[0101] R 1c ~R 5c Two or more of the following, R 5c and R 6c , R 6c and R 7c , R 5c and R x , and R x and R y These elements may bond to each other to form a ring, and each of these rings may independently contain an oxygen atom, a sulfur atom, a ketone group, an ester bond, or an amide bond. Examples of the above-mentioned rings include aromatic or non-aromatic hydrocarbon rings, aromatic or non-aromatic heterorings, and polycyclic fused rings formed by the combination of two or more of these rings. Examples of rings include 3- to 10-membered rings, with 4- to 8-membered rings being preferred, and 5- or 6-membered rings being more preferred.

[0102] R 1c ~R 5c Two or more of the following, R 6c and R 7c , and R x and R y Examples of groups formed by the bonding of these atoms include alkylene groups such as butylene and pentylene groups. The methylene group in this alkylene group may be substituted with a heteroatom such as an oxygen atom. R 5c and R 6c , and R 5c and R x The groups formed by the bonding of these elements are preferably single bonds or alkylene groups. Examples of alkylene groups include methylene groups and ethylene groups.

[0103] R 1c ~R 5c , R 6c , R 7c , R x , Ry , and R 1c ~R 5c Two or more of the following, R 5c and R 6c , R 6c and R 7c , R 5c and R x , and R x and R y The rings formed by the bonding of these elements to each other may have substituents.

[0104] Next, we will explain the cation (ZaI-4b). The cation (ZaI-4b) is a cation represented by the following formula (ZaI-4b).

[0105] [ka]

[0106] In equation (ZaI-4b), l represents an integer between 0 and 2, and r represents an integer between 0 and 8. R 13 This represents a group containing a hydrogen atom, a halogen atom (e.g., a fluorine atom and an iodine atom), a hydroxyl group, an alkyl group, an alkyl halide, an alkoxy group, a carboxyl group, an alkoxycarbonyl group, or a cycloalkyl group (which may be a cycloalkyl group itself or a group containing a cycloalkyl group as part). These groups may have substituents. R 14 R represents a hydroxyl group, a halogen atom (e.g., a fluorine atom and an iodine atom), an alkyl group, an alkyl halide, an alkoxy group, an alkoxycarbonyl group, an alkylcarbonyl group, an alkylsulfonyl group, a cycloalkylsulfonyl group, or a group containing a cycloalkyl group (which may be a cycloalkyl group itself or a group containing a cycloalkyl group in part). These groups may have substituents. 14 If multiple instances exist, each independently represents one of the above-mentioned groups, such as a hydroxyl group. R 15Each of these independently represents an alkyl group, a cycloalkyl group, or a naphthyl group. 15 They may bond to each other to form a ring. Two R 15 When these atoms bond to each other to form a ring, the ring skeleton may contain heteroatoms such as oxygen atoms or nitrogen atoms. In one embodiment, two R 15 It is preferable that the alkyl group is an alkylene group and that they bond to each other to form a ring structure. The alkyl group, cycloalkyl group and naphthyl group and the two R 15 The ring formed by the bonding of these elements may have substituents.

[0107] In equation (ZaI-4b), R 13 , R 14 , and R 15 The alkyl group may be linear or branched. The alkyl group preferably has 1 to 10 carbon atoms. The alkyl group is preferably a methyl group, ethyl group, n-butyl group, or t-butyl group. R 13 ~R 15 , and R x and R y It is also preferable that each substituent independently forms an acid-degradable group in any combination of substituents.

[0108] Next, we will explain equation (ZaII). In formula (ZaII), R 204 and R 205 Each of these independently represents an aryl group, an alkyl group, or a cycloalkyl group. R 204 and R 205 The aryl group is preferably a phenyl group or a naphthyl group, with the phenyl group being more preferred. 204 and R 205 The aryl group may be an aryl group having a heterocycle containing an oxygen atom, a nitrogen atom, or a sulfur atom, etc. Examples of heterocycle aryl group skeletons include pyrrole, furan, thiophene, indole, benzofuran, and benzothiophene. R204 and R 205 The alkyl and cycloalkyl groups are preferably linear alkyl groups having 1 to 10 carbon atoms or branched alkyl groups having 3 to 10 carbon atoms (e.g., methyl group, ethyl group, propyl group, butyl group, or pentyl group), or cycloalkyl groups having 3 to 10 carbon atoms (e.g., cyclopentyl group, cyclohexyl group, or norbornyl group).

[0109] R 204 and R 205 The aryl group, alkyl group, and cycloalkyl group may each independently have substituents. 204 and R 205 Examples of substituents that the aryl group, alkyl group, and cycloalkyl group may have include alkyl groups (e.g., 1 to 15 carbon atoms), cycloalkyl groups (e.g., 3 to 15 carbon atoms), aryl groups (e.g., 6 to 15 carbon atoms), alkoxy groups (e.g., 1 to 15 carbon atoms), halogen atoms, hydroxyl groups, and phenylthio groups. 204 and R 205 It is also preferable that each substituent independently forms an acid-degradable group in any combination of substituents.

[0110] Specific examples of organic cations are shown below, but the present invention is not limited thereto.

[0111] [ka]

[0112] [ka]

[0113] [ka]

[0114] The method for producing the onium salt (C) using the acid compound (CA) in step (2) is not particularly limited. For example, an onium salt (C) can be produced by reacting a salt consisting of an anion of a conjugate acid whose pKa is greater than that of the acid compound (CA) and a cation of the target onium salt (C) with the acid compound (CA) in a solvent, thereby exchanging the anions.

[0115] For example, if the onium salt (C) is a sulfonium salt containing a carboxylate ion, the onium salt (C) represented by general formula (C1) can be produced by reacting a salt represented by general formula (ca) (a salt consisting of a sulfonium cation and a bicarbonate ion) with a carboxylic acid represented by general formula (cb), which is the acid compound (CA), in a solvent, as shown in the formula below.

[0116] [ka]

[0117] In general formulas (ca) and (C1), R 201 , R 202 , and R 203 These are R in the above equation (ZaI), respectively. 201 , R 202 , and R 203 This expresses the same meaning, and the specific examples and preferred ranges are also the same. Q in general formulas (cb) and (C1) c3 represents an organic group. Examples of acid compounds represented by the general formula (cb) include compounds in which m1 of the aforementioned general formula (CA1) is 1, and compounds represented by the general formula (CA2).

[0118] The solvent used in the above reaction is not particularly limited and may be an organic solvent or water, for example, methylene chloride, chloroform, methanol, acetonitrile, water, etc.

[0119] The above reactions are typically carried out at a temperature range of 15–80°C for 0.5–24 hours, but are not limited to this range.

[0120] ·Process (3) Step (3) is a step of mixing the onium salt (C) obtained in step (2) with a resin (A) whose polarity increases due to the action of an acid.

[0121] The content of onium salt (C) in the photosensitive or radiation-sensitive resin composition (total if multiple types exist) is preferably 1% by mass or more, more preferably 5% by mass or more, and even more preferably 10% by mass or more, based on the total solid content of the photosensitive or radiation-sensitive resin composition. Furthermore, the content of onium salt (C) (total if multiple types exist) is preferably 40% by mass or less, more preferably 35% by mass, and even more preferably 30% by mass or less, based on the total solid content of the photosensitive or radiation-sensitive resin composition. In a photosensitive or radiation-sensitive resin composition, the onium salt (C) may be used alone or in combination of two or more types.

[0122] This section describes resin (A) (also simply referred to as "resin (A)") whose polarity increases with the action of acid. Resin (A) is an acid-degradable resin. Resin (A) typically contains groups that decompose and increase in polarity due to the action of acid (hereinafter also referred to as "acid-degradable groups"), and preferably contains repeating units having acid-degradable groups. When resin (A) has acid-degradable groups, in the pattern forming method described herein, typically, when an alkaline developer is used as the developer, a positive-type pattern is suitably formed, and when an organic developer is used as the developer, a negative-type pattern is suitably formed. In addition to the repeating units having acid-degradable groups described later, repeating units having acid-degradable groups that include unsaturated bonds are preferred as repeating units having acid-degradable groups.

[0123] (Repeating unit with acid-degradable group) An acid-degradable group is a group that decomposes upon the action of an acid to produce a polar group. Preferably, the acid-degradable group has a structure in which the polar group is protected by a leaving group (a group that is released upon the action of an acid). In other words, resin (A) has repeating units that decompose upon the action of an acid to produce a polar group. Resins having these repeating units become more polar upon the action of an acid, increasing their solubility in alkaline developers and decreasing their solubility in organic solvents. Preferred polar groups are alkali-soluble groups, such as carboxyl groups, phenolic hydroxyl groups, fluorinated alcohol groups, sulfonic acid groups, phosphoric acid groups, sulfonamide groups, sulfonylimide groups, (alkylsulfonyl)(alkylcarbonyl)methylene groups, (alkylsulfonyl)(alkylcarbonyl)imide groups, bis(alkylcarbonyl)methylene groups, bis(alkylcarbonyl)imide groups, bis(alkylsulfonyl)methylene groups, bis(alkylsulfonyl)imide groups, tris(alkylcarbonyl)methylene groups, and tris(alkylsulfonyl)methylene groups, as well as alcoholic hydroxyl groups. Among these, carboxyl groups, phenolic hydroxyl groups, fluorinated alcohol groups (preferably hexafluoroisopropanol groups), or sulfonic acid groups are preferred as polar groups.

[0124] Examples of groups that are eliminated by the action of an acid include those represented by formulas (Y1) to (Y4). Formula (Y1):-C(Rx1)(Rx2)(Rx3) Formula (Y2):-C(=O)OC(Rx1)(Rx2)(Rx3) Formula (Y3):-C(R 36 )(R 37 )(OR 38 ) Formula (Y4):-C(Rn)(H)(Ar)

[0125] In formulas (Y1) and (Y2), Rx1 to Rx3 each independently represent an alkyl group (linear or branched), a cycloalkyl group (monocyclic or polycyclic), an alkenyl group (linear or branched), or an aryl group (monocyclic or polycyclic). When all of Rx1 to Rx3 are alkyl groups (linear or branched), it is preferable that at least two of Rx1 to Rx3 are methyl groups. In particular, it is preferable that Rx1 to Rx3 each independently represent a linear or branched alkyl group, and it is more preferable that Rx1 to Rx3 each independently represent a linear alkyl group. Two of Rx1 to Rx3 may combine to form a monocycle or polycycle. The alkyl groups Rx1 to Rx3 are preferably C1 to C5 alkyl groups such as methyl group, ethyl group, n-propyl group, isopropyl group, n-butyl group, isobutyl group, and t-butyl group. The cycloalkyl groups Rx1 to Rx3 are preferably monocyclic cycloalkyl groups such as cyclopentyl and cyclohexyl groups, and polycyclic cycloalkyl groups such as norbornyl, tetracyclodecanyl, tetracyclododecanyl, and adamantyl groups. The aryl groups Rx1 to Rx3 are preferably aryl groups having 6 to 10 carbon atoms, such as phenyl groups, naphthyl groups, and anthyl groups. Vinyl groups are preferred for the alkenyl groups Rx1 to Rx3. A cycloalkyl group is preferred as the ring formed by the bonding of two Rx1 to Rx3. The cycloalkyl group formed by the bonding of two Rx1 to Rx3 is preferably a monocyclic cycloalkyl group such as a cyclopentyl group or a cyclohexyl group, or a polycyclic cycloalkyl group such as a norbornyl group, a tetracyclodecanyl group, a tetracyclododecanyl group, or an adamantyl group, and more preferably a monocyclic cycloalkyl group having 5 to 6 carbon atoms. In cycloalkyl groups formed by the bonding of two Rx1 to Rx3, one of the methylene groups constituting the ring may be replaced by a heteroatom such as an oxygen atom, a group containing a heteroatom such as a carbonyl group, or a vinylidene group. In these cycloalkyl groups, one or more of the ethylene groups constituting the cycloalkane ring may be replaced by vinylene groups. The group represented by formula (Y1) or formula (Y2) is preferably such that, for example, Rx1 is a methyl group or an ethyl group, and Rx2 and Rx3 are bonded to form the cycloalkyl group described above. When the photosensitive or radiation-sensitive resin composition is, for example, a resist composition for EUV exposure, it is preferable that the alkyl group, cycloalkyl group, alkenyl group, aryl group represented by Rx1 to Rx3, and the ring formed by the bonding of two Rx1 to Rx3, further have a fluorine atom or an iodine atom as a substituent.

[0126] In formula (Y3), R 36 ~R 38 Each of these independently represents a hydrogen atom or a monovalent organic group. 37 and R 38 These may bond to each other to form a ring. Examples of monovalent organic groups include alkyl groups, cycloalkyl groups, aryl groups, aralkyl groups, and alkenyl groups. 36 It is also preferable that it be a hydrogen atom. Furthermore, the alkyl groups, cycloalkyl groups, aryl groups, and aralkyl groups mentioned above may include groups containing heteroatoms such as oxygen atoms and / or carbonyl groups. For example, in the alkyl groups, cycloalkyl groups, aryl groups, and aralkyl groups mentioned above, one or more methylene groups may be replaced with groups containing heteroatoms such as oxygen atoms and / or carbonyl groups. R 38 It may bond with other substituents on the repeating main chain to form a ring. 38 The group formed by the bonding of this molecule with another substituent on the repeating main chain is preferably an alkylene group such as a methylene group. If the photosensitive or radiation-sensitive resin composition is, for example, a resist composition for EUV exposure, then R 36 ~R 38 A monovalent organic group represented by, and R 37 and R 38 The ring formed by the bonding of these elements may further preferably have a fluorine atom or an iodine atom as a substituent.

[0127] The group represented by formula (Y3-1) below is preferred for formula (Y3).

[0128] [ka]

[0129] Here, L1 and L2 each independently represent a hydrogen atom, an alkyl group, a cycloalkyl group, an aryl group, or a group combining these (for example, a group combining an alkyl group and an aryl group). M represents a single bond or a divalent linking group. Q represents an alkyl group which may contain a heteroatom, a cycloalkyl group which may contain a heteroatom, an aryl group which may contain a heteroatom, an amino group which may contain a heteroatom, an ammonium group which may contain a heteroatom, a mercapto group which may contain a cyano group which may contain an aldehyde group which may contain a heteroatom, or a group which is a combination thereof (for example, a group which is a combination of an alkyl group and a cycloalkyl group). Alkyl and cycloalkyl groups may have, for example, one of their methylene groups replaced by a heteroatom such as an oxygen atom, or a group containing a heteroatom such as a carbonyl group. Preferably, one of L1 and L2 is a hydrogen atom, and the other is an alkyl group, a cycloalkyl group, an aryl group, or a group formed by combining an alkylene group and an aryl group. At least two of Q, M, and L1 may be joined to form a ring (preferably a 5-membered or 6-membered ring). In terms of pattern refinement, L2 is preferably a secondary or tertiary alkyl group, and more preferably a tertiary alkyl group. Examples of secondary alkyl groups include isopropyl, cyclohexyl, and norbornyl groups, while examples of tertiary alkyl groups include tert-butyl and adamantane groups. In these embodiments, the glass transition temperature (Tg) and activation energy are increased, which ensures film strength and suppresses fogging.

[0130] When the photosensitive or radiation-sensitive resin composition is, for example, an EUV lithography resist composition, the alkyl groups, cycloalkyl groups, aryl groups, and combinations thereof represented by L1 and L2 may further have a fluorine atom or an iodine atom as a substituent. In addition to fluorine and iodine atoms, the alkyl groups, cycloalkyl groups, aryl groups, and aralkyl groups may also contain heteroatoms such as oxygen atoms. Specifically, in the alkyl groups, cycloalkyl groups, aryl groups, and aralkyl groups, for example, one of the methylene groups may be replaced with a heteroatom such as an oxygen atom, or a group containing a heteroatom such as a carbonyl group. When the photosensitive or radiation-sensitive resin composition is, for example, an EUV exposure resist composition, it is also preferable that the heteroatom in the alkyl group which may contain a heteroatom represented by Q, the cycloalkyl group which may contain a heteroatom, the aryl group which may contain a heteroatom, the amino group which may contain a heteroatom, the ammonium group which may contain a heteroatom, the mercapto group which may contain a cyano group which may contain an aldehyde group which may contain a heteroatom, and the groups which may contain a heteroatom, is a heteroatom selected from the group consisting of a fluorine atom which may contain a iodine atom which may contain an oxygen atom.

[0131] In formula (Y4), Ar represents an aromatic ring group. Rn represents an alkyl group, a cycloalkyl group, or an aryl group. Rn and Ar may bond to each other to form a non-aromatic ring. An aryl group is preferred as Ar. When the photosensitive or radiation-sensitive resin composition is, for example, a resist composition for EUV exposure, it is also preferable that the aromatic ring group represented by Ar, and the alkyl, cycloalkyl, and aryl groups represented by Rn, have a fluorine atom or an iodine atom as a substituent.

[0132] From the standpoint of excellent acid decomposition properties of repeating units, in the case of a leaving group that protects a polar group, if a non-aromatic ring is directly bonded to the polar group (or its residue), it is preferable that the ring member atoms in the non-aromatic ring adjacent to the ring member atom directly bonded to the polar group (or its residue) do not have halogen atoms such as fluorine atoms as substituents.

[0133] Other groups that may be removed by the action of an acid include a 2-cyclopentenyl group having a substituent (such as an alkyl group), such as a 3-methyl-2-cyclopentenyl group, and a cyclohexyl group having a substituent (such as an alkyl group), such as a 1,1,4,4-tetramethylcyclohexyl group.

[0134] As a repeating unit having an acid-degradable group, the repeating unit represented by formula (A) is also preferred.

[0135] [ka]

[0136] L1 represents a divalent linking group which may have a fluorine atom or an iodine atom; R1 represents a hydrogen atom, a fluorine atom, an iodine atom, an alkyl group which may have a fluorine atom or an iodine atom, or an aryl group which may have a fluorine atom or an iodine atom; and R2 represents a leaving group which is eliminated by the action of an acid and which may have a fluorine atom or an iodine atom. However, at least one of L1, R1, and R2 has a fluorine atom or an iodine atom. Examples of divalent linking groups represented by L1, which may have a fluorine atom or an iodine atom, include -CO-, -O-, -S-, -SO-, -SO2-, hydrocarbon groups which may have a fluorine atom or an iodine atom (e.g., alkylene groups, cycloalkylene groups, alkenylene groups, and arylene groups, etc.), and linking groups formed by linking multiple of these. Among these, L1 is preferably -CO-, an arylene group, or an arylene group-an alkylene group having a fluorine atom or an iodine atom-, and more preferably -CO-, or an arylene group-an alkylene group having a fluorine atom or an iodine atom-. A phenylene group is preferred as the arylene group. The alkylene group may be linear or branched. The number of carbon atoms in the alkylene group is not particularly limited, but 1 to 10 is preferred, and 1 to 3 is more preferred. The total number of fluorine atoms and iodine atoms contained in an alkylene group having a fluorine atom or an iodine atom is not particularly limited, but is preferably 2 or more, more preferably 2 to 10, and even more preferably 3 to 6.

[0137] The alkyl group represented by R1 may be linear or branched. The number of carbon atoms in the alkyl group is not particularly limited, but 1 to 10 is preferred, and 1 to 3 is more preferred. The total number of fluorine atoms and iodine atoms in the alkyl group having a fluorine atom or an iodine atom, represented by R1, is not particularly limited, but is preferably 1 or more, more preferably 1 to 5, and even more preferably 1 to 3. The alkyl group represented by R1 may contain heteroatoms other than halogen atoms, such as oxygen atoms.

[0138] Examples of leaving groups represented by R2 that may have a fluorine atom or an iodine atom include the leaving groups represented by the above formulas (Y1) to (Y4) and that have a fluorine atom or an iodine atom.

[0139] As a repeating unit having an acid-degradable group, a repeating unit represented by formula (AI) is also preferred.

[0140] [ka]

[0141] In formula (AI), Xa1 represents a hydrogen atom or an optionally substituted alkyl group. T represents a single bond or a divalent linking group. Rx1 to Rx3 each independently represent an alkyl group (linear or branched), a cycloalkyl group (monocyclic or polycyclic), an alkenyl group (linear or branched), or an aryl group (monocyclic or polycyclic). However, if all of Rx1 to Rx3 are alkyl groups (linear or branched), it is preferable that at least two of Rx1 to Rx3 are methyl groups. Two of Rx1 to Rx3 may bond together to form a monocyclic or polycyclic (such as a monocyclic or polycyclic cycloalkyl group).

[0142] Examples of alkyl groups that may have substituents, represented by Xa1, include a methyl group or a -CH2-R 11 The group represented by R is an example. 11 R represents a halogen atom (such as a fluorine atom), a hydroxyl group, or a monovalent organic group. 11 Examples of monovalent organic groups represented by include alkyl groups having 5 or fewer carbon atoms that may be substituted with halogen atoms, acyl groups having 5 or fewer carbon atoms that may be substituted with halogen atoms, and alkoxy groups having 5 or fewer carbon atoms that may be substituted with halogen atoms, with alkyl groups having 3 or fewer carbon atoms being preferred and methyl groups being more preferred. For Xa1, hydrogen atoms, methyl groups, trifluoromethyl groups, or hydroxymethyl groups are preferred.

[0143] Examples of divalent linking groups for T include alkylene groups, aromatic ring groups, -COO-Rt- groups, and -O-Rt- groups. In the formula, Rt represents an alkylene group or a cycloalkylene group. 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.

[0144] The alkyl groups Rx1 to Rx3 are preferably C1 to C4 alkyl groups such as methyl group, ethyl group, n-propyl group, isopropyl group, n-butyl group, isobutyl group, and t-butyl group. The cycloalkyl groups Rx1 to Rx3 are preferably monocyclic cycloalkyl groups such as cyclopentyl and cyclohexyl groups, or polycyclic cycloalkyl groups such as norbornyl, tetracyclodecanyl, tetracyclododecanyl, and adamantyl groups. The aryl groups Rx1 to Rx3 are preferably aryl groups having 6 to 10 carbon atoms, such as phenyl groups, naphthyl groups, and anthyl groups. Vinyl groups are preferred for the alkenyl groups Rx1 to Rx3. The cycloalkyl group formed by the bonding of two Rx1 to Rx3 is preferably a monocyclic cycloalkyl group such as a cyclopentyl group or a cyclohexyl group. Polycyclic cycloalkyl groups such as a norbornyl group, tetracyclodecanyl group, tetracyclododecanyl group, and adamantyl group are also preferred. Among these, monocyclic cycloalkyl groups having 5 to 6 carbon atoms are preferred. In a cycloalkyl group formed by the bonding of two Rx1 to Rx3, for example, one of the methylene groups constituting the ring may be replaced by a heteroatom such as an oxygen atom, a group containing a heteroatom such as a carbonyl group, or a vinylidene group. Furthermore, in these cycloalkyl groups, one or more of the ethylene groups constituting the cycloalkane ring may be replaced by vinylene groups. The repeating unit represented by formula (AI) is preferably configured such that, for example, Rx1 is a methyl group or an ethyl group, and Rx2 and Rx3 are bonded together to form the cycloalkyl group described above.

[0145] When each of the above groups has 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 substituent is preferably 8 or less.

[0146] The repeating unit represented by formula (AI) is preferably an acid-degradable (meth)acrylate tertiary alkyl ester repeating unit (a repeating unit in which Xa1 represents a hydrogen atom or a methyl group, and T represents a single bond).

[0147] Specific examples of repeating units having acid-degradable groups are shown below, but are not limited to these. In the formula, Xa1 represents H, CH3, CF3, or CH2OH, and Rxa and Rxb each independently represent a linear or branched alkyl group having 1 to 5 carbon atoms.

[0148] [ka]

[0149] [ka]

[0150] [ka]

[0151] [ka]

[0152] [ka]

[0153] Resin (A) may have repeating units having acid-degradable groups, including repeating units having acid-degradable groups containing unsaturated bonds. As a repeating unit having an acid-degradable group containing an unsaturated bond, the repeating unit represented by formula (B) is preferred.

[0154] [ka]

[0155] In formula (B), Xb represents a hydrogen atom, a halogen atom, or an optionally substituted alkyl group. L represents a single bond or an optionally substituted divalent linking group. Ry1 to Ry3 each independently represent a linear or branched alkyl group, a monocyclic or polycyclic cycloalkyl group, an alkenyl group, an alkynyl group, or a monocyclic or polycyclic aryl group. However, at least one of Ry1 to Ry3 represents an alkenyl group, an alkynyl group, a monocyclic or polycyclic cycloalkenyl group, or a monocyclic or polycyclic aryl group. Two of the Ry1-Ry3 groups may bond to form a monocyclic or polycyclic group (such as a monocyclic or polycyclic cycloalkyl group or cycloalkenyl group).

[0156] Examples of alkyl groups that may have substituents, represented by Xb, include a methyl group or a -CH2-R 11 The group represented by R is an example. 11 Xb represents a halogen atom (such as a fluorine atom), a hydroxyl group, or a monovalent organic group. Examples include alkyl groups having 5 or fewer carbon atoms that may be substituted with a halogen atom, acyl groups having 5 or fewer carbon atoms that may be substituted with a halogen atom, and alkoxy groups having 5 or fewer carbon atoms that may be substituted with a halogen atom. Alkyl groups having 3 or fewer carbon atoms are preferred, and methyl groups are more preferred. Xb is preferably a hydrogen atom, a fluorine atom, a methyl group, a trifluoromethyl group, or a hydroxymethyl group.

[0157] Examples of divalent linking groups for L include -Rt-, -CO-, -COO-Rt-, -COO-Rt-CO-, -Rt-CO-, and -O-Rt-. In the formula, Rt represents an alkylene group, a cycloalkylene group, or an aromatic ring group, with an aromatic ring group being preferred. L is preferably a -Rt- group, a -CO- group, a -COO-Rt-CO- group, or a -Rt-CO- group. Rt may have substituents such as a halogen atom, a hydroxyl group, or an alkoxy group.

[0158] The alkyl groups Ry1 to Ry3 are preferably C1 to C4 alkyl groups such as methyl, ethyl, n-propyl, isopropyl, n-butyl, isobutyl, and t-butyl groups. The cycloalkyl groups Ry1 to Ry3 are preferably monocyclic cycloalkyl groups such as cyclopentyl and cyclohexyl groups, or polycyclic cycloalkyl groups such as norbornyl, tetracyclodecanyl, tetracyclododecanyl, and adamantyl groups. The aryl groups Ry1 to Ry3 are preferably aryl groups having 6 to 10 carbon atoms, such as phenyl groups, naphthyl groups, and anthyl groups. A vinyl group is preferred as the alkenyl group for Ry1 to Ry3. Ethynyl groups are preferred as the alkynyl groups of Ry1 to Ry3. For the cycloalkenyl groups of Ry1 to Ry3, structures containing a double bond in part of a monocyclic cycloalkyl group such as a cyclopentyl group and a cyclohexyl group are preferred. The cycloalkyl group formed by the bonding of two Ry1 to Ry3 is preferably a monocyclic cycloalkyl group such as a cyclopentyl group or a cyclohexyl group, or a polycyclic cycloalkyl group such as a norbornyl group, a tetracyclodecanyl group, a tetracyclododecanyl group, or an adamantyl group. Among these, a monocyclic cycloalkyl group having 5 to 6 carbon atoms is more preferred. A cycloalkyl group or cycloalkenyl group formed by the bonding of two Ry1 to Ry3 may have, for example, one of the methylene groups constituting the ring replaced by a heteroatom such as an oxygen atom, a carbonyl group, a group containing heteroatoms such as -SO2- and -SO3- groups, a vinylidene group, or a combination thereof. Furthermore, in these cycloalkyl groups or cycloalkenyl groups, one or more of the ethylene groups constituting the cycloalkane ring or cycloalkene ring may be replaced by a vinylene group. In the repeating unit represented by formula (B), it is preferable that, for example, Ry1 is a methyl group, an ethyl group, a vinyl group, an allyl group, or an aryl group, and Ry2 and Ry3 are bonded together to form the above-mentioned cycloalkyl group or cycloalkenyl group.

[0159] When each of the above groups has 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 substituent is preferably 8 or less.

[0160] The repeating units represented by formula (B) are preferably acid-degradable (meth)acrylic acid tertiary ester repeating units (where Xb represents a hydrogen atom or a methyl group and L represents a -CO- group), acid-degradable hydroxystyrene tertiary alkyl ether repeating units (where Xb represents a hydrogen atom or a methyl group and L represents a phenyl group), or acid-degradable styrene carboxylic acid tertiary ester repeating units (where Xb represents a hydrogen atom or a methyl group and L represents a -Rt-CO- group (where Rt is an aromatic group)).

[0161] The content of repeating units having acid-degradable groups containing unsaturated bonds is preferably 15 mol% or more, more preferably 20 mol% or more, and even more preferably 30 mol% or more, relative to the total repeating units in resin (A). Furthermore, the upper limit is preferably 80 mol% or less, more preferably 70 mol% or less, and even more preferably 60 mol% or less, relative to the total repeating units in resin (A).

[0162] Specific examples of repeating units having an acid-degradable group containing an unsaturated bond are shown below, but are not limited thereto. In the formula, Xb and L1 represent any of the substituents or linking groups described above, Ar represents an aromatic group, R represents a substituent such as a hydrogen atom, alkyl group, cycloalkyl group, aryl group, aralkyl group, alkenyl group, hydroxyl group, alkoxy group, acyloxy group, cyano group, nitro group, amino group, halogen atom, ester group (-OCOR''' or -COOR''', R''' is an alkyl group or fluorinated alkyl group having 1 to 20 carbon atoms), or carboxyl group, R' represents a linear or branched alkyl group, monocyclic or polycyclic cycloalkyl group, alkenyl group, alkynyl group, or monocyclic or polycyclic aryl group, Q represents a heteroatom such as an oxygen atom, a carbonyl group, a group containing a heteroatom such as a -SO2- group and a -SO3- group, a vinylidene group, or a combination thereof, and n, m, and l represent integers of 0 or more.

[0163] [ka]

[0164] [ka]

[0165] [ka]

[0166] [ka]

[0167] It is particularly preferable that the resin (A) has at least one selected from the group consisting of repeating units represented by the following general formula (A1), repeating units represented by the following general formula (A2), and repeating units represented by the following general formula (A3).

[0168] [ka]

[0169] In general formula (A1), R a1 , R a2 and R a3 Each of these independently represents a hydrogen atom, an alkyl group, a cycloalkyl group, a halogen atom, a cyano group, or an alkoxycarbonyl group. a1 Ar represents a single bond or a divalent linking group. a1 R represents an aromatic ring group. a4 R represents a hydrogen atom, alkyl group, cycloalkyl group, aryl group, aralkyl group, or alkenyl group. a5 and R a6 Each of these independently represents an alkyl group, a cycloalkyl group, an aryl group, an aralkyl group, or an alkenyl group. a4 and R a5 They may combine with each other to form a ring. a1 is R a3 or R a4 It may also combine with other elements to form a ring. In general formula (A2), R a7 , R a8 and R a9 Each of these independently represents a hydrogen atom, an alkyl group, a cycloalkyl group, a halogen atom, a cyano group, or an alkoxycarbonyl group. a2 Ar represents a single bond or a divalent linking group. a2 R represents an aromatic ring group. a10 , R a11 and R a12 Each of these independently represents an alkyl group, a cycloalkyl group, an aryl group, an aralkyl group, or an alkenyl group. a10 , R a11 and R a12 Two of them may be joined together to form a ring. In general formula (A3), R a13 , R a14 and R a15 Each of these independently represents a hydrogen atom, an alkyl group, a cycloalkyl group, a halogen atom, a cyano group, or an alkoxycarbonyl group. a3 Ar represents a single bond or a divalent linking group. a3 R represents an aromatic ring group.a16 , R a17 and R a18 Each of these independently represents an alkyl group, a cycloalkyl group, an aryl group, an aralkyl group, or an alkenyl group. a16 , R a17 and R a18 Two of them may be joined together to form a ring.

[0170] The repeating units represented by general formula (A1), general formula (A2), and general formula (A3) are repeating units that have an acid-degradable group.

[0171] The repeating unit represented by general formula (A1) will be explained. R a1 , R a2 and R a3 The alkyl group represented by may be either linear or branched. The number of carbon atoms in the alkyl group is not particularly limited, but 1 to 5 is preferred, and 1 to 3 is more preferred. R a1 , R a2 and R a3 The cycloalkyl groups represented by are preferably monocyclic cycloalkyl groups such as cyclopentyl and cyclohexyl groups, and polycyclic cycloalkyl groups such as norbornyl, tetracyclodecanyl, tetracyclododecanyl, and adamantyl groups. R a1 , R a2 and R a3 Examples of halogen atoms represented by include fluorine atoms, chlorine atoms, bromine atoms, and iodine atoms, with fluorine atoms or iodine atoms being preferred. R a1 , R a2 and R a3 The alkyl group contained in the alkoxycarbonyl group represented by may be either linear or branched. The number of carbon atoms in the alkyl group contained in the alkoxycarbonyl group is not particularly limited, but 1 to 5 is preferred, and 1 to 3 is more preferred.

[0172] L a1Examples of divalent linking groups when represents a divalent linking group include -CO-, -O-, -S-, -SO-, -SO2-, hydrocarbon groups (e.g., alkylene groups, cycloalkylene groups, alkenylene groups, arylene groups, etc.), and linking groups formed by linking multiple of these groups.

[0173] Ar a1 The aromatic ring group represented by is not particularly limited, but examples include a phenylene group or a naphthylene group, with a phenylene group being preferred.

[0174] R a4 , R a5 and R a6 The alkyl group represented by may be either linear or branched. The number of carbon atoms in the alkyl group is not particularly limited, but 1 to 5 is preferred, and 1 to 3 is more preferred. a4 , R a5 and R a6 The alkyl group represented by may have a methylene group substituted with at least one of -CO- and -O-. R a4 , R a5 and R a6 The cycloalkyl groups represented by are preferably monocyclic cycloalkyl groups such as cyclopentyl and cyclohexyl groups, and polycyclic cycloalkyl groups such as norbornyl, tetracyclodecanyl, tetracyclododecanyl, and adamantyl groups. R a4 , R a5 and R a6 A phenyl group is preferred as the aryl group represented by . R a4 , R a5 and R a6 The aralkyl group represented by the above-mentioned R a4 , R a5 and R a6 A preferred group is one in which one hydrogen atom in the alkyl group represented by is replaced with an aryl group (preferably a phenyl group) having 6 to 10 carbon atoms, for example, a benzyl group. R a4 , R a5 and R a6A vinyl group is preferred as the alkenyl group represented by . R a4 and R a5 A cycloalkyl group is preferred as the ring formed by the bonding of the two. a4 and R a5 The cycloalkyl group formed by the bonding of these groups is preferably a monocyclic cycloalkyl group such as a cyclopentyl group or a cyclohexyl group, or a polycyclic cycloalkyl group such as a norbornyl group, a tetracyclodecanyl group, a tetracyclododecanyl group, or an adamantyl group, with monocyclic cycloalkyl groups having 5 to 6 carbon atoms being more preferred. R a4 and R a5 The cycloalkyl group formed by the bonding of these two groups may, for example, have one of the methylene groups constituting the ring replaced by a heteroatom such as an oxygen atom, a group having a heteroatom such as a carbonyl group, or a vinylidene group. Furthermore, in these cycloalkyl groups, one or more of the ethylene groups constituting the cycloalkane ring may be replaced by vinylene groups.

[0175] Each of the above groups in general formula (A1) may have substituents, and examples of substituents include the substituent T.

[0176] The repeating unit represented by general formula (A2) will be explained. R a7 , R a8 and R a9 R in general formula (A1) a1 , R a2 and R a3 This is synonymous with the same thing, and the preferred embodiment is also the same. L a2 L in general formula (A1) a1 This is synonymous with the same thing, and the preferred embodiment is also the same. Ar a2 This is Ar in general formula (A1). a1 This is synonymous with the same thing, and the preferred embodiment is also the same. R a10 , R a11 and R a12 R in general formula (A1) a4 , Ra5 and R a6 This is synonymous with the same thing, and the preferred embodiment is also the same. R a10 , R a11 and R a12 A cycloalkyl group is preferred as the ring formed by the bonding of two of these groups. a10 , R a11 and R a12 The cycloalkyl group formed by the bonding of two of these groups is preferably a monocyclic cycloalkyl group such as a cyclopentyl group or a cyclohexyl group, or a polycyclic cycloalkyl group such as a norbornyl group, a tetracyclodecanyl group, a tetracyclododecanyl group, or an adamantyl group, with monocyclic cycloalkyl groups having 5 to 6 carbon atoms being more preferred. R a10 , R a11 and R a12 In a cycloalkyl group formed by the bonding of two of these groups, for example, one of the methylene groups constituting the ring may be replaced by a heteroatom such as an oxygen atom, a group having a heteroatom such as a carbonyl group, or a vinylidene group. Furthermore, in these cycloalkyl groups, one or more of the ethylene groups constituting the cycloalkane ring may be replaced by vinylene groups.

[0177] Each of the above groups in general formula (A2) may have substituents, and examples of substituents include the substituent T.

[0178] This section explains the repeating units represented by the general formula (A3). R a13 , R a14 and R a15 R in general formula (A1) a1 , R a2 and R a3 This is synonymous with the same thing, and the preferred embodiment is also the same. L a3 L in general formula (A1) a1 This is synonymous with the same thing, and the preferred embodiment is also the same. Ar a3 This is Ar in general formula (A1). a1 This is synonymous with the same thing, and the preferred embodiment is also the same. R a16 , R a17 and R a18 R in general formula (A1) a4 , R a5 and R a6 This is synonymous with the same thing, and the preferred embodiment is also the same. R a16 , R a17 and R a18 The ring formed when two of these are bonded together is R in general formula (A2). a10 , R a11 and R a12 It is similar to a ring formed when two of them are joined together.

[0179] Each of the above groups in general formula (A3) may have substituents, and examples of substituents include the substituent T.

[0180] Specific examples of repeating units represented by general formula (A1), general formula (A2), and general formula (A3) are shown below, but are not limited to these.

[0181] [ka]

[0182] [ka]

[0183] The content of repeating units having acid-degradable groups is preferably 15 mol% or more, more preferably 20 mol% or more, and even more preferably 30 mol% or more, relative to the total repeating units in resin (A). Furthermore, the upper limit is preferably 90 mol% or less, more preferably 80 mol% or less, even more preferably 70 mol% or less, and particularly preferably 60 mol% or less, relative to the total repeating units in resin (A).

[0184] The resin (A) may contain at least one repeating unit selected from the group consisting of group A below, and / or at least one repeating unit selected from the group consisting of group B below. Group A: A group consisting of the following repeating units (20) to (25). (20) Repeating units having an acid group, as described later (21) Repeating units having a fluorine atom, a bromine atom, or an iodine atom, which are described later and do not have either an acid-degradable group or an acid group. (22) Repeating units having a lactone group, a sultone group, or a carbonate group, as described later (23) Repeating units having a photoacid generating group, as described later (24) Repeating units represented by formula (V-1) or formula (V-2) below, as described later. (25) Repeating units for reducing the mobility of the main chain Furthermore, the repeating units represented by formulas (A) to (E), which will be described later, correspond to (25) repeating units for reducing the mobility of the main chain. Group B: A group consisting of the following repeating units (30) to (32). (30) Repeating units having at least one group selected from lactone groups, sultone groups, carbonate groups, hydroxyl groups, cyano groups, and alkali-soluble groups, as described later. (31) Repeating units having an alicyclic hydrocarbon structure and not exhibiting acid decomposition, as described later. (32) Repeating units represented by formula (III) that do not have either a hydroxyl group or a cyano group, as described later.

[0185] The resin (A) preferably has acidic groups, and more preferably contains repeating units having acidic groups, as will be described later. The definition of acidic groups will be explained later, along with preferred embodiments of the repeating units having acidic groups. When resin (A) has acidic groups, the interaction between resin (A) and the acid generated from the photoacid generator is improved. As a result, acid diffusion is further suppressed, and the cross-sectional shape of the formed pattern can become more rectangular.

[0186] The resin (A) may have at least one repeating unit selected from the group consisting of A above. When the photosensitive or radiation-sensitive resin composition is used as a photosensitive or radiation-sensitive resin composition for EUV exposure, it is preferable that the resin (A) has at least one repeating unit selected from the group consisting of A above. Resin (A) may contain at least one of fluorine atoms and iodine atoms. When the photosensitive or radiation-sensitive resin composition is used as a photosensitive or radiation-sensitive resin composition for EUV exposure, it is preferable that resin (A) contains at least one of fluorine atoms and iodine atoms. If resin (A) contains both fluorine atoms and iodine atoms, resin (A) may have one repeating unit containing both fluorine atoms and iodine atoms, or resin (A) may contain two types of repeating units: repeating units containing fluorine atoms and repeating units containing iodine atoms. Resin (A) may have repeating units having aromatic groups. When the photosensitive or radiation-sensitive resin composition is used as a photosensitive or radiation-sensitive resin composition for EUV exposure, it is also preferable that resin (A) has repeating units having aromatic groups. Resin (A) may have at least one repeating unit selected from the group consisting of group B. When the photosensitive or radiation-sensitive resin composition is used as a photosensitive or radiation-sensitive resin composition for ArF, it is preferable that resin (A) has at least one repeating unit selected from the group consisting of group B. Furthermore, when a photosensitive or radiation-sensitive resin composition is used as a photosensitive or radiation-sensitive resin composition for ArF, it is preferable that resin (A) does not contain either fluorine atoms or silicon atoms. When a photosensitive or radiation-sensitive resin composition is used as a photosensitive or radiation-sensitive resin composition for ArF, it is preferable that resin (A) does not have aromatic groups.

[0187] (Repeating units containing acidic groups) The resin (A) may have repeating units having acidic groups. As for the acid group, an acid group with a pKa of 13 or less is preferred. The acid dissociation constant of the above acid group is preferably 13 or less, more preferably 3 to 13, and even more preferably 5 to 10. When resin (A) has acid groups with a pKa of 13 or less, the content of acid groups in resin (A) is not particularly limited, but is often between 0.2 and 6.0 mmol / g. Among these, 0.8 to 6.0 mmol / g is preferred, 1.2 to 5.0 mmol / g is more preferred, and 1.6 to 4.0 mmol / g is even more preferred. If the acid group content is within the above range, development proceeds smoothly, the resulting pattern shape is excellent, and the resolution is also excellent. Preferred acid groups include, for example, carboxyl groups, phenolic hydroxyl groups, fluorinated alcohol groups (preferably hexafluoroisopropanol groups), sulfonic acid groups, sulfonamide groups, or isopropanol groups. The hexafluoroisopropanol group described above may have one or more fluorine atoms (preferably one to two) substituted with a group other than a fluorine atom (such as an alkoxycarbonyl group). The acid group thus formed, -C(CF3)(OH)-CF2-, is also preferred. Alternatively, one or more fluorine atoms may be substituted with a group other than a fluorine atom to form a ring containing -C(CF3)(OH)-CF2-. The repeating unit having an acidic group is preferably different from the repeating unit having a structure in which the polar group is protected by a group that is removed by the action of the acid described above, and from the repeating unit having a lactone group, sultone group, or carbonate group described later. The repeating unit having an acidic group may also have a fluorine atom or an iodine atom.

[0188] Examples of repeating units having an acidic group include the following:

[0189] [ka]

[0190] As a repeating unit having an acid group, the repeating unit represented by the following formula (1) is preferred.

[0191] [ka]

[0192] In formula (1), A represents a hydrogen atom, an alkyl group, a cycloalkyl group, a halogen atom, or a cyano group. R represents a halogen atom, an alkyl group, a cycloalkyl group, an aryl group, an alkenyl group, an aralkyl group, an alkoxy group, an alkylcarbonyloxy group, an alkylsulfonyloxy group, an alkyloxycarbonyl group, or an aryloxycarbonyl group, and if there are multiple Rs, they may be the same or different. If there are multiple Rs, they may cooperate to form a ring. A hydrogen atom is preferred as R. a represents an integer from 1 to 3. b represents an integer from 0 to (5-a).

[0193] The following are examples of repeating units having an acid group. In the formulas, a represents 1 or 2.

[0194] [ka]

[0195] [ka]

[0196] [ka]

[0197] [ka]

[0198] Of 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.

[0199] [ka]

[0200] [ka]

[0201] The content of repeating units having acid groups is preferably 10 mol% or more, and more preferably 15 mol% or more, relative to the total repeating units in resin (A). Furthermore, the upper limit is preferably 70 mol% or less, more preferably 65 mol% or less, and even more preferably 60 mol% or less, relative to the total repeating units in resin (A).

[0202] (A repeating unit that does not possess either an acid-degradable group or an acidic group, but has a fluorine atom, a bromine atom, or an iodine atom.) Resin (A) may have repeating units (hereinafter also referred to as unit X) that do not have either an acid-degradable group or an acid group, but have a fluorine atom, a bromine atom, or an iodine atom, in addition to the <repeating units having an acid-degradable group> and <repeating units having an acid group> described above. It is preferable that the <repeating units having either an acid-degradable group or an acid group, but having a fluorine atom, a bromine atom, or an iodine atom> referred to here are different from other types of repeating units belonging to group A, such as the <repeating units having a lactone group, a sultone group, or a carbonate group> and <repeating units having a photoacid-generating group> described later.

[0203] The repeating unit X is preferably represented by formula (C).

[0204] [ka]

[0205] L5 represents a single bond or an ester group. R9 represents an alkyl group which may have a hydrogen atom, a fluorine atom, or an iodine atom. 10This represents an alkyl group which may have a hydrogen atom, a fluorine atom, or an iodine atom, a cycloalkyl group which may have a fluorine atom or an iodine atom, an aryl group which may have a fluorine atom or an iodine atom, or a group which is a combination thereof.

[0206] Examples of repeating units having fluorine or iodine atoms are shown below.

[0207] [ka]

[0208] The content of unit X is preferably 0 mol% or more, more preferably 5 mol% or more, and even more preferably 10 mol% or more, relative to the total repeating units in resin (A). Furthermore, the upper limit is preferably 50 mol% or less, more preferably 45 mol% or less, and even more preferably 40 mol% or less, relative to the total repeating units in resin (A).

[0209] The total content of repeating units in resin (A) that contain at least one of fluorine, bromine, and iodine atoms is preferably 10 mol% or more, more preferably 20 mol% or more, even more preferably 30 mol% or more, and particularly preferably 40 mol% or more, relative to the total repeating units of resin (A). There is no particular upper limit, but for example, it is 100 mol% or less relative to the total repeating units of resin (A). Examples of repeating units containing at least one of a fluorine atom, a bromine atom, and an iodine atom include a repeating unit having a fluorine atom, a bromine atom, or an iodine atom and having an acid-degradable group, a repeating unit having a fluorine atom, a bromine atom, or an iodine atom and having an acidic group, and a repeating unit having a fluorine atom, a bromine atom, or an iodine atom.

[0210] (Repeating units having a lactone group, sultone group, or carbonate group) The resin (A) may have repeating units (hereinafter also referred to as "unit Y") having at least one selected from the group consisting of lactone groups, sultone groups, and carbonate groups. It is also preferable that unit Y does not have acidic groups such as hydroxyl groups and hexafluoropropanol groups.

[0211] The lactone group or sultone group may have a lactone structure or a sultone structure. The lactone structure or sultone structure is preferably a 5-7 membered ring lactone structure or a 5-7 membered ring sultone structure. In particular, a structure in which another ring structure is fused to a 5-7 membered ring lactone structure in the form of a bicyclo or spiro structure, or a structure in which another ring structure is fused to a 5-7 membered ring sultone structure in the form of a bicyclo or spiro structure, is more preferable. The resin (A) preferably has repeating units having lactone groups or sultone groups obtained by abstracting one or more hydrogen atoms from ring member atoms of a lactone structure represented by any of the following formulas (LC1-1) to (LC1-21), or a sultone structure represented by any of the following formulas (SL1-1) to (SL1-3), and the lactone groups or sultone groups may be directly bonded to the main chain. For example, the ring member atoms of the lactone groups or sultone groups may constitute the main chain of the resin (A).

[0212] [ka]

[0213] The above lactone or sultone structure may have substituents (Rb2). Preferred substituents (Rb2) include C1-C8 alkyl groups, C4-C7 cycloalkyl groups, C1-C8 alkoxy groups, C1-C8 alkoxycarbonyl groups, carboxyl groups, halogen atoms, cyano groups, and acid-degradable groups. n2 represents an integer from 0 to 4. When n2 is 2 or more, the multiple Rb2 groups may be different, and the multiple Rb2 groups may bond to each other to form a ring.

[0214] Examples of repeating units having a lactone structure represented by any of the formulas (LC1-1) to (LC1-21), or a sultone structure represented by any of the formulas (SL1-1) to (SL1-3), include the repeating unit represented by the following formula (AI).

[0215] [ka]

[0216] In formula (AI), Rb0 represents a hydrogen atom, a halogen atom, or an alkyl group having 1 to 4 carbon atoms. Preferred substituents that the alkyl group of Rb0 may have include a hydroxyl group and a halogen atom. Examples of halogen atoms for Rb0 include fluorine, chlorine, bromine, and iodine. Rb0 is preferably a hydrogen atom or a methyl group. Ab represents a single bond, an alkylene group, a divalent linking group having a monocyclic or polycyclic alicyclic hydrocarbon structure, an ether group, an ester group, a carbonyl group, a carboxyl group, or a divalent linking group combining these. Among these, a single bond or a linking group represented as -Ab1-CO2- is preferred for Ab. Ab1 is a linear or branched alkylene group, or a monocyclic or polycyclic cycloalkylene group, and is preferably a methylene group, ethylene group, cyclohexylene group, adamantylene group, or norbornylene group. V represents a group obtained by removing one hydrogen atom from a ring member atom of a lactone structure represented by any of the formulas (LC1-1) to (LC1-21), or a group obtained by removing one hydrogen atom from a ring member atom of a sultone structure represented by any of the formulas (SL1-1) to (SL1-3).

[0217] If optical isomers exist for a repeating unit having a lactone group or a sultone group, either optical isomer may be used. Furthermore, one optical isomer may be used alone, or multiple optical isomers may be used in mixture form. When primarily using one optical isomer, its optical purity (ee) is preferably 90 or higher, and more preferably 95 or higher.

[0218] A cyclic carbonate ester group is preferred as the carbonate group. As a repeating unit having a cyclic carbonate ester group, the repeating unit represented by the following formula (A-1) is preferred.

[0219] [ka]

[0220] In formula (A-1), R A 1 R represents a hydrogen atom, a halogen atom, or a monovalent organic group (preferably a methyl group). n represents an integer of 0 or greater. A 2 represents a substituent. If n is 2 or greater, there are multiple R A 2 These may be the same or different. A represents a single bond or a divalent linking group. Preferred divalent linking groups include alkylene groups, divalent linking groups having a monocyclic or polycyclic alicyclic hydrocarbon structure, ether groups, ester groups, carbonyl groups, carboxyl groups, or divalent linking groups that are combinations thereof. Z represents an atomic group that forms a monocyclic or polycyclic ring together with the group represented by -O-CO-O- in the formula.

[0221] The unit Y is exemplified below. In the formula, Rx represents a hydrogen atom, -CH3, -CH2OH, or -CF3.

[0222] [ka]

[0223] [ka]

[0224] [ka]

[0225] The content of unit Y is preferably 1 mol% or more, and more preferably 10 mol% or more, relative to the total repeating units in resin (A). Furthermore, the upper limit is preferably 85 mol% or less, more preferably 80 mol% or less, even more preferably 70 mol% or less, and particularly preferably 60 mol% or less, relative to the total repeating units in resin (A).

[0226] (Repeating unit with photoacid-generating group) The resin (A) may also have repeating units other than those described above, which include a group that generates acid upon irradiation with active light or radiation (also called a "photoacid generating group"). An example of a repeating unit having a photoacid-generating group is the repeating unit represented by formula (4).

[0227] [ka]

[0228] R 41 L represents a hydrogen atom or a methyl group. 41 L represents a single bond or a divalent linking group. 42 R represents a divalent linking group. 40 This represents a structural site that decomposes upon irradiation with active light or radiation, generating acid in the side chain. Examples of repeating units having a photoacid-generating group are shown below.

[0229] [ka]

[0230] Other examples of repeating units represented by formula (4) include the repeating units described in paragraphs

[0094] to

[0105] of Japanese Patent Publication No. 2014-041327, and the repeating units described in paragraph

[0094] of International Publication No. 2018 / 193954.

[0231] The content of repeating units having photoacid generating groups is preferably 1 mol% or more, and more preferably 5 mol% or more, relative to the total repeating units in resin (A). Furthermore, the upper limit is preferably 40 mol% or less, more preferably 35 mol% or less, and even more preferably 30 mol% or less, relative to the total repeating units in resin (A).

[0232] (The repeating unit is represented by formula (V-1) or formula (V-2) below) The resin (A) may have repeating units represented by the following formula (V-1) or the following formula (V-2). The repeating units represented by the following formulas (V-1) and (V-2) are preferably different from the repeating units described above.

[0233] [ka]

[0234] During the ceremony, R6 and R7 each independently represent a hydrogen atom, a hydroxyl group, an alkyl group, an alkoxy group, an acyloxy group, a cyano group, a nitro group, an amino group, a halogen atom, an ester group (-OCOR or -COOR: R is an alkyl group or fluorinated alkyl group having 1 to 6 carbon atoms), or a carboxyl group. Linear, branched, or cyclic alkyl groups having 1 to 10 carbon atoms are preferred as the alkyl group. n3 represents an integer between 0 and 6. n4 represents an integer between 0 and 4. X4 is a methylene group, an oxygen atom, or a sulfur atom. Examples of repeating units represented by formula (V-1) or (V-2) are shown below. Examples of repeating units represented by formula (V-1) or (V-2) include the repeating units described in paragraph

[0100] of International Publication No. 2018 / 193954.

[0235] (A repeating unit that reduces the mobility of the main chain) Resin (A) is preferable to have a high glass transition temperature (Tg) in order to suppress excessive diffusion of generated acid or pattern collapse during development. The 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. Furthermore, in order to have a good dissolution rate in the developer, the Tg is preferably 400°C or lower, and more preferably 350°C or lower. In this specification, the glass transition temperature (Tg) of a polymer such as resin (A) (hereinafter referred to as "Tg of the repeating unit") is calculated by the following method. First, the Tg of each homopolymer consisting only of each repeating unit contained in the polymer is calculated using the Bicerano method. Next, the mass percentage (%) of each repeating unit relative to the total number of repeating units in the polymer is calculated. Then, the Tg for each mass percentage is calculated using Fox's formula (described in Materials Letters 62 (2008) 3152, etc.), and these are summed up to obtain the polymer's Tg (°C). The Bicerano method is described in *Prediction of polymer properties*, Marcel Dekker Inc, New York (1993). The calculation of Tg using the Bicerano method can be performed using the polymer property estimation software MDL Polymer (MDL Information Systems, Inc.).

[0236] To increase the Tg of resin (A) (preferably to make the Tg greater than 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). (a) Introduction of bulky substituents into the main chain (b) Introduction of multiple substituents into the main chain (c) Introduction of substituents that induce interactions between resins (A) near the main chain (d) Main chain formation in a cyclic structure (e) Linking of annular structures to the main chain Furthermore, it is preferable that resin (A) has repeating units in which the Tg of the homopolymer is 130°C or higher. Furthermore, there are no particular restrictions on the type of repeating units in which the homopolymer Tg is 130°C or higher; any repeating unit in which the homopolymer Tg calculated by the Bicerano method is 130°C or higher is acceptable. Note that depending on the type of functional group in the repeating units represented by formulas (A) to (E) described later, some repeating units may be considered to have a homopolymer Tg of 130°C or higher.

[0237] One example of a specific means of achieving (a) above is to introduce repeating units represented by formula (A) into resin (A).

[0238] [ka]

[0239] Formula (A), R A R represents a group containing a polycyclic structure. x represents a hydrogen atom, a methyl group, or an ethyl group. A group containing a polycyclic structure is a group containing multiple ring structures, which may or may not be condensed. Specific examples of repeating units represented by formula (A) are those described in paragraphs

[0107] to

[0119] of International Publication No. 2018 / 193954.

[0240] One example of a specific means of achieving (b) above is to introduce repeating units represented by formula (B) into resin (A).

[0241] [ka]

[0242] In formula (B), R b1 ~R b4 Each of these independently represents a hydrogen atom or an organic group, and R b1 ~R b4 At least two of these represent organic groups. If at least one of the organic groups is a group in which a ring structure is directly linked to the main chain in the repeating unit, the types of other organic groups are not particularly limited. Furthermore, if none of the organic groups are directly linked to the main chain in the repeating unit, then at least two of the organic groups are substituents with three or more constituent atoms excluding hydrogen atoms. Specific examples of repeating units represented by formula (B) are those described in paragraphs

[0113] to

[0115] of International Publication No. 2018 / 193954.

[0243] One example of a specific means of achieving (c) above is to introduce repeating units represented by formula (C) into resin (A).

[0244] [ka]

[0245] In formula (C), R c1 ~R c4 Each of these independently represents a hydrogen atom or an organic group, and R c1 ~R c4 At least one of these groups contains hydrogen-bonding hydrogen atoms within three atoms of the main chain carbon. In particular, it is preferable to have hydrogen-bonding hydrogen atoms within two atoms (closer to the main chain) in order to induce interactions between the main chains of resin (A). Specific examples of repeating units represented by formula (C) are those described in paragraphs

[0119] to

[0121] of International Publication No. 2018 / 193954.

[0246] One example of a specific means of achieving (d) above is to introduce repeating units represented by formula (D) into resin (A).

[0247] [ka]

[0248] In formula (D), "Cyclic" represents a group that forms the main chain in a cyclic structure. The number of constituent atoms in the ring is not particularly limited. Specific examples of repeating units represented by formula (D) are those described in paragraphs

[0126] to

[0127] of International Publication No. 2018 / 193954.

[0249] One example of a specific means of achieving (e) above is to introduce repeating units represented by formula (E) into resin (A).

[0250] [ka]

[0251] In formula (E), Re independently represents either a hydrogen atom or an organic group. Examples of organic groups include alkyl groups, cycloalkyl groups, aryl groups, aralkyl groups, and alkenyl groups, which may have substituents. A "Cyclic" is a cyclic group that contains carbon atoms in its main chain. There are no particular restrictions on the number of atoms that can be included in a cyclic group. Specific examples of repeating units represented by formula (E) are those described in paragraphs

[0131] to

[0133] of International Publication No. 2018 / 193954.

[0252] (A repeating unit having at least one group selected from lactone groups, sultone groups, carbonate groups, hydroxyl groups, cyano groups, and alkali-soluble groups) The resin (A) may have repeating units having at least one group selected from lactone groups, sultone groups, carbonate groups, hydroxyl groups, cyano groups, and alkali-soluble groups. Examples of repeating units having lactone groups, sultone groups, or carbonate groups in resin (A) include the repeating units described above in <Repeating units having lactone groups, sultone groups, or carbonate groups>. The preferred content is also as described above in <Repeating units having lactone groups, sultone groups, or carbonate groups>.

[0253] The resin (A) may have repeating units having hydroxyl groups or cyano groups. This improves substrate adhesion and developer affinity. The repeating unit having a hydroxyl group or a cyano group is preferably a repeating unit having an alicyclic hydrocarbon structure substituted with a hydroxyl group or a cyano group. It is preferable that the repeating units having a hydroxyl group or a cyano group do not have an acid-degradable group. Examples of repeating units having a hydroxyl group or a cyano group are those described in paragraphs

[0081] to

[0084] of Japanese Patent Application Publication No. 2014-098921.

[0254] The resin (A) may have repeating units having alkali-soluble groups. Examples of alkali-soluble groups include carboxyl groups, sulfonamide groups, sulfonylimide groups, bissulfonylimide groups, and aliphatic alcohol groups (e.g., hexafluoroisopropanol group) whose α-position is substituted with an electron-withdrawing group, with carboxyl groups being preferred. The inclusion of repeating units having alkali-soluble groups in resin (A) increases the resolution in contact hole applications. Examples of repeating units having alkali-soluble groups are those described in paragraphs

[0085] and

[0086] of Japanese Patent Application Publication No. 2014-098921.

[0255] (A repeating unit having an alicyclic hydrocarbon structure and not exhibiting acid decomposition) Resin (A) may have repeating units that have an alicyclic hydrocarbon structure and do not exhibit acid decomposition. This reduces the elution of low molecular weight components from the resist film into the immersion liquid during immersion exposure. Examples of repeating units that have an alicyclic hydrocarbon structure and do not exhibit acid decomposition include repeating units derived from 1-adamantyl (meth)acrylate, diamantyl (meth)acrylate, tricyclodecanyl (meth)acrylate, or cyclohexyl (meth)acrylate.

[0256] (A repeating unit represented by formula (III) that does not have either a hydroxyl group or a cyano group) Resin (A) may have repeating units represented by formula (III) that do not have either a hydroxyl group or a cyano group.

[0257] [ka]

[0258] In formula (III), R5 represents a hydrocarbon group having at least one cyclic structure and lacking both a hydroxyl group and a cyano group. 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. Examples of repeating units represented by formula (III) that do not have either a hydroxyl group or a cyano group include those described in paragraphs

[0087] to

[0094] of Japanese Patent Publication No. 2014-098921.

[0259] (Other repeating units) Furthermore, resin (A) may have other repeating units besides those described above. For example, resin (A) may have repeating units selected from the group consisting of repeating units having an oxatian ring group, repeating units having an oxazolone ring group, repeating units having a dioxane ring group, and repeating units having a hydantoin ring group. The following are examples of other repeating units besides those mentioned above.

[0260] [ka]

[0261] In addition to the repeating structural units described above, resin (A) may have various repeating structural units for the purpose of adjusting dry etching resistance, suitability for standard developers, substrate adhesion, resist profile, resolution, heat resistance, and sensitivity.

[0262] As for resin (A), in particular when the composition is used as an activated photosensitive or radiation-sensitive resin composition for ArF, it is preferable that all of the repeating units are composed of repeating units derived from a compound having an ethylenically unsaturated bond. In particular, it is also preferable that all of the repeating units are composed of (meth)acrylate repeating units. When all of the repeating units are composed of (meth)acrylate repeating units, any of the following can be used: all of the repeating units are methacrylate repeating units, all of the repeating units are acrylate repeating units, or all of the repeating units are a combination of methacrylate and acrylate repeating units, and it is preferable that the acrylate repeating units make up 50 mol% or less of the total repeating units.

[0263] Resin (A) can be synthesized according to conventional methods (e.g., radical polymerization). According to the GPC method, the weight-average molecular weight of resin (A), expressed as polystyrene equivalent, is preferably 30,000 or less, more preferably 1,000 to 30,000, even more preferably 3,000 to 30,000, and particularly preferably 5,000 to 15,000. The degree of dispersion (molecular weight distribution) of resin (A) is preferably 1 to 5, more preferably 1 to 3, even more preferably 1.2 to 3.0, and particularly preferably 1.2 to 2.0. The lower the degree of dispersion, the better the resolution and resist shape, and furthermore, the smoother the sidewalls of the resist pattern and the better the roughness.

[0264] In a photosensitive or radiation-sensitive resin composition, the content of resin (A) is preferably 40.0 to 99.9% by mass, and more preferably 60.0 to 90.0% by mass, relative to the total solid content of the photosensitive or radiation-sensitive resin composition. Resin (A) may be used alone or in combination of multiple types.

[0265] <Compounds that generate acid upon irradiation with active light or radiation (B)> The photosensitive or radiation-sensitive resin composition may contain a compound (B) (also referred to as "compound (B)" or "photoacid generator (B)") that generates acid upon irradiation with active light or radiation. In step (3) described above, a photoacid generator (B) may be mixed in addition to the onium salt (C) and resin (A). The photoacid generator (B) may be in the form of a low molecular weight compound, or it may be incorporated into a polymer (for example, resin (A) described later). Alternatively, both the form of a low molecular weight compound and the form incorporated into a polymer (for example, resin (A) described later) may be used in combination. When the photoacid generator (B) is in the form of a low molecular weight compound, the molecular weight of the photoacid generator is preferably 3000 or less, more preferably 2000 or less, and even more preferably 1000 or less. There is no particular lower limit, but 100 or more is preferred. If the photoacid generator (B) is incorporated into a polymer, it may be incorporated into a resin (A) or into a resin different from resin (A). In this specification, the photoacid generator (B) is preferably in the form of a low molecular weight compound.

[0266] For example, the photoacid generator (B) is "M + X - Examples include compounds represented by '' (onium salts), and it is preferable that these compounds generate organic acids upon exposure. Examples of the above-mentioned organic acids include sulfonic acids (aliphatic sulfonic acids, aromatic sulfonic acids, and camphor sulfonic acids, etc.), carboxylic acids (aliphatic carboxylic acids, aromatic carboxylic acids, and aralkyl carboxylic acids, etc.), carbonylsulfonylimide acids, bis(alkylsulfonyl)imide acids, and tris(alkylsulfonyl)methidic acids.

[0267] "M + X - In the compound represented by ", M + This represents an organic cation. The description, specific examples, and preferred range of organic cations are the same as those described above for the organic cations of onium salts (C).

[0268] "M + X - In the compound represented by ", X - This represents an organic anion. The organic anion is not particularly limited and can be any organic anion with one or more valents. As for the organic anion, anion with a remarkably low ability to undergo nucleophilic reactions is preferred, and non-nucleophilic anions are more preferred.

[0269] Examples of non-nucleophilic anions include sulfonate anions (aliphatic sulfonate anions, aromatic sulfonate anions, and camphor sulfonate anions, etc.), carboxylic acid anions (aliphatic carboxylic acid anions, aromatic carboxylic acid anions, and aralkyl carboxylic acid anions, etc.), sulfonylimide anions, bis(alkylsulfonyl)imide anions, and tris(alkylsulfonyl)methide anions.

[0270] The aliphatic moiety in aliphatic sulfonic acid anions and aliphatic carboxylic acid anions may be a linear or branched alkyl group or a cycloalkyl group, with linear or branched alkyl groups having 1 to 30 carbon atoms or cycloalkyl groups having 3 to 30 carbon atoms being preferred. The alkyl group described above may be, for example, a fluoroalkyl group (which may have substituents other than a fluorine atom; it may also be a perfluoroalkyl group).

[0271] In aromatic sulfonic acid anions and aromatic carboxylic acid anions, aryl groups having 6 to 14 carbon atoms are preferred, such as phenyl groups, tolyl groups, and naphthyl groups.

[0272] The alkyl, cycloalkyl, and aryl groups listed above may have substituents. Substituents are not particularly limited, but examples include nitro groups, halogen atoms such as fluorine and chlorine atoms, carboxyl groups, hydroxyl groups, amino groups, cyano groups, alkoxy groups (preferably having 1 to 15 carbon atoms), alkyl groups (preferably having 1 to 10 carbon atoms), cycloalkyl groups (preferably having 3 to 15 carbon atoms), aryl groups (preferably having 6 to 14 carbon atoms), alkoxycarbonyl groups (preferably having 2 to 7 carbon atoms), acyl groups (preferably having 2 to 12 carbon atoms), alkoxycarbonyloxy groups (preferably having 2 to 7 carbon atoms), alkylthio groups (preferably having 1 to 15 carbon atoms), alkylsulfonyl groups (preferably having 1 to 15 carbon atoms), alkyliminosulfonyl groups (preferably having 1 to 15 carbon atoms), and aryloxysulfonyl groups (preferably having 6 to 20 carbon atoms).

[0273] In aralkyl carboxylic acid anions, an aralkyl group having 7 to 14 carbon atoms is preferred. Examples of aralkyl groups having 7 to 14 carbon atoms include the benzyl group, phenethyl group, naphthylmethyl group, naphthylethyl group, and naphthylbutyl group.

[0274] An example of a sulfonylimid anion is the saccharin anion.

[0275] For bis(alkylsulfonyl)imide anions and tris(alkylsulfonyl)methide anions, alkyl groups having 1 to 5 carbon atoms are preferred. Substituents for these alkyl groups include halogen atoms, alkyl groups substituted with halogen atoms, alkoxy groups, alkylthio groups, alkyloxysulfonyl groups, aryloxysulfonyl groups, and cycloalkylaryloxysulfonyl groups, with fluorine atoms or alkyl groups substituted with fluorine atoms being preferred. Furthermore, the alkyl groups in the bis(alkylsulfonyl)imide anion may bond to each other to form a ring structure. This increases the acid strength.

[0276] Other non-nucleophilic anions include, for example, fluorinated phosphorus (e.g., PF6). - ), fluorinated boron (for example, BF4 - ), and fluorinated antimony (e.g., SbF6) - ) are some examples.

[0277] As non-nucleophilic anions, aliphatic sulfonic acid anions in which at least the α-position of the sulfonic acid is substituted with a fluorine atom, aromatic sulfonic acid anions substituted with a fluorine atom or a group having a fluorine atom, bis(alkylsulfonyl)imide anions in which the alkyl group is substituted with a fluorine atom, or tris(alkylsulfonyl)methide anions in which the alkyl group is substituted with a fluorine atom are preferred. Among these, perfluoroaliphatic sulfonic acid anions (preferably with 4 to 8 carbon atoms) or benzenesulfonic acid anions having a fluorine atom are more preferred, and nonafluorobutanesulfonic acid anions, perfluorooctanesulfonic acid anions, pentafluorobenzenesulfonic acid anions, or 3,5-bis(trifluoromethyl)benzenesulfonic acid anions are even more preferred.

[0278] As a non-nucleophilic anion, the anion represented by the following formula (AN1) is also preferred.

[0279] [ka]

[0280] In formula (AN1), R 1 and R 2 Each of these independently represents either a hydrogen atom or a substituent. The substituents are not particularly limited, but groups that are not electron-withdrawing groups are preferred. Examples of groups that are not electron-withdrawing groups include hydrocarbon groups, hydroxyl groups, oxy hydrocarbon groups, oxycarbonyl hydrocarbon groups, amino groups, hydrocarbon-substituted amino groups, and hydrocarbon-substituted amide groups. The non-electron-withdrawing groups are, independently, -R', -OH, -OR', -OCOR', -NH2, -NR'2, -NHR', or -NHCOR'. R' is a monovalent hydrocarbon group.

[0281] Examples of monovalent hydrocarbon groups represented by R' above include alkyl groups such as methyl, ethyl, propyl, and butyl groups; alkenyl groups such as ethenyl, propenyl, and butenyl groups; monovalent linear or branched hydrocarbon groups such as alkynyl groups such as ethynyl, propynyl, and butynyl groups; cycloalkyl groups such as cyclopropyl, cyclobutyl, cyclopentyl, cyclohexyl, norbornyl, and adamantyl groups; monovalent alicyclic hydrocarbon groups such as cyclopropenyl, cyclobutenyl, cyclopentenyl, and norbornenyl groups; aryl groups such as phenyl, tolyl, xylyl, mesityl, naphthyl, methylnaphthyl, anthryl, and methylanthryl groups; and monovalent aromatic hydrocarbon groups such as benzyl, phenethyl, phenylpropyl, naphthylmethyl, and anthrylmethyl groups. Among them, R 1 and R 2 Each of these is independently preferably a hydrocarbon group (cycloalkyl group preferred) or a hydrogen atom.

[0282] L represents a divalent linking group. If there are multiple Ls, each L may be the same or different. Examples of divalent linking groups include -O-CO-O-, -COO-, -CONH-, -CO-, -O-, -S-, -SO-, -SO2-, alkylene groups (preferably with 1 to 6 carbon atoms), cycloalkylene groups (preferably with 3 to 15 carbon atoms), alkenylene groups (preferably with 2 to 6 carbon atoms), and divalent linking groups formed by combining multiple thereof. Among these, preferred divalent linking groups are -O-CO-O-, -COO-, -CONH-, -CO-, -O-, -SO2-, -O-CO-O-alkylene group-, -COO-alkylene group-, or -CONH-alkylene group-, and more preferred are -O-CO-O-, -O-CO-O-alkylene group-, -COO-, -CONH-, -SO2-, or -COO-alkylene group-.

[0283] For L, a group represented by the following formula (AN1-1) is preferred. * a -(CR 2a 2) X -Q-(CR 2b 2) Y -* b (AN1-1)

[0284] In formula (AN1-1), * a R in equation (AN1) 3 This indicates the connection point with [the other element]. * b -C(R 1 )(R 2 )- indicates the connection position with. X and Y each independently represent integers between 0 and 10, preferably between 0 and 3. R 2a and R 2b Each of these independently represents a hydrogen atom or a substituent. R 2a and R 2b If there are multiple instances of each, then there are multiple instances of R 2a and R 2b These may be the same or different. However, if Y is 1 or greater, -C(R) in equation (AN1) 1 )(R 2)- and CR which bind directly 2b R in 2 2b These are atoms other than fluorine atoms. Q is * 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 It represents. However, X+Y in equation (AN1-1) is 1 or greater, and R in equation (AN1-1) 2a and R 2b If all of them are hydrogen atoms, then Q is * A -O-CO-O-* B , * A -CO-* B , * A -O-CO-* B , * A -O-* B , * A -S-* B , or, * A -SO2-* B It represents. * A R in equation (AN1) 3 This indicates the connection position on the side, * B -SO3 in equation (AN1) - This indicates the connection point on the side.

[0285] In formula (AN1), R 3 This represents an organic group. The above organic group is not particularly limited as long as it has one or more carbon atoms, and may be a linear group (e.g., a linear alkyl group), a branched group (e.g., a branched alkyl group such as a t-butyl group), or a cyclic group. The above organic group may or may not have substituents. The above organic group may or may not have heteroatoms (oxygen atom, sulfur atom, and / or nitrogen atom, etc.).

[0286] Among them, R 3 It is preferable that the organic group has a cyclic structure. The cyclic structure may be monocyclic or polycyclic, and may have substituents. It is preferable that the ring in the organic group containing the cyclic structure is directly bonded to L in formula (AN1). The organic group having the above cyclic structure may or may not have heteroatoms (such as oxygen atoms, sulfur atoms, and / or nitrogen atoms). The heteroatoms may substitute for one or more carbon atoms that form the cyclic structure. The organic group having the above-mentioned cyclic structure is preferably a cyclic hydrocarbon group, a lactone ring group, or a sultone ring group. Among these, the organic group having the above-mentioned cyclic structure is preferably a cyclic hydrocarbon group. The hydrocarbon group in the above cyclic structure is preferably a monocyclic or polycyclic cycloalkyl group. These groups may have substituents. The above cycloalkyl group may be monocyclic (e.g., cyclohexyl group) or polycyclic (e.g., adamantyl group), and preferably has 5 to 12 carbon atoms. The lactone group and sultone group described above are preferably groups obtained by removing one hydrogen atom from the ring member atoms constituting the lactone or sultone structure in either of the structures represented by formulas (LC1-1) to (LC1-21) and (SL1-1) to (SL1-3) described above.

[0287] The non-nucleophilic anion may be a benzenesulfonic acid anion, and it is preferable that the benzenesulfonic acid anion is substituted with a branched alkyl group or a cycloalkyl group.

[0288] As a non-nucleophilic anion, the anion represented by the following formula (AN2) is also preferred.

[0289] [ka]

[0290] In equation (AN2), o represents an integer between 1 and 3. p represents an integer between 0 and 10. q represents an integer between 0 and 10.

[0291] Xf represents a hydrogen atom, a fluorine atom, an alkyl group substituted with at least one fluorine atom, or an organic group without a fluorine atom. The number of carbon atoms in this alkyl group is preferably 1 to 10, and more preferably 1 to 4. As the alkyl group substituted with at least one fluorine atom, a perfluoroalkyl group is preferred. Xf is preferably a fluorine atom or a perfluoroalkyl group having 1 to 4 carbon atoms, more preferably a fluorine atom or CF3, and even more preferably both Xf are fluorine atoms.

[0292] R 4 and R 5 Each of these independently represents a hydrogen atom, a fluorine atom, an alkyl group, or an alkyl group substituted with at least one fluorine atom. 4 and R 5 If there are multiple instances, R 4 and R 5 These may be the same or different. R 4 and R 5 The alkyl group represented by preferably has 1 to 4 carbon atoms. The alkyl group may have substituents. Hydrogen atoms are preferred for R4 and R5.

[0293] L represents a divalent linking group. The definition of L is the same as L in formula (AN1).

[0294] W represents an organic group containing a cyclic structure. Among these, a cyclic organic group is preferred. Examples of cyclic organic groups include alicyclic groups, aryl groups, and heterocyclic groups. The alicyclic group may be monocyclic or polycyclic. Examples of monocyclic alicyclic groups include monocyclic cycloalkyl groups such as cyclopentyl, cyclohexyl, and cyclooctyl groups. Examples of polycyclic alicyclic groups include polycyclic cycloalkyl groups such as norbornyl, tricyclodecanyl, tetracyclodecanyl, tetracyclododecanyl, and adamantyl groups. Among these, alicyclic groups having a bulky structure with 7 or more carbon atoms, such as norbornyl, tricyclodecanyl, tetracyclodecanyl, tetracyclododecanyl, and adamantyl groups, are preferred.

[0295] The aryl group may be monocyclic or polycyclic. Examples of the aryl group include the phenyl group, naphthyl group, phenanthryl group, and anthryl group. The heterocyclic group may be monocyclic or polycyclic. In particular, a polycyclic heterocyclic group can more effectively suppress acid diffusion. The heterocyclic group may or may not be aromatic. Examples of aromatic heterocyclic rings include furan rings, thiophene rings, benzofuran rings, benzothiophene rings, dibenzofuran rings, dibenzothiophene rings, and pyridine rings. Examples of heterocyclic rings that are not aromatic include tetrahydropyran rings, lactone rings, sultone rings, and decahydroisoquinoline rings. The heterocyclic ring in the heterocyclic group is preferably a furan ring, thiophene ring, pyridine ring, or decahydroisoquinoline ring.

[0296] The above-mentioned cyclic organic group may have substituents. Examples of substituents include alkyl groups (which may be linear or branched, preferably having 1 to 12 carbon atoms), cycloalkyl groups (which may be monocyclic, polycyclic, or spirocyclic, preferably having 3 to 20 carbon atoms), aryl groups (preferably having 6 to 14 carbon atoms), hydroxyl groups, alkoxy groups, ester groups, amide groups, urethane groups, ureido groups, thioether groups, sulfonamide groups, and sulfonic acid ester groups. The carbon atoms constituting the cyclic organic group (carbon atoms contributing to ring formation) may be carbonyl carbons.

[0297] The anion represented by formula (AN2) is SO3. - -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) q -W, or SO3 - -CF2-CH(CF3)-OCO-(L) q’ -W is preferred. Here, L, q, and W are the same as in equation (AN2). q' represents an integer from 0 to 10.

[0298] As a non-nucleophilic anion, an aromatic sulfonic acid anion represented by the following formula (AN3) is also preferred.

[0299] [ka]

[0300] In formula (AN3), Ar represents an aryl group (such as a phenyl group), and may further have substituents other than a sulfonic acid anion and a -(DB) group. Examples of further substituents include a fluorine atom and a hydroxyl group. n represents a non-negative integer. n is preferably between 1 and 4, more preferably between 2 and 3, and even more preferably 3.

[0301] D represents a single bond or a divalent linking group. Examples of divalent linking groups include ether groups, thioether groups, carbonyl groups, sulfoxide groups, sulfone groups, sulfonic acid ester groups, ester groups, and groups consisting of two or more combinations of these.

[0302] B represents a hydrocarbon group. For B, an aliphatic hydrocarbon group is preferred, and an isopropyl group, a cyclohexyl group, or an aryl group which may have further substituents (such as a tricyclohexylphenyl group) is more preferred.

[0303] As a non-nucleophilic anion, disulfonamide anions are also preferred. Disulfonamide anions are, for example, N - (SO2-R q This is an anion represented by 2. Here, R q R represents an alkyl group which may have substituents, fluoroalkyl groups are preferred, and perfluoroalkyl groups are more preferred. q They may be joined to each other to form a ring. Two R q The group formed by the bonding of these atoms is preferably an alkylene group, which may have substituents, preferably a fluoroalkylene group, and more preferably a perfluoroalkylene group. The alkylene group preferably has 2 to 4 carbon atoms.

[0304] Furthermore, non-nucleophilic anions include those represented by the following formulas (d1-1) to (d1-4).

[0305] [ka]

[0306] [ka]

[0307] In formula (d1-1), R 51 represents a hydrocarbon group (for example, an aryl group such as a phenyl group) which may have substituents (for example, a hydroxyl group).

[0308] In formula (d1-2), Z 2c represents a hydrocarbon group having 1 to 30 carbon atoms, which may have substituents (however, carbon atoms adjacent to S are not substituted with fluorine atoms). Z 2c The hydrocarbon group in the above may be linear, branched, or have a cyclic structure. Furthermore, the carbon atoms in the hydrocarbon group (preferably, the ring member atoms when the hydrocarbon group has a cyclic structure) may be carbonyl carbons (-CO-). Examples of the hydrocarbon group include a group having a norbornyl group, which may have substituents. The carbon atoms forming the norbornyl group may also be carbonyl carbons. In equation (d1-2), "Z 2c -SO3 - It is preferable that the anion is different from the anion represented by the above formulas (AN1) to (AN3). For example, Z 2c The group other than an aryl group is preferable. For example, Z 2c -SO3 - For the α and β positions, atoms other than carbon atoms having a fluorine atom as a substituent are preferred. For example, Z 2c is, -SO3 - Preferably, the atom at the α position and / or the atom at the β position are ring member atoms in the cyclic group.

[0309] In formula (d1-3), R 52 represents an organic group (preferably a hydrocarbon group having a fluorine atom), Y 3 Rf represents a linear, branched, or cyclic alkylene, arylene, or carbonyl group, while Rf represents a hydrocarbon group.

[0310] In formula (d1-4), R 53 and R 54 Each of these independently represents an organic group (preferably a hydrocarbon group having a fluorine atom).53 and R 54 They may be joined to each other to form a ring.

[0311] Organic anions may be used individually or in combination of two or more.

[0312] The photoacid generator is preferably at least one selected from the group consisting of compounds (I) to (II).

[0313] (Compound (I)) Compound (I) is a compound having one or more of the following structural sites X and one or more of the following structural sites Y, which generates an acid containing a first acidic site derived from the following structural site X and a second acidic site derived from the following structural site Y upon irradiation with active light or radiation. Structural part X: Anion part A1 - and cation site M1 + It consists of the above, and upon irradiation with active light or radiation, it forms a structural site that forms a first acidic site represented by HA1. Structural site Y: Anionic site A2 - and cation site M2 + It consists of the above, and upon irradiation with active light or radiation, a structural site which forms a second acidic site represented by HA2. The above compound (I) satisfies the following condition I.

[0314] Condition I: In the above compound (I), the above cation site M1 in the above structural site X + and the cation portion M2 in the structural portion Y + to H + The compound PI obtained by replacing the above structural site X is the above cation site M1 + to H + The acid dissociation constant a1 derived from the acidic site represented by HA1, which is replaced by the above-mentioned cation site M2 in the above-mentioned structural site Y + to H + It has an acid dissociation constant a2 derived from the acidic site represented by HA2, which is replaced by the above acid dissociation constant a1, and the above acid dissociation constant a2 is greater than the above acid dissociation constant a1.

[0315] Condition I will be explained in more detail below. If compound (I) is a compound that generates an acid having, for example, one first acidic site derived from structural site X and one second acidic site derived from structural site Y, then compound PI falls under the category of "a compound having HA1 and HA2". More specifically, when the acid dissociation constants a1 and a2 of compound PI are determined, if compound PI is "A1 - The pKa of the compound having HA2 is the acid dissociation constant a1, and the above "A1 - "A compound having HA2" is "A1 - and A2 - The pKa of the compound having the above characteristics is the acid dissociation constant a2.

[0316] If compound (I) is a compound that generates an acid having, for example, two first acidic sites derived from structural site X and one second acidic site derived from structural site Y, then compound PI falls under the category of "a compound having two HA1 and one HA2". When the acid dissociation constant of compound PI is determined, compound PI is "one A1 - The acid dissociation constant when a compound having one HA1 and one HA2 is formed, and the acid dissociation constant when a compound having one A1 - "A compound having one HA1 and one HA2" is "two A1 - The acid dissociation constant when a compound is formed that has "two A1" corresponds to the acid dissociation constant a1 mentioned above. - A compound having one HA2 is a compound having two A1 - and A2 - The acid dissociation constant when a compound has the above-mentioned cation site M1 corresponds to the acid dissociation constant a2. In other words, in the case of compound PI, the above-mentioned cation site M1 in the above-mentioned structural site X + to H +When there are a plurality of acid dissociation constants derived from the acidic site represented by HA1 which is replaced, the value of the acid dissociation constant a2 is larger than the largest value among the plurality of acid dissociation constants a1. In addition, when the compound PI is "one A1 - and a compound having one HA1 and one HA2", the acid dissociation constant is aa, and "one A1 - and a compound having one HA1 and one HA2" becomes "two A1 - and a compound having one HA2", when the acid dissociation constant is ab, the relationship between aa and ab satisfies aa < ab.

[0317] The acid dissociation constant a1 and the acid dissociation constant a2 are determined by the measurement method of the acid dissociation constant described above. The above compound PI corresponds to the acid generated when the compound (I) is irradiated with actinic rays or radiation. When the compound (I) has two or more structural sites X, the structural sites X may be the same or different from each other. Also, two or more of the above A1 - and two or more of the above M1 + may be the same or different from each other. In the compound (I), the above A1 - and the above A2 - and the above M1 + and the above M2 + may be the same or different from each other, but the above A1 - and the above A2 - are preferably different from each other.

[0318] In the above compound PI, the difference (absolute value) between the acid dissociation constant a1 (when there are a plurality of acid dissociation constants a1, the maximum value thereof) and the acid dissociation constant a2 is preferably 0.1 or more, more preferably 0.5 or more, and still more preferably 1.0 or more. The upper limit value of the difference (absolute value) between the acid dissociation constant a1 (when there are a plurality of acid dissociation constants a1, the maximum value thereof) and the acid dissociation constant a2 is not particularly limited, but for example, it is 16 or less.

[0319] In the above compound PI, the acid dissociation constant a2 is preferably 20 or less, and more preferably 15 or less. The lower limit of the acid dissociation constant a2 is preferably -4.0 or higher.

[0320] In the above compound PI, the acid dissociation constant a1 is preferably 2.0 or less, and more preferably 0 or less. The lower limit of the acid dissociation constant a1 is preferably -20.0 or higher.

[0321] Anion part A1 - and anion part A2 - This refers to a structural site containing a negatively charged atom or group of atoms, and examples include structural sites selected from the group consisting of formulas (AA-1) to (AA-3) and formulas (BB-1) to (BB-6) shown below. Anion part A1 - Preferably, the acidic site can form an acidic site with a small acid dissociation constant, and among these, it is more preferably one of formulas (AA-1) to (AA-3), and even more preferably one of formulas (AA-1) and (AA-3). Also, anion part A2 - For example, Anion part A1 - It is preferable that the material can form an acidic site with a larger acid dissociation constant than the other material, more preferably one of formulas (BB-1) to (BB-6), and even more preferably one of formulas (BB-1) and (BB-4). In the following equations (AA-1) to (AA-3) and (BB-1) to (BB-6), * indicates the bond position. In formula (AA-2), R A R represents a monovalent organic group. A The monovalent organic group represented by is not particularly limited, but examples include a cyano group, a trifluoromethyl group, and a methanesulfonyl group.

[0322] [ka]

[0323] [ka]

[0324] Cation site M1 + and cation site M2 + This is a structural site containing a positively charged atom or group of atoms, for example, a monovalent organic cation. Examples of organic cations include the M mentioned above. + Examples of organic cations represented by the following are given.

[0325] The specific structure of compound (I) is not particularly limited, but examples include compounds represented by formulas (Ia-1) to (Ia-5) described later.

[0326] - Compound represented by formula (Ia-1) - In the following, we will first discuss the compound represented by formula (Ia-1).

[0327] M 11 + A 11 - -L1-A 12 - M 12 + (Ia-1)

[0328] The compound represented by formula (Ia-1) is HA when irradiated with active light or radiation. 11 -L1-A 12 It produces an acid represented by H.

[0329] In formula (Ia-1), M 11 + and M 12 + Each of these independently represents an organic cation. A 11 - and A 12 - Each of these independently represents a monovalent anionic functional group. L1 represents a divalent linking group. M 11 + and M 12+ These may be the same or different. A 11 - and A 12 - These may be the same or different, but it is preferable that they are different from each other. However, in the above formula (Ia-1), M 11 + and M 12 + The cation represented by H + The compound PIa(HA) is formed by replacing it with PIa(HA) 11 -L1-A 12 In H), A 12 The acid dissociation constant a2, which originates from the acidic site represented by H, is HA 11 It is greater than the acid dissociation constant a1 derived from the acidic site represented by (Ia-1). The preferred values ​​for the acid dissociation constants a1 and a2 are as described above. The acid generated from compound PIa and the compound represented by formula (Ia-1) upon irradiation with active light or radiation is the same. Also, M 11 + M 12 + , A 11 - , A 12 - , and at least one of L1 may have an acid-degradable group as a substituent.

[0330] In formula (Ia-1), M1 + and M2 + The organic cation represented by is as described above.

[0331] A 11 - The monovalent anionic functional group represented by is the anionic moiety A1 mentioned above. - This refers to a monovalent group including A. 12 - The monovalent anionic functional group represented by is the anionic moiety A2 mentioned above. - This refers to a monovalent group that includes [the specified element]. A 11- and A 12 - The monovalent anionic functional group represented by is preferably a monovalent anionic functional group containing any of the anionic moieties of formulas (AA-1) to (AA-3) and formulas (BB-1) to (BB-6) described above, and more preferably a monovalent anionic functional group selected from the group consisting of formulas (AX-1) to (AX-3) and formulas (BX-1) to (BX-7). 11 - Among the monovalent anionic functional groups represented by (AX-1) to (AX-3), it is preferable that the monovalent anionic functional group is represented by any of the formulas (AX-1) to (AX-3). 12 - Among the monovalent anionic functional groups represented by (BX-1) to (BX-7), a monovalent anionic functional group represented by any of the formulas (BX-1) to (BX-6) is preferred, and a monovalent anionic functional group represented by any of the formulas (BX-1) to (BX-6) is more preferred.

[0332] [ka]

[0333] In formulas (AX-1) to (AX-3), R A1 and R A2 Each of these independently represents a monovalent organic group. * represents a bond position. R A1 The monovalent organic group represented by is not particularly limited, but examples include a cyano group, a trifluoromethyl group, and a methanesulfonyl group.

[0334] R A2 The monovalent organic group represented by is preferably a linear, branched, or cyclic alkyl group, or an aryl group. The number of carbon atoms in the alkyl group is preferably 1 to 15, more preferably 1 to 10, and even more preferably 1 to 6. The alkyl group described above may have substituents. Preferably, the substituents are fluorine atoms or cyano groups, and more preferably fluorine atoms. If the alkyl group has a fluorine atom as a substituent, it may be a perfluoroalkyl group.

[0335] The aryl group is preferably a phenyl group or a naphthyl group, and more preferably a phenyl group. The above aryl group may have substituents. Preferred substituents are fluorine atoms, iodine atoms, perfluoroalkyl groups (for example, those having 1 to 10 carbon atoms are preferred, and those having 1 to 6 carbon atoms are more preferred), or cyano groups, with fluorine atoms, iodine atoms, or perfluoroalkyl groups being more preferred.

[0336] In equations (BX-1) to (BX-4) and (BX-6), R B represents a monovalent organic group. * represents a bond position. R B The monovalent organic group represented by is preferably a linear, branched, or cyclic alkyl group, or an aryl group. The number of carbon atoms in the alkyl group is preferably 1 to 15, more preferably 1 to 10, and even more preferably 1 to 6. The alkyl group described above may have substituents. While the substituents are not particularly limited, fluorine atoms or cyano groups are preferred, with fluorine atoms being more preferred. If the alkyl group has a fluorine atom as a substituent, it may be a perfluoroalkyl group. Furthermore, if the carbon atom at the bonding position in the alkyl group has a substituent, it is also preferable that the substituent is not a fluorine atom or a cyano group. Here, the carbon atom at the bonding position in the alkyl group is, for example, in the case of formulas (BX-1) and (BX-4), the carbon atom directly bonded to the -CO- explicitly stated in the formula of the alkyl group; in the case of formulas (BX-2) and (BX-3), the carbon atom directly bonded to the -SO2- explicitly stated in the formula of the alkyl group; and in the case of formula (BX-6), the carbon atom directly bonded to the N explicitly stated in the formula of the alkyl group. - This refers to carbon atoms that are directly bonded to it. The alkyl group described above may have a carbon atom substituted with a carbonyl carbon.

[0337] The aryl group is preferably a phenyl group or a naphthyl group, and more preferably a phenyl group. The above aryl group may have substituents. Preferred substituents include fluorine atoms, iodine atoms, perfluoroalkyl groups (for example, those having 1 to 10 carbon atoms are preferred, and those having 1 to 6 carbon atoms are more preferred), cyano groups, alkyl groups (for example, those having 1 to 10 carbon atoms are preferred, and those having 1 to 6 carbon atoms are more preferred), alkoxy groups (for example, those having 1 to 10 carbon atoms are preferred, and those having 1 to 6 carbon atoms are more preferred), and fluorine atoms, iodine atoms, perfluoroalkyl groups, alkyl groups, alkoxy groups, or alkoxycarbonyl groups are more preferred.

[0338] In formula (Ia-1), the divalent linking group represented by L1 is not particularly limited and may include -CO-, -NR-, -O-, -S-, -SO-, -SO2-, alkylene group (preferably having 1 to 6 carbon atoms, which may be linear or branched), cycloalkylene group (preferably having 3 to 15 carbon atoms), alkenylene group (preferably having 2 to 6 carbon atoms), and divalent aliphatic heterocyclic group (having at least one N, O, S, or Se atom in the ring structure, which may be 5 to 15 carbon atoms). Examples include 10-membered rings, more preferably 5-7 membered rings, and even more preferably 5-6 membered rings), divalent aromatic heterocyclic groups (5-10 membered rings having at least one N, O, S, or Se atom in the ring structure, more preferably 5-7 membered rings, and even more preferably 5-6 membered rings), divalent aromatic hydrocarbon ring groups (6-10 membered rings, and even more preferably 6 membered rings), and divalent linking groups formed by combining several of these. The above R can be a hydrogen atom or a monovalent organic group. The monovalent organic group is not particularly limited, but for example, alkyl groups (preferably having 1 to 6 carbon atoms) are preferred. The alkylene group, cycloalkylene group, alkenylene group, divalent aliphatic heterocyclic group, divalent aromatic heterocyclic group, and divalent aromatic hydrocarbon ring group may have substituents. Examples of substituents include halogen atoms (preferably fluorine atoms).

[0339] In particular, the divalent linking group represented by L1 is preferably the divalent linking group represented by formula (L1).

[0340] [ka]

[0341] In formula (L1), L 111 This represents a single bond or a divalent linking group. L 111 The divalent linking group represented by is not particularly limited and includes, for example, -CO-, -NH-, -O-, -SO-, -SO2-, optionally substituted alkylene groups (preferably having 1 to 6 carbon atoms, and may be linear or branched), optionally substituted cycloalkylene groups (preferably having 3 to 15 carbon atoms), optionally substituted aryl groups (preferably having 6 to 10 carbon atoms), and divalent linking groups formed by combining several of these. The substituent is not particularly limited and includes, for example, halogen atoms. p represents an integer between 0 and 3, preferably an integer between 1 and 3. v represents an integer, either 0 or 1. Each Xf1 independently represents a fluorine atom or an alkyl group substituted with at least one fluorine atom. The number of carbon atoms in this alkyl group is preferably 1 to 10, and more preferably 1 to 4. Perfluoroalkyl groups are preferred as alkyl groups substituted with at least one fluorine atom. Each Xf2 independently represents a hydrogen atom, an alkyl group which may have a fluorine atom as a substituent, or a fluorine atom. The number of carbon atoms in this alkyl group is preferably 1 to 10, and more preferably 1 to 4. Among these, Xf2 preferably represents a fluorine atom or an alkyl group substituted with at least one fluorine atom, and more preferably a fluorine atom or a perfluoroalkyl group. In particular, Xf1 and Xf2 are preferably independently a fluorine atom or a perfluoroalkyl group having 1 to 4 carbon atoms, and more preferably a fluorine atom or CF3. It is especially preferable that both Xf1 and Xf2 are fluorine atoms. * indicates the connection position. L in equation (Ia-1) 11 When represents a divalent linking group represented by formula (L1), the L in formula (L1) 111 The side joint (*) is A in equation (Ia-1). 12 - It is preferable that it be bonded with.

[0342] - Compounds represented by formulas (Ia-2) to (Ia-4) - Next, we will explain the compounds represented by formulas (Ia-2) to (Ia-4).

[0343] [ka]

[0344] In equation (Ia-2), A 21a - and A 21b - Each of these independently represents a monovalent anionic functional group. Here, A 21a - and A 21b - The monovalent anionic functional group represented by is the anionic moiety A1 mentioned above. - This refers to a monovalent group containing A. 21a - and A 21b -The monovalent anionic functional group represented by is not particularly limited, but examples include monovalent anionic functional groups selected from the group consisting of the above formulas (AX-1) to (AX-3). A 22 - A represents a divalent anionic functional group. Here, A 22 - The divalent anionic functional group represented by is the anionic moiety A2 mentioned above. - This refers to a divalent linking group containing A. 22 - Examples of divalent anionic functional groups represented by the formulas (BX-8) to (BX-11) shown below include the divalent anionic functional groups represented by the formulas (BX-8) to (BX-11).

[0345] [ka]

[0346] M 21a + M 21b + , and M 22 + Each of these independently represents an organic cation. 21a + M 21b + , and M 22 + The organic cation represented by the above M1 + This is synonymous with the same thing, and the preferred embodiment is also the same. L 21 and L 22 Each of these independently represents a divalent organic group.

[0347] In the above equation (Ia-2), M 21a + M 21b + , and M 22 + The organic cation represented by H + In compound PIa-2, which is obtained by substituting A, 22 The acid dissociation constant a2, which originates from the acidic site represented by H, is A 21aAcid dissociation constants a1-1 and A derived from H 21b It is greater than the acid dissociation constant a1-2, which originates from the acidic site represented by H. Note that the acid dissociation constants a1-1 and a1-2 correspond to the acid dissociation constant a1 mentioned above. Note A 21a - and A 21b - They may be the same or different from each other. 21a + M 21b + , and M 22 + They may be the same or different from one another. M 21a + M 21b + M 22 + , A 21a - , A 21b - , L 21 , and L 22 At least one of these may have an acid-degradable group as a substituent.

[0348] In equation (Ia-3), A 31a - and A 32 - Each of these independently represents a monovalent anionic functional group. 31a - The definition of a monovalent anionic functional group represented by is A in formula (Ia-2) above. 21a - and A 21b - This is synonymous with the same thing, and the preferred embodiment is also the same. A 32 - The monovalent anionic functional group represented by is the anionic moiety A2 described above. - This refers to a monovalent group containing A. 32 - The monovalent anionic functional group represented by is not particularly limited, but examples include monovalent anionic functional groups selected from the group consisting of the above formulas (BX-1) to (BX-7). A 31b - A represents a divalent anionic functional group. Here, A 31b - The divalent anionic functional group represented by is the anionic moiety A1 mentioned above. - This refers to a divalent linking group containing A. 31b - Examples of divalent anionic functional groups represented by the formula (AX-4) shown below include the divalent anionic functional group represented by the formula (AX-4).

[0349] [ka]

[0350] M 31a + M 31b + , and M 32 + Each of these independently represents a monovalent organic cation. 31a + M 31b + , and M 32 + The organic cation represented by the above M1 + This is synonymous with the same thing, and the preferred embodiment is also the same. L 31 and L 32 Each of these independently represents a divalent organic group.

[0351] In the above equation (Ia-3), M 31a + M 31b + , and M 32 + The organic cation represented by H + In compound PIa-3, which is obtained by substituting A, 32 The acid dissociation constant a2, which originates from the acidic site represented by H, is A 31a Acid dissociation constants a1-3 and A, derived from the acidic site represented by H. 31bIt is larger than the acid dissociation constant a1-4, which originates from the acidic site represented by H. Note that the acid dissociation constants a1-3 and a1-4 correspond to the acid dissociation constant a1 mentioned above. Note A 31a - and A 32 - They may be the same or different from each other. Also, M 31a + M 31b + , and M 32 + They may be the same or different from one another. M 31a + M 31b + M 32 + , A 31a - , A 32 - , L 31 , and L 32 At least one of these may have an acid-degradable group as a substituent.

[0352] In equation (Ia-4), A 41a - , A 41b - , and A 42 - Each of these independently represents a monovalent anionic functional group. 41a - and A 41b - The definition of a monovalent anionic functional group represented by is A in formula (Ia-2) above. 21a - and A 21b - It is synonymous with A. 42 - The definition of a monovalent anionic functional group represented by is A in formula (Ia-3) above. 32 - This is synonymous with the same thing, and the preferred embodiment is also the same. M 41a + M 41b + , and M 42+ Each of these independently represents an organic cation. L 41 This represents a trivalent organic group.

[0353] In the above equation (Ia-4), M 41a + M 41b + , and M 42 + The organic cation represented by H + In compound PIa-4, which is obtained by substituting A, 42 The acid dissociation constant a2, which originates from the acidic site represented by H, is A 41a Acid dissociation constants a1-5 and A, derived from the acidic site represented by H. 41b It is larger than the acid dissociation constant a1-6, which originates from the acidic site represented by H. Note that the acid dissociation constants a1-5 and a1-6 correspond to the acid dissociation constant a1 mentioned above. Note A 41a - , A 41b - , and A 42 - They may be the same or different from each other. Also, M 41a + M 41b + , and M 42 + They may be the same or different from one another. M 41a + M 41b + M 42 + , A 41a - , A 41b - , A 42 - , and L 41 At least one of these may have an acid-degradable group as a substituent.

[0354] L in equation (Ia-2) 21 and L 22 , and also L in equation (Ia-3) 31 and L32 The divalent organic group represented by is not particularly limited and includes, for example, -CO-, -NR-, -O-, -S-, -SO-, -SO2-, alkylene groups (preferably having 1 to 6 carbon atoms, which may be linear or branched), cycloalkylene groups (preferably having 3 to 15 carbon atoms), alkenylene groups (preferably having 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), divalent aromatic 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), divalent aromatic hydrocarbon ring groups (preferably 6 to 10-membered rings, and even more preferably 6-membered rings), and divalent organic groups formed by combining several of these. In the above -NR-, R can be a hydrogen atom or a monovalent organic group. The monovalent organic group is not particularly limited, but for example, an alkyl group (preferably having 1 to 6 carbon atoms) is preferred. The alkylene group, cycloalkylene group, alkenylene group, divalent aliphatic heterocyclic group, divalent aromatic heterocyclic group, and divalent aromatic hydrocarbon ring group may have substituents. Examples of substituents include halogen atoms (preferably fluorine atoms).

[0355] L in equation (Ia-2) 21 and L 22 , and also L in equation (Ia-3) 31 and L 32 The divalent organic group represented by is preferably, for example, the divalent organic group represented by the following formula (L2).

[0356] [ka]

[0357] In equation (L2), q represents an integer between 1 and 3. * indicates the joining position. Each Xf independently represents a fluorine atom or an alkyl group substituted with at least one fluorine atom. The number of carbon atoms in this alkyl group is preferably 1 to 10, and more preferably 1 to 4. Perfluoroalkyl groups are preferred as alkyl groups substituted with at least one fluorine atom. Xf is preferably a fluorine atom or a perfluoroalkyl group having 1 to 4 carbon atoms, and more preferably a fluorine atom or CF3. In particular, it is even more preferable that both Xf are fluorine atoms.

[0358] L A This represents a single bond or a divalent linking group. L A The divalent linking group represented by is not particularly limited and includes, for example, -CO-, -O-, -SO-, -SO2-, alkylene groups (preferably having 1 to 6 carbon atoms; may be linear or branched), cycloalkylene groups (preferably having 3 to 15 carbon atoms), divalent aromatic hydrocarbon ring groups (preferably 6 to 10 membered rings, more preferably 6 membered rings), and divalent linking groups formed by combining several of these. The alkylene group, the cycloalkylene group, and the divalent aromatic hydrocarbon ring group may have substituents. Examples of substituents include halogen atoms (preferably fluorine atoms).

[0359] Examples of divalent organic groups represented by formula (L2) include *-CF2-*, *-CF2-CF2-*, *-CF2-CF2-CF2-*, *-Ph-O-SO2-CF2-*, *-Ph-O-SO2-CF2-CF2-*, *-Ph-O-SO2-CF2-CF2-CF2-*, and *-Ph-OCO-CF2-*. Herein, Ph is a phenylene group which may have substituents, and is preferably a 1,4-phenylene group. The substituent is not particularly limited, but alkyl groups (for example, those having 1 to 10 carbon atoms are preferred, and those having 1 to 6 carbon atoms are preferred), alkoxy groups (for example, those having 1 to 10 carbon atoms are preferred, and those having 1 to 6 carbon atoms are preferred), or alkoxycarbonyl groups (for example, those having 2 to 10 carbon atoms are preferred, and those having 2 to 6 carbon atoms are preferred). L in equation (Ia-2) 21 and L 22 When represents a divalent organic group represented by formula (L2), the L in formula (L2) A The side joint (*) is A in equation (Ia-2). 21a - and A 21b - It is preferable that it be bonded with. L in equation (Ia-3) 31 and L 32 When represents a divalent organic group represented by formula (L2), the L in formula (L2) A The side joint (*) is A in equation (Ia-3). 31a - and A 32 - It is preferable that it be bonded with.

[0360] - Compound represented by formula (Ia-5) - Next, let's explain equation (Ia-5).

[0361] [ka]

[0362] In equation (Ia-5), A 51a - , A 51b - , and A 51c - Each of these independently represents a monovalent anionic functional group. Here, A 51a - , A 51b - , and A 51c - The monovalent anionic functional group represented by is the anionic moiety A1 mentioned above. - This refers to a monovalent group containing A. 51a - , A 51b - , and A 51c -The monovalent anionic functional group represented by is not particularly limited, and examples thereof include a monovalent anionic functional group selected from the group consisting of the above-described formulas (AX-1) to (AX-3). A 52a - and A 52b - represent a divalent anionic functional group. Here, A 52a - and A 52b - The divalent anionic functional group represented by is intended to be a divalent linking group containing the above-described anion moiety A2 - A 22 - Examples of the divalent anionic functional group represented by include a divalent anionic functional group selected from the group consisting of the above-described formulas (BX-8) to (BX-11).

[0363] M 51a + , M 51b + , M 51c + , M 52a + , and M 52b + each independently represent an organic cation. M 51a + , M 51b + , M 51c + , M 52a + , and M 52b + The organic cation represented by has the same meaning as M1 + described above, and the preferred embodiments are also the same. L 51 and L 53 each independently represent a divalent organic group. L 51 and L 53 The divalent organic group represented by has the same meaning as L 21 and L 22 in the above-described formula (Ia-2), and the preferred embodiments are also the same. L 52 represents a trivalent organic group. L 52As a trivalent organic group represented by the above formula (Ia-4), L 41 This is synonymous with the same thing, and the preferred embodiment is also the same.

[0364] In the above equation (Ia-5), M 51a + M 51b + M 51c + M 52a + , and M 52b + The organic cation represented by H + In compound PIa-5, which is obtained by substituting A, 52a Acid dissociation constants a2-1 and A, which originate from the acidic site represented by H. 52b The acid dissociation constant a2-2, which originates from the acidic site represented by H, is A 51a Acid dissociation constants a1-1 and A derived from H. 51b Acid dissociation constants a1-2 and A originate from the acidic site represented by H. 51c This is greater than the acid dissociation constant a1-3 derived from the acidic site represented by H. Note that acid dissociation constants a1-1 to a1-3 correspond to the acid dissociation constant a1 mentioned above, and acid dissociation constants a2-1 and a2-2 correspond to the acid dissociation constant a2 mentioned above. Note A 51a - , A 51b - , and A 51c - They may be the same or different from each other. Also, A 52a - and A 52b - They may be the same or different from each other. 51a + M 51b + M 51c + M 52a + , and M 52b + They may be the same or different from one another. M 51b + M 51c +, M 52a + , M 52b + , A 51a - , A 51b - , A 51c - , L 51 , L 52 , and L 53 At least one of them may have an acid-decomposable group as a substituent.

[0365] (Compound (II)) Compound (II) is a compound having two or more of the above structural moieties X and one or more of the following structural moieties Z, and upon irradiation with actinic rays or radiation, the above first acidic moiety derived from the above structural moiety X and two or more of the above structural moieties Z and an acid-generating compound containing an acid-generating compound. Structural moiety Z: A non-ionic moiety capable of neutralizing an acid

[0366] In compound (II), the definition of the structural moiety X, and A1 - and M1 + The definitions of are synonymous with the definitions of the structural moiety X in the above-mentioned compound (I), and A1 - and M1 + and the preferred embodiments are also the same.

[0367] In the above compound (II), in the acidic moiety HA1 represented by replacing the cationic moiety M1 + in the above structural moiety X with H + in the compound PII obtained by replacement, the preferred range of the acid dissociation constant a1 derived from the acidic moiety HA1 represented by replacing the cationic moiety M1 + in the above structural moiety X with H + is the same as the acid dissociation constant a1 in the above compound PI. Incidentally, when compound (II) is, for example, an acid-generating compound having two of the above first acidic moieties derived from the above structural moiety X and the above structural moiety Z, compound PII corresponds to "a compound having two HA1s". When the acid dissociation constant of this compound PII is determined, if compound PII is "one A1- The acid dissociation constant when a compound having "one HA1" is formed, and "one A1 - A compound having one HA1 is a compound having two A1 - The acid dissociation constant when a compound becomes "a compound having " corresponds to the acid dissociation constant a1.

[0368] The acid dissociation constant a1 is determined by the acid dissociation constant measurement method described above. The above compound PII refers to the acid generated when compound (II) is irradiated with active light or radiation. Note that the two or more structural parts X described above may be the same or different. - , and two or more of the above M1 + These may be the same or different.

[0369] The nonionic site in structural site Z that can neutralize the acid is not particularly limited, but is preferably, for example, a site that can electrostatically interact with a proton or a site that contains an electron-containing functional group. Examples of functional groups that can electrostatically interact with protons, or that have electrons, include functional groups having a macrocyclic structure such as cyclic polyethers, or functional groups having a nitrogen atom with a lone pair of electrons that does not contribute to π-conjugation. A nitrogen atom having a lone pair of electrons that does not contribute to π-conjugation is, for example, a nitrogen atom having the substructure shown in the following formula.

[0370] [ka]

[0371] Examples of substructures of functional groups having a group or electron that can electrostatically interact with a proton include crown ether structures, azacrown ether structures, primary to tertiary amine structures, pyridine structures, imidazole structures, and pyrazine structures, among which primary to tertiary amine structures are preferred.

[0372] Compound (II) is not particularly limited, but examples include compounds represented by the following formulas (IIa-1) and (IIa-2).

[0373] [ka]

[0374] In the above equation (IIa-1), A 61a - and A 61b - These are A in equation (Ia-1) mentioned above. 11 - It is synonymous with the same as the preferred embodiment. Also, M 61a + and M 61b + These are M in equation (Ia-1) described above. 11 + This is synonymous with the same thing, and the preferred embodiment is also the same. In the above equation (IIa-1), L 61 and L 62 These terms are equivalent to L1 in the above-mentioned formula (Ia-1), and the preferred embodiments are the same.

[0375] In formula (IIa-1), R 2X R represents a monovalent organic group. 2X The monovalent organic group represented by is not particularly limited and includes alkyl groups (preferably having 1 to 10 carbon atoms, which may be linear or branched), cycloalkyl groups (preferably having 3 to 15 carbon atoms), or alkenyl groups (preferably having 2 to 6 carbon atoms). 2X The -CH2- contained in the alkyl, cycloalkyl, and alkenyl groups in the monovalent organic group represented by may be substituted with one or more selected from the group consisting of -CO-, -NH-, -O-, -S-, -SO-, and -SO2-. The alkylene group, cycloalkylene group, and alkenylene group may have substituents. The substituents are not particularly limited, but examples include halogen atoms (preferably fluorine atoms).

[0376] In the above equation (IIa-1), M 61a + and M 61b + The organic cation represented by H + In compound PIIa-1, which is obtained by substituting A, 61a Acid dissociation constants a1-7 and A, derived from the acidic site represented by H. 61b The acid dissociation constants a1-8, derived from the acidic site represented by H, correspond to the acid dissociation constant a1 mentioned above. Furthermore, in the above compound (IIa-1), the above cation site M in the above structural site X. 61a + and M 61b + to H + Compound PIIa-1, which is obtained by replacing HA, 61a -L 61 -N(R 2X )-L 62 -A 61b H is the corresponding element. Furthermore, compound PIIa-1 and the acid generated from the compound represented by formula (IIa-1) upon irradiation with active light or radiation are the same. M 61a + M 61b + , A 61a - , A 61b - , L 61 , L 62 , and R 2X At least one of these may have an acid-degradable group as a substituent.

[0377] In the above equation (IIa-2), A 71a - , A 71b - , and A 71c - These are A in equation (Ia-1) mentioned above. 11 - This is synonymous with the same thing, and the preferred embodiment is also the same. 71a + M 71b + , and M 71c+ These are M in equation (Ia-1) described above. 11 + This is synonymous with the same thing, and the preferred embodiment is also the same. In the above equation (IIa-2), L 71 , L 72 , and L 73 These terms are equivalent to L1 in the above-mentioned formula (Ia-1), and the preferred embodiments are the same.

[0378] In the above equation (IIa-2), M 71a + M 71b + , and M 71c + The organic cation represented by H + In compound PIIa-2, which is obtained by substituting A, 71a Acid dissociation constants a1-9 and A, derived from the acidic site represented by H. 71b Acid dissociation constants a1-10 and A originate from the acidic site represented by H. 71c The acid dissociation constants a1-11, derived from the acidic site represented by H, correspond to the acid dissociation constant a1 mentioned above. Furthermore, in the above compound (IIa-1), the above cation site M in the above structural site X. 71a + M 71b + , and M 71c + to H + Compound PIIa-2, which is obtained by replacing HA, 71a -L 71 -N(L 73 -A 71c H)-L 72 -A 71b H is the corresponding element. Furthermore, compound PIIa-2 and the acid generated from the compound represented by formula (IIa-2) upon irradiation with active light or radiation are the same. M 71a + M 71b + M 71c + , A 71a - , A 71b - , A71c - , L 71 , L 72 , and L 73 At least one of these may have an acid-degradable group as a substituent.

[0379] Examples of non-cationic sites that compound (I) and compound (II) may possess are given below.

[0380] [ka]

[0381] [ka]

[0382] The following are specific examples of photoacid generators, but are not limited to these.

[0383] [ka]

[0384] [ka]

[0385] When the photosensitive or radiation-sensitive resin composition contains a photoacid generator (B), its content is not particularly limited, but in terms of making the cross-sectional shape of the formed pattern more rectangular, it is preferably 0.5% by mass or more, and more preferably 1.0% by mass or more, relative to the total solid content of the photosensitive or radiation-sensitive resin composition. The above content is preferably 50.0% by mass or less, more preferably 30.0% by mass or less, and even more preferably 25.0% by mass or less, relative to the total solid content of the photosensitive or radiation-sensitive resin composition.

[0386] The mass content of onium salt (C) in the photosensitive or radiation-sensitive resin composition is A C The mass-based content of the photoacid generator (B) is set to A BIn that case, A C :A B The ratio is preferably 1:4 to 4:1, more preferably 1:3 to 3:1, and even more preferably 1:2 to 2:1.

[0387] The photoacid generator (B) may be used alone or in combination of two or more types.

[0388] <Acid diffusion control agents other than onium salts (C)> As mentioned above, onium salts (C) can function as acid diffusion control agents. The photosensitive or radiation-sensitive resin composition may contain an acid diffusion control agent other than onium salt (C). In step (3) described above, an acid diffusion control agent other than the onium salt (C) may be mixed in addition to the onium salt (C) and the resin (A). The types of acid diffusion control agents other than onium salts (C) are not particularly limited, and examples include basic compounds, low molecular weight compounds having a nitrogen atom and a group that is eliminated by the action of an acid, basic compounds whose basicity is reduced or lost by irradiation with active light or radiation, and onium salt compounds having a nitrogen atom in the cation. Specific examples of basic compounds include those described in paragraphs

[0132] to

[0136] of International Publication No. 2020 / 066824; specific examples of basic compounds whose basicity is reduced or lost by irradiation with active light or radiation include those described in paragraphs

[0137] to

[0155] of International Publication No. 2020 / 066824; specific examples of low molecular weight compounds having a nitrogen atom and a group that is eliminated by the action of an acid include those described in paragraphs

[0156] to

[0163] of International Publication No. 2020 / 066824; and specific examples of onium salt compounds having a nitrogen atom in the cation include those described in paragraph

[0164] of International Publication No. 2020 / 066824.

[0389] In addition to the above, known compounds disclosed in paragraphs

[0627] to

[0664] of U.S. Patent Application Publication 2016 / 0070167A1, paragraphs

[0095] to

[0187] of U.S. Patent Application Publication 2015 / 0004544A1, paragraphs

[0403] to

[0423] of U.S. Patent Application Publication 2016 / 0237190A1, and paragraphs

[0259] to

[0328] of U.S. Patent Application Publication 2016 / 0274458A1 can be suitably used as acid diffusion control agents.

[0390] If the photosensitive or radiation-sensitive resin composition contains an acid diffusion control agent other than onium salt (C), the content of the acid diffusion control agent other than onium salt (C) (the total if there are multiple types) is preferably 0.01 to 10% by mass relative to the total solid content of the photosensitive or radiation-sensitive resin composition. In a photosensitive or radiation-sensitive resin composition, an acid diffusion control agent other than onium salt (C) may be used alone or in combination of two or more.

[0391] <Hydrophobic resin (D)> The photosensitive or radiation-sensitive resin composition may further contain a hydrophobic resin different from resin (A). In step (3) described above, a hydrophobic resin may be mixed in addition to the onium salt (C) and resin (A). Hydrophobic resins are preferably designed to be unevenly distributed on the surface of the resist film, but unlike surfactants, they do not necessarily need to have hydrophilic groups within their molecules and do not need to contribute to the uniform mixing of polar and nonpolar substances. The effects of adding hydrophobic resins include controlling the static and dynamic contact angles of the resist film surface with respect to water, as well as suppressing outgassing.

[0392] From the viewpoint of uneven distribution on the film surface, the hydrophobic resin preferably has one or more of the following: fluorine atoms, silicon atoms, and CH3 substructures contained in the side chain portion of the resin, and more preferably two or more. The hydrophobic resin preferably has hydrocarbon groups having 5 or more carbon atoms. These groups may be present in the main chain of the resin or substituted in the side chains. Examples of hydrophobic resins include the compounds described in paragraphs

[0275] to

[0279] of International Publication No. 2020 / 004306.

[0393] When the photosensitive or radiation-sensitive resin composition contains a hydrophobic resin, the hydrophobic resin content is preferably 0.01 to 20.0% by mass, and more preferably 0.1 to 15.0% by mass, relative to the total solid content of the photosensitive or radiation-sensitive resin composition.

[0394] <Surfactant (E)> The photosensitive or radiation-sensitive resin composition may contain a surfactant. The inclusion of a surfactant improves adhesion and allows for the formation of patterns with fewer development defects. In step (3) described above, a surfactant may be added to the onium salt (C) and resin (A). The surfactant is preferably a fluorine-based and / or silicone-based surfactant. Examples of fluorinated and / or silicone-based surfactants include those disclosed in paragraphs

[0218] and

[0219] of International Publication No. 2018 / 19395.

[0395] These surfactants may be used individually or in combination of two or more types.

[0396] If the photosensitive or radiation-sensitive resin composition contains a surfactant, the surfactant content is preferably 0.0001 to 2.0% by mass, more preferably 0.0005 to 1.0% by mass, and even more preferably 0.1 to 1.0% by mass, relative to the total solid content of the photosensitive or radiation-sensitive resin composition.

[0397] <Solvent (F)> The photosensitive or radiation-sensitive resin composition preferably contains a solvent. The solvent preferably contains (M1) propylene glycol monoalkyl ether carboxylate and (M2) at least one selected from the group consisting of propylene glycol monoalkyl ether, lactic acid ester, acetate ester, alkoxypropionic acid ester, linear ketone, cyclic ketone, lactone, and alkylene carbonate. The solvent may further contain components other than components (M1) and (M2).

[0398] Combining the solvent and resin described above is preferable in terms of improving the coatability of the photosensitive or radiation-sensitive resin composition and reducing the number of development defects in the pattern. The solvent described above has a good balance of solubility, boiling point, and viscosity with the resin described above, which can suppress unevenness in the thickness of the resist film and the generation of precipitates during spin coating. Details of components (M1) and (M2) are described in paragraphs

[0218] to

[0226] of International Publication No. 2020 / 004306, and these contents are incorporated herein by reference.

[0399] If the solvent further contains components other than components (M1) and (M2), the content of the components other than components (M1) and (M2) is preferably 5 to 30% by mass relative to the total amount of the solvent.

[0400] The solvent content in the photosensitive or radiation-sensitive resin composition is preferably set so that the solid content concentration is 0.5 to 30% by mass, and more preferably 1 to 20% by mass. This further improves the coatability of the photosensitive or radiation-sensitive resin composition.

[0401] <Other additives> The photosensitive or radiation-sensitive resin composition may further contain a dissolution-inhibiting compound, a dye, a plasticizer, a photosensitizer, a light absorber, and / or a compound that promotes solubility in a developer (for example, a phenol compound with a molecular weight of 1000 or less, or an alicyclic or aliphatic compound containing a carboxyl group).

[0402] The above-mentioned "dissolution-inhibiting compounds" are compounds with a molecular weight of 3000 or less that decompose due to the action of acid, thereby reducing their solubility in organic developing solutions.

[0403] The photosensitive or radiation-sensitive resin compositions described herein are suitably used as photosensitive compositions for EUV exposure. EUV light has a wavelength of 13.5 nm, which is shorter than ArF light (wavelength 193 nm), resulting in fewer incident photons when exposed at the same sensitivity. Consequently, the "photon shot noise," where the number of photons varies probabilistically, has a greater impact, leading to deterioration of the LER and bridge defects. One way to reduce photon shot noise is to increase the exposure dose to increase the number of incident photons, but this comes at the cost of higher sensitivity.

[0404] A high A value, calculated using the following formula (1), indicates that the EUV light and electron beam absorption efficiency of the resist film formed from the resist composition is high, which is effective in reducing photon shot noise. The A value represents the EUV light and electron beam absorption efficiency of the mass percentage of the resist film. Formula (1): A=([H]×0.04+[C]×1.0+[N]×2.1+[O]×3.6+[F]×5.6+[S]×1.5+[I]×39.5) / ([H]×1+[C]×12+[N]×14+[O]×16+[F]×19+[S]×32+[I]×127) A value of 0.120 or higher is preferred. There is no particular upper limit, but if the A value is too high, the EUV light and electron beam transmittance of the resist film decreases, the optical image profile in the resist film deteriorates, and as a result it becomes difficult to obtain a good pattern shape. Therefore, 0.240 or lower is preferred, and 0.220 or lower is more preferred.

[0405] In formula (1), [H] represents the molar ratio of hydrogen atoms derived from the total solids to the total atoms of the total solids in the photosensitive or radiation-sensitive resin composition, [C] represents the molar ratio of carbon atoms derived from the total solids to the total atoms of the total solids in the photosensitive or radiation-sensitive resin composition, [N] represents the molar ratio of nitrogen atoms derived from the total solids to the total atoms of the total solids in the photosensitive or radiation-sensitive resin composition, and [O] represents the molar ratio of nitrogen atoms derived from the total solids in the photosensitive or radiation-sensitive resin composition. [F] represents the molar ratio of oxygen atoms derived from the total solids to the total atoms of the total solids in the photosensitive or radiation-sensitive resin composition, [S] represents the molar ratio of sulfur atoms derived from the total solids to the total atoms of the total solids in the photosensitive or radiation-sensitive resin composition, and [I] represents the molar ratio of iodine atoms derived from the total solids to the total atoms of the total solids in the photosensitive or radiation-sensitive resin composition. For example, if the resist composition contains an acid-degradable resin, a photoacid generator, an acid diffusion control agent, and a solvent, the acid-degradable resin, the photoacid generator, and the acid diffusion control agent constitute the solid content. In other words, the total atoms of the total solid content refer to the sum of the total atoms derived from the resin, the total atoms derived from the photoacid generator, and the total atoms derived from the acid diffusion control agent. For example, [H] represents the molar ratio of hydrogen atoms derived from the total solid content to the total atoms of the total solid content. Based on the above example, [H] represents the molar ratio of the total hydrogen atoms derived from the acid-degradable resin, the total atoms derived from the photoacid generator, and the total atoms derived from the acid diffusion control agent to the sum of the total atoms derived from the acid-degradable resin, the total atoms derived from the photoacid generator, and the total atoms derived from the acid diffusion control agent.

[0406] The A value can be calculated by determining the atomic ratio of the constituent components if the structure and content of the total solid components in the resist composition are known. Even if the constituent components are unknown, the atomic ratio can be calculated by analytical methods such as elemental analysis of the resist film obtained by evaporating the solvent components of the resist composition.

[0407] <Method for forming resist films and patterns> The procedure for a pattern-forming method using the above-mentioned photosensitive or radiation-sensitive resin composition is not particularly limited, but it is preferable to have the following steps. Step 1: A step of forming a resist film on a substrate using the photosensitive or radiation-sensitive resin composition produced by the method for producing the photosensitive or radiation-sensitive resin composition of the present invention. Step 2: Exposure of the resist film Step 3: Developing the exposed resist film using a developer solution. The following details the steps for each of the above processes.

[0408] (Step 1: Resist film formation process) Step 1 is a step of forming a resist film on a substrate using a photosensitive or radiation-sensitive resin composition. The definition of a photosensitive or radiation-sensitive resin composition is as described above.

[0409] One method for forming a resist film on a substrate using a photosensitive or radiation-sensitive resin composition is to coat the substrate with the photosensitive or radiation-sensitive resin composition. Furthermore, it is preferable to filter the photosensitive or radiation-sensitive resin composition before application, if necessary. 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.

[0410] The photosensitive or radiation-sensitive resin composition can be applied to a substrate (e.g., silicon, silicon dioxide coated) used in the manufacture of integrated circuit elements by a suitable coating method such as a spinner or coater. Spin coating using a spinner is preferred. The preferred rotation speed when spin coating using a spinner is 1000 to 3000 rpm. After applying the photosensitive or radiation-sensitive resin composition, the substrate may be dried to form a resist film. If necessary, various undercoats (inorganic films, organic films, anti-reflective films) may be formed beneath the resist film.

[0411] As for drying methods, one example is drying by heating. Heating can be carried out using means provided in a normal exposure machine and / or developing machine, or it may be carried out using a hot plate 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.

[0412] The thickness of the resist film is not particularly limited, but 10 to 120 nm is preferred in order to form finer patterns with higher precision. In particular, when using EUV exposure, the thickness of the resist film is more preferably 10 to 65 nm, and even more preferably 15 to 50 nm. When using ArF immersion exposure, the thickness of the resist film is more preferably 10 to 120 nm, and even more preferably 15 to 90 nm.

[0413] Alternatively, a topcoat may be formed on the upper layer of the resist film using a topcoat composition. Preferably, the topcoat composition is not mixed with the resist film and can be uniformly applied to the upper layer of the resist film. The topcoat is not particularly limited, and conventionally known topcoats can be formed by conventionally known methods. For example, a topcoat can be formed based on the description in paragraphs

[0072] to

[0082] of Japanese Patent Application Publication No. 2014-059543. For example, it is preferable to form a topcoat containing a basic compound, such as that described in Japanese Patent Publication No. 2013-61648, on the resist film. Specific examples of basic compounds that the topcoat may contain include basic compounds that may also be included in photosensitive or radiation-sensitive resin compositions. The top coat may also preferably contain a compound comprising at least one group or bond selected from the group consisting of ether bonds, thioether bonds, hydroxyl groups, thiol groups, carbonyl bonds, and ester bonds.

[0414] (Step 2: Exposure process) Step 2 is the process of exposing the resist film. One method of exposure is to irradiate the formed resist film with active light or radiation through a predetermined mask. Examples of active light or radiation include infrared light, visible light, ultraviolet light, far ultraviolet light, extreme ultraviolet light, X-rays, and electron beams, with wavelengths of 250 nm or less being preferred, more preferably 220 nm or less, and far ultraviolet light with wavelengths of 1 to 200 nm, specifically KrF excimer laser (248 nm), ArF excimer laser (193 nm), F2 excimer laser (157 nm), EUV (13.5 nm), X-rays, and electron beams being particularly preferred.

[0415] It is preferable to bake (heat) the image after exposure but before developing. Baking accelerates the reaction in the exposed areas, resulting in better sensitivity and pattern shape. 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 10 to 1000 seconds, more preferably 10 to 180 seconds, and even more preferably 30 to 120 seconds. Heating can be performed using the means provided in a standard exposure and / or developing machine, or it may be done using a hot plate or the like. This process is also called post-exposure baking.

[0416] (Process 3: Development process) Step 3 is the process of developing the exposed resist film using a developer solution to form a pattern. The developer may be an alkaline developer or a developer containing an organic solvent (hereinafter also referred to as an organic developer).

[0417] Examples of development methods include immersing the substrate in a tank filled with developer solution for a certain period of time (dip method), puddling the developer solution onto the substrate surface using surface tension and letting it stand for a certain period of time (paddle method), spraying the developer solution onto the substrate surface (spray method), and continuously dispensing the developer solution while scanning a developer solution dispensing nozzle at a constant speed onto a substrate rotating at a constant speed (dynamic dispensing method). Alternatively, after the developing process, a step may be performed to stop the development process while substituting with another solvent. The development time is not particularly limited as long as it is enough time for the resin in the unexposed areas to dissolve sufficiently, but 10 to 300 seconds is preferred, and 20 to 120 seconds is more preferred. The temperature of the developer is preferably 0 to 50°C, and more preferably 15 to 35°C.

[0418] It is preferable to use an alkaline aqueous solution containing alkali as the alkaline developer. The type of alkaline aqueous solution is not particularly limited, but examples include alkaline aqueous solutions containing quaternary ammonium salts represented by tetramethylammonium hydroxide, inorganic alkalis, primary amines, secondary amines, tertiary amines, alcohol amines, or cyclic amines. Among these, it is preferable that the alkaline developer be an aqueous solution of a quaternary ammonium salt represented by tetramethylammonium hydroxide (TMAH). Appropriate amounts of alcohols, surfactants, etc., may be added to the alkaline developer. The alkali concentration of the alkaline developer is usually preferably 0.1 to 20% by mass. The pH of the alkaline developer is usually preferably 10.0 to 15.0.

[0419] The organic developer is preferably a developer containing at least one organic solvent selected from the group consisting of ketone solvents, ester solvents, alcohol solvents, amide solvents, ether solvents, and hydrocarbon solvents.

[0420] The above solvents may be mixed in multiple quantities, or mixed with other solvents or 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 particularly preferably substantially water-free. The content of the organic solvent in the organic developer is preferably 50% to 100% by mass, more preferably 80% to 100% by mass, even more preferably 90% to 100% by mass, and particularly preferably 95% to 100% by mass, based on the total amount of the developer.

[0421] (Other processes) The above pattern forming method preferably includes a step of washing with a rinsing solution after step 3.

[0422] Examples of rinsing solutions used in the rinsing step after the development process using an alkaline developer include pure water. A suitable amount of surfactant may be added to the pure water. A suitable amount of surfactant may be added to the rinse solution.

[0423] The rinsing solution used in the rinsing step after the development step using an organic developer is not particularly limited as long as it does not dissolve the pattern, and a solution containing a general organic solvent can be used. Preferably, the rinsing solution contains at least one organic solvent selected from the group consisting of hydrocarbon solvents, ketone solvents, ester solvents, alcohol solvents, amide solvents, and ether solvents.

[0424] The rinsing process is not particularly limited and can be performed in any way, for example, by continuously discharging rinsing solution onto a substrate rotating at a constant speed (rotary coating method), by immersing the substrate in a tank filled with rinsing solution for a certain period of time (dip method), or by spraying rinsing solution onto the surface of the substrate (spray method). Furthermore, the pattern formation method may include a heating step (Post Bake) after the rinsing step. This step removes any developer and rinsing solution remaining between and inside the patterns due to baking. This step also has the effect of smoothing the resist pattern and improving the surface roughness of the pattern. The heating step after the rinsing step is usually performed at 40 to 250°C (preferably 90 to 200°C) for 10 seconds to 3 minutes (preferably 30 seconds to 120 seconds).

[0425] Alternatively, the formed pattern may be used as a mask to perform an etching process on the substrate. In other words, the pattern formed in step 3 may be used as a mask to process the substrate (or the underlying film and the substrate) to form a pattern on the substrate. The processing method for the substrate (or the underlying film and substrate) is not particularly limited, but a preferred method is to form a pattern on the substrate by performing dry etching on the substrate (or the underlying film and substrate) using the pattern formed in step 3 as a mask. Dry etching is preferably performed using oxygen plasma etching.

[0426] It is preferable that the photosensitive or radiation-sensitive resin compositions and the various materials used in the pattern-forming methods of this specification (e.g., solvents, developers, rinses, anti-reflective film-forming compositions, topcoat-forming compositions, etc.) do not contain impurities such as metals. The impurity content in these materials is preferably 1 ppm (parts per million) or less, more preferably 10 ppb (parts per billion) or less, even more preferably 100 ppt (parts per trillion) or less, particularly preferably 10 ppt or less, and most preferably 1 ppt or less. There is no particular lower limit, but 0 ppt or more is preferred. Examples of metal impurities include Na, K, Ca, Fe, Cu, Mg, Al, Li, Cr, Ni, Sn, Ag, As, Au, Ba, Cd, Co, Pb, Ti, V, W, and Zn.

[0427] One method for removing impurities such as metals from various materials is filtration using a filter. Details of filtration using a filter are described in paragraph

[0321] of International Publication No. 2020 / 004306.

[0428] Methods for reducing impurities such as metals contained in various materials include, for example, selecting raw materials with low metal content as constituent materials for various materials, filtering the constituent materials, and performing distillation under conditions that suppress contamination as much as possible, such as by lining the inside of the apparatus with Teflon®.

[0429] In addition to filter filtration, impurities may be removed using adsorbents, or a combination of filter filtration and adsorbents may be used. Known adsorbents can be used, such as inorganic adsorbents like silica gel and zeolite, and organic adsorbents like activated carbon. To reduce impurities such as metals contained in the above materials, it is necessary to prevent the introduction of metal impurities during the manufacturing process. Whether metal impurities have been sufficiently removed from the manufacturing equipment can be confirmed by measuring the content of metal components in the cleaning solution used to clean the equipment. The content of metal components in the cleaning solution after use is preferably 100 ppt by mass or less, more preferably 10 ppt by mass or less, and even more preferably 1 ppt by mass or less. There is no particular lower limit, but 0 ppt by mass or more is preferred.

[0430] In organic processing solutions such as rinsing solutions, a conductive compound may be added to prevent malfunctions of chemical piping and various parts (filters, O-rings, and tubes, etc.) due to electrostatic charging and subsequent electrostatic discharge. The conductive compound is not particularly limited, but methanol is an example. The amount added is not particularly limited, but in terms of maintaining desirable developing or rinsing characteristics, 10% by mass or less is preferred, and 5% by mass or less is more preferred. There is no particular lower limit, but 0.01% by mass or more is preferred. For chemical piping, various types of piping can be used, such as SUS (stainless steel), or polyethylene, polypropylene, or fluororesin (polytetrafluoroethylene or perfluoroalkoxy resin, etc.) that has been treated with an antistatic coating. Similarly, for filters and O-rings, polyethylene, polypropylene, or fluororesin (polytetrafluoroethylene or perfluoroalkoxy resin, etc.) that has been treated with an antistatic coating can be used.

[0431] <Methods for manufacturing electronic devices> This specification also relates to a method for manufacturing an electronic device, including the pattern forming method described above, and to an electronic device manufactured by this manufacturing method. Preferred embodiments of the electronic devices described herein include those mounted in electrical and electronic equipment (such as home appliances, office automation equipment, media-related equipment, optical equipment, and communication equipment).

[0432] <Method for producing onium salt> The present invention also relates to a method for producing an onium salt, comprising the steps of (1) passing a solution containing an acid compound (CA) with a pKa of 2.0 or higher through a column packed with an ion exchange resin, and (2) producing an onium salt (C) using the acid compound (CA) after it has passed through the column. [Examples]

[0433] The present invention will be described in more detail below based on examples. The materials, amounts used, proportions, processing content, and processing procedures shown in the following examples can be modified as appropriate without departing from the spirit of the present invention. Therefore, the scope of the present invention should not be interpreted as being limited by the examples shown below.

[0434] The compounds used in the examples and comparative examples are listed below.

[0435] <Acid compounds> The following acid compounds, CH-1 to CH-10 and XH-1, were used. Me represents a methyl group.

[0436] [ka]

[0437] The pKa values ​​for CH-1 to CH-10 and XH-1 are shown in Table 1 below.

[0438] [Table 1]

[0439] As shown in Table 1, CH-1 to CH-10 are acidic compounds (CA) with a pKa of 2.0 or higher, while XH-1 is not an acidic compound (CA).

[0440] <Resin (A)> Resins A-1 to A-15 were used as resin (A). Table 2 shows the content (mol%), weight-average molecular weight (Mw), and dispersion (Mw / Mn) of each repeating unit in each resin. The content of each repeating unit is the ratio (molar ratio) of each repeating unit to the total number of repeating units in each resin. Each repeating unit is indicated by the structure of its corresponding monomer. The weight-average molecular weight (Mw) and dispersion (Mw / Mn) of the resin were measured by GPC (carrier: tetrahydrofuran (THF)) (in polystyrene equivalent). The repeating unit content was also determined. 13 The measurement was performed using 1C-NMR (nuclear magnetic resonance).

[0441] [ka]

[0442] [ka]

[0443] [ka]

[0444] [ka]

[0445] [ka]

[0446] [Table 2]

[0447] <Photoacid Generator (B)> Compounds B-1 to B-7 were used as photoacid generators (B).

[0448] [ka]

[0449] [ka]

[0450] <Hydrophobic resin> D-1 was used as the hydrophobic resin. The content (mol%), weight-average molecular weight (Mw), and degree of dispersion (Mw / Mn) of each repeating unit contained in D-1 are shown. The content of each repeating unit is the ratio (mol ratio) of each repeating unit to the total number of repeating units.

[0451] [ka]

[0452] <Surfactants> The surfactants used were W-1 to W-4 listed below. W-1: Megafuck R08 (manufactured by DIC Corporation) W-2: Megafuck F176 (manufactured by DIC) W-3: Troisol S-366 (manufactured by Troy Chemical Co., Ltd.) W-4:PF656 (manufactured by OMNOVA)

[0453] <Solvent> The solvents used are listed below. S-1: Propylene glycol monomethyl ether acetate (PGMEA) S-2: Propylene glycol monomethyl ether (PGME) S-3: Cyclohexanone S-4: Ethyl lactate (EL) S-5: γ-Butyrolactone

[0454] <Onium salt (acid diffusion control agent)> The structure of the onium salt is shown below. Me represents the methyl group.

[0455] [ka]

[0456] [ka]

[0457] [ka]

[0458] In Examples 1 to 42 and Comparative Example 3, onium salts were produced by a step (1) of passing a solution containing an acid compound through a column packed with ion exchange resin, and a step (2) of producing an onium salt using the acid compound after it has passed through the column. As an example, the operations performed in Example 5 are shown below.

[0459] <Process (1): Purification of acid compounds> A glass column was packed with 300g of washed ion exchange resin (DIAION SK112L: manufactured by Mitsubishi Chemical Corporation). The washing and packing of the ion exchange resin was performed as follows: 300g of ion exchange resin was placed in 500ml of 0.1mol / L hydrochloric acid and allowed to stand for 30 minutes, after which it was packed into the glass column. Then, 1000g of distilled water was passed through to replace the hydrochloric acid with distilled water, and then 1000g of methanol was passed through to replace the distilled water with methanol. A solution of 30.0 g of the acid compound (CH-2) was dissolved in 240 g of methanol and passed through a column packed with ion exchange resin at 23°C and atmospheric pressure. 500 g of methanol was then passed through the column. The resulting solution was removed by distillation under reduced pressure to remove methanol. 240 g of diisopropyl ether and 60 g of 1 mol / L hydrochloric acid were added, and liquid-liquid extraction was performed. 60 g of distilled water was added to the organic layer, and the liquid-liquid extraction was repeated four times. After removing the solvent from the organic layer under reduced pressure, 900 g of heptane was added, and the mixture was stirred at 23°C. The mixture was filtered to obtain 25.0 g of the acid compound (CH-2).

[0460] <Process (2): Production of Onium Salt> 532 g of methylene chloride was added to 20.0 g of the acid compound (CH-2) obtained in step (1). Next, 246 g of a 20% by mass aqueous solution of triphenylsulfonium bicarbonate was added and the mixture was stirred at 23°C for 30 minutes. After removing the aqueous layer, 80 g of distilled water was added and the liquid-liquid separation operation was repeated four times. The solvent of the organic layer was removed by vacuum distillation, and 796 g of acetonitrile was added to the obtained solid and heated to 60°C to dissolve it. 223 g of diisopropyl ether was added and the mixture was stirred at 23°C, and the obtained solid was filtered to obtain 41.6 g of onium salt (C-2).

[0461] [ka]

[0462] Examples 19, 22, 23, 26, 27, 29-32, 35, 38-40, and 42 were carried out in the same manner as in Example 5. In Example 36, the onium salt was produced in the same manner as in Example 5, except that a salt consisting of the sulfonium cation and bicarbonate ion present in the onium salt (C-11) to be produced was used instead of triphenylsulfonium bicarbonate. In Example 37, an onium salt was produced in the same manner as in Example 5, except that a salt consisting of a sulfonium cation and bicarbonate ions from C-11 was used in addition to triphenylsulfonium bicarbonate. In Examples 1, 2, 4, 6, 8-18, 20, 21, 24, 25, 28, 33, 34, 41 and Comparative Example 3, onium salts were produced in the same manner as in Example 5, except that the acid compounds shown in Tables 3 and 4 below were used instead of the acid compound (CH-2), and the ion exchange resins shown in Tables 3 and 4 below were used instead of DIAION SK112L. In Examples 3, 7, 14, and 18, the onium salt was produced in the same manner as in Example 5, except that the acid compounds shown in Tables 3 and 4 below were used instead of the acid compound (CH-2), the ion exchange resins shown in Tables 3 and 4 below were used instead of DIAION SK112L, and the salts consisting of sulfonium cations and bicarbonate ions of the onium salts (C-3 and C-7) to be produced were used instead of triphenylsulfonium bicarbonate.

[0463] In Comparative Example 1, the purification using ion exchange resin as in Example 1 was not performed.

[0464] In Comparative Example 2, acid washing was performed instead of purification with ion exchange resin as in Example 1. Acid washing was carried out by the following method: 30.0 g of the acid compound (CH-1) was dissolved in 240 g of diisopropyl ether, then 60 g of 0.1 mol / L hydrochloric acid was added and liquid-liquid extraction was performed. This was repeated twice, then 60 g of distilled water was added to the organic layer, and liquid-liquid extraction was repeated four times. After removing the solvent from the organic layer under reduced pressure, 900 g of heptane was added and the mixture was stirred at 23°C. This was filtered to obtain 25.0 g of the acid compound (CH-1).

[0465] In Comparative Example 4, instead of purifying the acid compound with an ion exchange resin as in Example 1, the onium salt (C-1) was purified with an ion exchange resin.

[0466] Tables 3 and 4 below show the acid compounds used in each example and for comparison, as well as the onium salts produced. Tables 3 and 4 also indicate the type of ion exchange resin used, the value obtained by subtracting the pKa(X2) of the ion exchange group of the ion exchange resin from the pKa(X1) of the acid compound (X1-X2), and whether or not step (1) (purification of the acid compound using ion exchange resin) was performed.

[0467] [Table 3]

[0468] [Table 4]

[0469] The types of ion exchange groups, pKa values, and degree of crosslinking of the ion exchange resins used are shown in Table 5 below. All ion exchange resins were manufactured by Mitsubishi Chemical Corporation.

[0470] [Table 5]

[0471] <Step (3): Preparation of the resist composition> The components shown in Tables 6 and 7 were dissolved in the solvents shown in Table 6 to prepare solutions, which were then filtered through a polyethylene filter with a pore size of 0.03 μm to prepare a resist composition. In Tables 6 and 7, the mass percentages of resin (A), photoacid generator (B), onium salt (acid diffusion control agent), and surfactant represent their mass-based content relative to the total solid content of the resist composition. The onium salts used were prepared using the methods described above. The solid content concentration of the resist composition was set to 3.0% by mass.

[0472] [Table 6]

[0473] [Table 7]

[0474] [Application of resist composition] We prepared an 8-inch wafer coated with Cr oxidnitridation (a wafer treated with a shielding film typically used for photomask blanks). A resist composition was applied to the above 8-inch wafer using a Mark8 spin coater manufactured by Tokyo Electron Ltd., and dried on a hot plate at 120°C for 600 seconds to obtain a resist film with a thickness of 100 nm. In other words, a resist-coated wafer was obtained.

[0475] [EB exposure and development] The resist film obtained above was pattern-irradiated using an electron beam lithography system (Advantest Corporation; F7000S, acceleration voltage 50 keV). After irradiation, it was heated on a hot plate at 100°C for 600 seconds, immersed in a 2.38 mass% tetramethylammonium hydroxide (TMAH) aqueous solution for 60 seconds, and then rinsed with water for 30 seconds and dried. In this way, a resist pattern was formed on an 8-inch wafer. Although the exposure using the above-mentioned electron beam irradiation device (F7000S) is a single-beam method, it is expected that the evaluation results will be equivalent even if exposure is performed using a multi-beam method that simultaneously scans multiple single beams.

[0476] [etching] A hard mask pattern was formed on an 8-inch wafer with a resist pattern by dry etching. For dry etching, a fluorine-based gas (SF6) was used as the etching gas, and the etching time was 20 seconds.

[0477] [evaluation] The obtained patterns were evaluated for LWR performance after etching using the following method.

[0478] <Sensitivity> The irradiation energy required to resolve a 1:1 line-and-space pattern with a line width of 50 nm was defined as the sensitivity (Eop).

[0479] <LWR performance after etching> The LWR (Line Width Roughness) after etching was calculated by measuring the line width at 50 arbitrary points along the longitudinal direction of a 50 nm line-and-space pattern (line:space = 1:1) in the Eop described above, determining the standard deviation (σ), and calculating 3σ (nm). A smaller 3σ value indicates better LWR performance after etching. The 3σ values ​​are shown in Tables 8 and 9.

[0480] [Table 8]

[0481] [Table 9]

[0482] The results in Tables 8 and 9 show that Examples 1-42 exhibit superior LWR performance after etching compared to Comparative Examples 1-4.

Claims

1. (1) A step of passing a solution containing an acid compound (CA) with a pKa of 2.0 or higher through a column packed with ion exchange resin. A step (2) to produce an onium salt (C) using the acid compound (CA) after passing it through the column, and A method for producing a photosensitive or radiation-sensitive resin composition, comprising the step (3) of mixing the onium salt (C) with a resin (A) whose polarity increases by the action of an acid, A method for producing a photosensitive or radiation-sensitive resin composition, wherein the resin (A) has at least one selected from the group consisting of repeating units represented by the following general formula (A1), repeating units represented by the following general formula (A2), and repeating units represented by the following general formula (A3). 【Chemistry 1】 In general formula (A1), Ra1, Ra2, and Ra3 each independently represent a hydrogen atom, an alkyl group, a cycloalkyl group, a halogen atom, a cyano group, or an alkoxycarbonyl group. Ra1 represents a single bond or a divalent linking group. Ar a1 represents an aromatic ring group. Ra4 represents a hydrogen atom, an alkyl group, a cycloalkyl group, an aryl group, an aralkyl group, or an alkenyl group. Ra5 and Ra6 each independently represent an alkyl group, a cycloalkyl group, an aryl group, an aralkyl group, or an alkenyl group. Ra4 and Ra5 may bond to each other to form a ring. Ar a1 may bond to Ra3 or Ra4 to form a ring. In general formula (A2), Ra7, Ra8, and Ra9 each independently represent a hydrogen atom, an alkyl group, a cycloalkyl group, a halogen atom, a cyano group, or an alkoxycarbonyl group. L a2 represents a single bond or a divalent linking group. Ar a2 represents an aromatic ring group. Ra10, Ra11, and Ra12 each independently represent an alkyl group, a cycloalkyl group, an aryl group, an aralkyl group, or an alkenyl group. Two of Ra10, Ra11, and Ra12 may be bonded to each other to form a ring. In general formula (A3), R a13, R a14, and R a15 each independently represent a hydrogen atom, an alkyl group, a cycloalkyl group, a halogen atom, a cyano group, or an alkoxycarbonyl group. L a3 represents a single bond or a divalent linking group. Ar a3 represents an aromatic ring group. R a16, R a17, and R a18 each independently represent an alkyl group, a cycloalkyl group, an aryl group, an aralkyl group, or an alkenyl group. Two of R a16, R a17, and R a18 may be bonded to each other to form a ring.

2. A step (1) of passing a solution containing an acid compound (CA) with a pKa of 2.0 or more through a column packed with an ion exchange resin, A step (2) to produce an onium salt (C) using the acid compound (CA) after passing it through the column, and A method for producing a photosensitive or radiation-sensitive resin composition, comprising the step (3) of mixing the onium salt (C) with a resin (A) whose polarity increases by the action of an acid, A method for producing a photosensitive or radiation-sensitive resin composition, wherein the resin (A) has repeating units having groups that generate acid upon irradiation with active light or radiation.

3. A method for producing a photosensitive or radiation-sensitive resin composition according to claim 1 or 2, wherein the ion exchange resin has a strongly acidic cation exchange group as an ion exchange group.

4. A method for producing a photosensitive or radiation-sensitive resin composition according to claim 3, wherein the strongly acidic cation exchange group is a sulfonic acid group.

5. A method for producing a photosensitive or radiation-sensitive resin composition according to claim 1 or 2, wherein the pKa of the acid compound (CA) is 3.0 or higher.

6. A method for producing a photosensitive or radiation-sensitive resin composition according to claim 1 or 2, wherein the acid compound (CA) is a carboxylic acid or a phenol.

7. A method for producing a photosensitive or radiation-sensitive resin composition according to claim 1 or 2, wherein the acid compound (CA) is a compound represented by the following general formula (CA1) or (CA2). 【Chemistry 2】 In general formula (CA1), j represents either 0 or 1. Q Ｃ１ represents a substituent. m1 and m2 each independently represent either 0 or 1. m3 represents an integer greater than or equal to 0 and less than or equal to (6 + 2j - m1 - m2). However, the sum of m1 and m2 is either 1 or 2. *Each of these symbols represents a bond that attaches to an aromatic hydrocarbon listed in the general formula (CA1). 【Transformation 3】 In general formula (CA2), Q Ｃ２ represents an alkyl group or cycloalkyl group.

8. A method for producing a photosensitive or radiation-sensitive resin composition according to claim 1 or 2, wherein the value obtained by subtracting the pKa of the ion exchange group having the ion exchange resin from the pKa of the acid compound (CA) is 3.0 or more.

9. A method for producing a photosensitive or radiation-sensitive resin composition according to claim 1 or 2, wherein the degree of crosslinking of the ion exchange resin is 10% or less.

10. A method for producing a photosensitive or radiation-sensitive resin composition according to claim 1 or 2, wherein the photosensitive or radiation-sensitive resin composition contains 10% by mass or more of the onium salt (C) relative to the total solid content.

11. The aforementioned photosensitive or radiation-sensitive resin composition further contains a compound (B) that generates acid upon irradiation with active light or radiation. The mass-based content of the onium salt (C) in the aforementioned photosensitive or radiation-sensitive resin composition is A Ｃ The mass-based content of the compound (B) is set to A Ｂ In that case, A Ｃ : A Ｂ A method for producing a photosensitive or radiation-sensitive resin composition according to claim 1 or 2, wherein the ratio is 1:4 to 4:

1.

12. A pattern forming method comprising the steps of: forming a resist film on a substrate using a photosensitive or radiation-sensitive resin composition produced by the method for producing a photosensitive or radiation-sensitive resin composition according to claim 1 or 2; exposing the resist film; and developing the exposed resist film using a developer.

13. A method for manufacturing an electronic device, comprising the pattern forming method described in claim 12.

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