Organic treatment liquid

Abstract

A pattern forming method capable of obtaining a pattern with excellent in-plane uniformity of line width is provided. [Solution] A pattern formation method comprising: (1) a step of forming a film using an actinic ray- or radiation-sensitive resin composition containing a resin (A) that decomposes under the action of an acid to increase its polarity, and a compound (B) that generates an acid upon irradiation with actinic rays or radiation; (2) a step of exposing the film to light; and (3) a step of at least one of developing and rinsing the exposed film with an organic treatment liquid containing butyl acetate and a hydrocarbon having 11 or more carbon atoms, wherein the content of the hydrocarbon having 11 or more carbon atoms in the organic treatment liquid is 1% by mass or more and 35% by mass or less, and a method for manufacturing an electronic device comprising the pattern formation method.

Description

[Technical Field] 【0001】 The present invention relates to a pattern formation method and a method for manufacturing electronic devices. More specifically, the present invention relates to an ultramicrolithography process applicable to the manufacturing processes of ultra-large-scale integrated circuits (ULSIs) and high-capacity microchips, the manufacturing processes of nanoimprint molds, and the manufacturing processes of high-density information recording media, as well as a pattern formation method and a method for manufacturing electronic devices that are suitably used in 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】 For example, Patent Document 1 describes a pattern formation method in which a resist film is developed or washed (rinsed) using an organic processing solution in which the content of an oxidizing agent is within a specific range. In addition, Patent Document 2 describes a pattern formation method in which a resist film is formed using a negative-type chemically amplified resist composition that is negated by a crosslinking reaction, and after exposure, development is performed using a developer containing an organic solvent that satisfies specific conditions. Furthermore, Patent Document 3 describes a pattern formation method in which a resist film containing a resin having an acid-decomposable repeating unit that decomposes by the action of an acid to generate an acid having a specific pKa range is exposed, and development is performed using a developer containing an organic solvent. 【Prior Art Documents】 【Patent Documents】 【0005】 【Patent Document 1】 International Publication No. 2016 / 104565 【Patent Document 2】 Japanese Patent Application Laid-Open No. 2011-065105 【Patent Document 3】 International Publication No. 2016 / 158711 【Summary of the Invention】 【Problems to be Solved by the Invention】 【0006】 As described in the above-mentioned Patent Documents 1 to 3, in the pattern formation method, performing development or rinsing using an organic solvent has been conventionally known. However, as a result of the study by the present inventors, particularly, with respect to a resist film formed using a polarity conversion type resist composition containing an acid-decomposable resin and a photoacid generator, when a conventional developer or rinsing liquid containing an organic solvent is used, it has been found that there is room for improvement in the in-plane uniformity of the line width of the obtained pattern. 【0007】 Therefore, an object of the present invention is to provide a pattern formation method capable of obtaining a pattern excellent in in-plane uniformity of line width, and a method for manufacturing an electronic device including the above pattern formation method. 【Means for Solving the Problems】 【0008】 The inventors have found that the above problems can be solved by the following configuration. <1> An organic treatment solution containing butyl acetate and hydrocarbons having 11 or more carbon atoms, The butyl acetate content in the above organic treatment liquid is 65% by mass or more and 95% by mass or less, and the hydrocarbon content with 11 or more carbon atoms is 5% by mass or more and 35% by mass or less. The hydrocarbons with 11 or more carbon atoms mentioned above are alkanes with 11 to 15 carbon atoms. The above-mentioned organic processing solution is an organic processing solution used for developing or rinsing resist films. <2> The hydrocarbon having 11 or more carbon atoms is undecane or dodecane. <1> The organic treatment solution described above. <3> The above organic treatment liquid contains two or more hydrocarbons with 11 or more carbon atoms. <1> The organic treatment solution described above. <4> The content of butyl acetate in the above organic treatment liquid is 80% by mass or more and 95% by mass or less, and the content of hydrocarbons having 11 or more carbon atoms is 5% by mass or more and 20% by mass or less. <1> The organic treatment solution described above. <5> The above organic treatment solution is for rinsing the resist film. <1> The organic treatment solution described above. <6> The above organic processing solution is for developing resist films. <1> The organic treatment solution described above. <7> The amount of impurities contained in the above organic treatment solution is 1 ppm (parts per million) or less by mass. <1> The organic treatment solution described above. <8> The above organic treatment solution contains a conductive compound. <1> The organic treatment solution described above. The present invention, the above <1> ~ <8> This specification primarily concerns the above, but other matters are also included for reference. 【0009】 [1] (1) A step of forming a film using a photosensitive or radiation-sensitive resin composition comprising a resin (A) that decomposes and becomes more polar due to the action of an acid, and a compound (B) that generates an acid upon irradiation with active light or radiation. (2) A step of exposing the above film, (3) A pattern forming method comprising the step of developing and rinsing the exposed film with an organic treatment solution containing butyl acetate and a hydrocarbon having 11 or more carbon atoms, A pattern forming method wherein the content of the above-mentioned hydrocarbon having 11 or more carbon atoms in the above-mentioned organic treatment liquid is 1% by mass or more and 35% by mass or less. [2] The pattern-forming method according to [1], wherein the hydrocarbon having 11 or more carbon atoms is undecane. [3] The pattern-forming method according to [1] or [2], wherein the resin (A) that decomposes and becomes more polar due to the action of the above acid contains at least one selected from the group consisting of a group in which a hydrogen atom of a carboxyl group is replaced by a leaving group that is removed by the action of an acid, a group in which a hydrogen atom of an alcoholic hydroxyl group is replaced by a leaving group that is removed by the action of an acid, and a group in which a hydrogen atom of a phenolic hydroxyl group is replaced by a leaving group that is removed by the action of an acid. [4] A pattern forming method according to any one of [1] to [3], wherein the resin (A) that decomposes and becomes more polar due to the action of the above acid has repeating units represented by the following general formula (AX). 【0010】 [ka] 【0011】 In the general formula (AX), Xa1 represents a hydrogen atom or an alkyl group. Rx1 to Rx3 each independently represent an alkyl group, a cycloalkyl group, an alkenyl group, or an aryl group. Two of the Rx1 to Rx3 elements may combine to form a ring. [5] The pattern forming method according to any one of [1] to [4], wherein the resin (A) that decomposes and becomes more polar due to the action of the above acid has at least one selected from the group consisting of a lactone group, a carbonate group, a sultone group, and a cyclic group having a hydroxyl group. [6] A pattern forming method according to any one of [1] to [5], wherein the resin (A) that decomposes and becomes more polar due to the action of the above acid has repeating units represented by the following general formula (Y). 【0012】 [ka] 【0013】 In general formula (Y), A represents a hydrogen atom, alkyl group, cycloalkyl group, halogen atom, or cyano group. L represents a single bond or a divalent linking group having an oxygen atom. 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 when there are a plurality of them, they may be the same or different. When there are a plurality of Rs, they may jointly form a ring with each other. a represents an integer of 1 to 3. b represents an integer of 0 to (5 - a). 〔7〕 The pattern forming method according to any one of 〔1〕~〔6〕, wherein the compound (B) that generates an acid upon irradiation with the above active light or radiation has a cation represented by the following general formula (ZaI) or a cation represented by the following general formula (ZaII). 【0014】 【Chemical formula】 [[ID=...]] (remaining lines unchanged as there are no specific translations provided for them) In the general formula (ZaI), R 205 , R 202 , and R 203 each independently represents an organic group. In the general formula (ZaII), R 204 and R 205 each independently represents an organic group. 〔8〕 In the general formula (ZaI), at least one of R 201 , R 202 [[ID=4..." (remaining lines unchanged as there are no specific translations provided for them) In the general formula (ZaII), at least one of R 204 and R 205 is an aryl group, the pattern forming method according to 〔7〕. 〔9〕 In the general formula (ZaI), at least one of R 201 , R 202 , and R 203 has an acid - decomposable group, or in the general formula (ZaII), R​​​​​204 and R 205 The pattern-forming method according to [7] or [8], wherein at least one of the groups has an acid-degradable group.

[10] The pattern formation method according to any one of [1] to [9], wherein the molecular weight of the acid generated by compound (B), which generates acid upon irradiation with the above-mentioned active light or radiation, is 250 or more.

[11] The pattern forming method according to any one of [1] to

[10] , wherein the content of compound (B) that generates acid upon irradiation with the above-mentioned active light or radiation is 10% by mass or more with respect to the total solid content of the above-mentioned photosensitive or radiation-sensitive resin composition.

[12] The pattern forming method according to any one of [1] to

[11] , wherein the above-mentioned photosensitive or radiation-sensitive resin composition contains two or more compounds (B) that generate acid upon irradiation with the above-mentioned active light or radiation, or the compound (B) that generates acid upon irradiation with the above-mentioned active light or radiation is at least one selected from the group consisting of the following compounds (I) and (II). Compound (I): 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 a structural site which forms a first acidic site represented by HA1 upon irradiation with active light or radiation. Structural site Y: Anionic site A2 - and cation site M2 + It consists of a structural site which forms a second acidic site represented by HA2 upon irradiation with active light or radiation. However, compound (I) satisfies the following condition I. 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 above 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. Compound (II): A compound having two or more of the above-mentioned structural sites X and one or more of the following structural sites Z, wherein upon irradiation with active light or radiation, the compound generates an acid containing two or more of the above-mentioned first acidic sites derived from the above-mentioned structural sites X and the above-mentioned structural sites Z. Structural site Z: A nonionic site capable of neutralizing acids.

[13] A method for manufacturing an electronic device, comprising a pattern formation method described in any one of [1] to

[12] . [Effects of the Invention] 【0016】 According to the present invention, a pattern forming method can be provided that can obtain a pattern with excellent in-plane uniformity of line width, and a method for manufacturing an electronic device including the above pattern forming method. [Modes for carrying out the invention] 【0017】 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. 【0018】 In this specification, "active light" or "radiation" means, for example, the emission spectrum of a mercury lamp, far ultraviolet light represented by an excimer laser, extreme ultraviolet (EUV), 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 with emission line spectra from mercury lamps, far ultraviolet light represented by excimer lasers, extreme ultraviolet light, X-rays, and EUV light, but also drawing with 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. 【0019】 In this specification, the bonding direction of the divalent group as expressed 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-. Furthermore, the above compound may also be "X-CO-OZ" or "XO-CO-Z". 【0020】 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 defined as polystyrene-converted values ​​obtained by GPC (Gel Permeation Chromatography) measurement using a GPC (Gel Permeation Chromatography) instrument (HLC-8120GPC manufactured by Tosoh Corporation) (solvent: tetrahydrofuran, flow rate (sample injection volume): 10 μL, column: TSK gel Multipore HXL-M manufactured by Tosoh Corporation, column temperature: 40°C, flow rate: 1.0 mL / min, detector: differential refractive index detector). 【0021】 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. All pKa values ​​described herein are those calculated using this software package. Software Package 1: Advanced Chemistry Development (ACD / Labs) Software V8.14 for Solaris (1994-2007 ACD / Labs). 【0022】 Furthermore, pKa can also be determined by molecular orbital calculations. Specifically, this method involves calculating the H₂ in aqueous solution based on the thermodynamic cycle. + 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. 【0023】 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. Furthermore, 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. 【0024】 [Pattern formation method] The pattern forming method of the present invention is (1) A step of forming a film using a photosensitive or radiation-sensitive resin composition comprising a resin (A) that decomposes and becomes more polar due to the action of an acid, and a compound (B) that generates an acid upon irradiation with active light or radiation. (2) A step of exposing the above film, (3) A pattern forming method comprising the step of developing and rinsing the exposed film with an organic treatment solution containing butyl acetate and a hydrocarbon having 11 or more carbon atoms, The pattern formation method is characterized in that the content of the above-mentioned hydrocarbon having 11 or more carbon atoms in the above-mentioned organic treatment liquid is 1% by mass or more and 35% by mass or less. 【0025】 Although the details of the mechanism by which the pattern forming method of the present invention can obtain a pattern with excellent in-plane uniformity of line width are not clear, the inventors speculate as follows. An organic processing solution having a specific composition containing butyl acetate and hydrocarbons having 11 or more carbon atoms, with a hydrocarbon content of 1% by mass or more and 35% by mass or less, exhibits excellent affinity for films formed from photosensitive or radiation-sensitive resin compositions containing a resin (A) that decomposes and becomes more polar due to the action of acid, and a compound (B) that generates acid upon irradiation with active light or radiation. Therefore, it is believed that by performing at least one of developing and rinsing using the above organic processing solution, the organic processing solution spreads uniformly across the entire wafer, improving the in-plane uniformity of line width. 【0026】 The following details the steps for each of the above processes. 【0027】 <Process (1)> Step (1) is a step of forming a film using a photosensitive or radiation-sensitive resin composition that includes a resin (A) that decomposes and becomes more polar due to the action of an acid, and a compound (B) that generates an acid when irradiated with active light or radiation. The photosensitive or radiation-sensitive resin composition used in step (1) is typically a resist composition, and hereafter, the photosensitive or radiation-sensitive resin composition will also be referred to as the "resist composition." Furthermore, the film formed using the photosensitive or radiation-sensitive resin composition is typically a resist film, and hereafter, the film formed using the photosensitive or radiation-sensitive resin composition will also be referred to as the "resist film." Details of the photosensitive or radiation-sensitive resin compositions will be described later. 【0028】 Step (1) is typically a step of forming a resist film on a substrate using a resist composition. 【0029】 One method for forming a resist film on a substrate using a resist composition is to coat the resist composition onto the substrate. Furthermore, it is preferable to filter the resist composition before coating, 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. 【0030】 The resist 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 (rotations per minute). After applying the resist 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. 【0031】 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. 【0032】 While the thickness of the resist film is not particularly limited, 10 to 120 nm is preferred because it allows for the formation of finer patterns with higher precision. In particular, when using EUV exposure, 10 to 65 nm is more preferred for the resist film thickness, and 15 to 50 nm is even more preferred. When using ArF immersion exposure, 10 to 120 nm is more preferred for the resist film thickness, and 15 to 90 nm is even more preferred. 【0033】 Alternatively, a topcoat may be formed on the upper layer of the resist film using a topcoat composition. Preferably, the topcoat composition does not mix 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 be included in the resist composition. Furthermore, it is preferable that the top coat contains 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. 【0034】 <Process (2)> Step (2) is the step 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, preferably with wavelengths of 250 nm or less, more preferably 220 nm or less, and particularly preferably far ultraviolet light with wavelengths of 1 to 200 nm. Specifically, examples include KrF excimer laser (248 nm), ArF excimer laser (193 nm), F2 excimer laser (157 nm), EUV (13 nm), X-rays, and electron beams. 【0035】 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. 【0036】 <Process (3)> Step (3) is a step in which the resist film exposed in step (2) is developed and rinsed with an organic processing solution containing butyl acetate and hydrocarbons having 11 or more carbon atoms. The content of the hydrocarbons having 11 or more carbon atoms in the organic processing solution is 1% by mass or more and 35% by mass or less. 【0037】 The organic treatment solution used in step (3) contains butyl acetate and a hydrocarbon having 11 or more carbon atoms. The hydrocarbon having 11 or more carbon atoms is preferably an alkane, more preferably an alkane having 11 to 15 carbon atoms, even more preferably an alkane having 11 to 13 carbon atoms, particularly preferably undecane or dodecane, and most preferably undecane. If structural isomers exist for the hydrocarbon having 11 or more carbon atoms, such as undecane or dodecane, the solution may also contain these structural isomers. The organic treatment liquid may contain only one type of hydrocarbon with 11 or more carbon atoms, or two or more types. The content of hydrocarbons having 11 or more carbon atoms in the organic treatment liquid (the total amount if multiple types of hydrocarbons having 11 or more carbon atoms are included) is preferably 1% by mass or more and 35% by mass or less, with 5% by mass or more and 30% by mass or less, and more preferably 10% by mass or more and 25% by mass or less, based on 100% by mass of the entire organic treatment liquid. 【0038】 The organic treatment solution used in step (3) contains butyl acetate (n-butyl acetate). The butyl acetate content in the organic treatment solution is preferably 65% ​​to 99% by mass, more preferably 70% to 95% by mass, and even more preferably 75% to 90% by mass, based on 100% by mass of the entire organic treatment solution. 【0039】 The organic treatment solution may contain other components in addition to butyl acetate and hydrocarbons having 11 or more carbon atoms. Examples of other components include surfactants, antioxidants, and basic compounds. The content of other components in the organic treatment solution is preferably 0% to 5% by mass, more preferably 0% to 1% by mass, even more preferably 0% to 0.5% by mass, and particularly preferably 0% by mass (i.e., no other components are present), based on 100% by mass of the entire organic treatment solution. 【0040】 Step (3) is a step in which the resist film exposed in step (2) is developed and rinsed (washed) with the organic processing solution described above. Step (3) may involve developing only, rinsing only, or developing and rinsing. The following describes the case where development is performed in step (3) (hereinafter, the process of developing using the above-mentioned organic processing solution will also be referred to as step (3A)) and the case where rinsing is performed in step (3) (hereinafter, the process of rinsing using the above-mentioned organic processing solution will also be referred to as step (3B)). Step (3) may include only step (3A), only step (3B), or both step (3A) and step (3B). If step (3) includes both step (3A) and step (3B), the organic processing solution used as the developer in step (3A) and the organic processing solution used as the rinse solution in step (3B) may be the same or different. A particularly preferred embodiment of the present invention is one in which an organic treatment solution containing butyl acetate and undecane, wherein the mass ratio of "butyl acetate / undecane" is "90 / 10", is used as a rinsing solution. 【0041】 [Process (3A)] The case in step (3) where development is performed using the above-mentioned organic processing solution (step (3A)) will be explained. In step (3A), the above-mentioned organic processing solution is used as the developer. 【0042】 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 leaving it still for a certain period of time for development (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 area to be removed 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. 【0043】 By performing step (3A), a resist pattern (also simply called a "pattern") is formed. It is preferable to perform rinsing after carrying out step (3A). Rinsing can be carried out by step (3B) described later, or by using a rinsing solution other than the organic treatment solution described above. Other than the organic treatment solution mentioned above, the rinsing solution 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 other than the organic treatment solution mentioned above 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. Even when rinsing is performed using a rinsing solution other than the organic treatment solution mentioned above, the rinsing method can be carried out in the same way as the rinsing method in step (3B) described later. 【0044】 [Process (3B)] The case in step (3) where development is performed using the above-mentioned organic processing solution (step (3B)) will be explained. In step (3B), the above-mentioned organic processing solution is used as a rinsing solution. 【0045】 The rinsing method is not particularly limited and includes, for example, a method in which rinsing liquid is continuously discharged onto a substrate rotating at a constant speed (rotary coating method), a method in which the substrate is immersed in a tank filled with rinsing liquid for a certain period of time (dip method), and a method in which rinsing liquid is sprayed onto the surface of the substrate (spray method). 【0046】 It is preferable to perform development before carrying out step (3B). Development can be carried out by the aforementioned step (3A), or it can be carried out using a developer other than the organic processing solution described above. As a developer other than the organic processing solution mentioned above, it is preferable to use an organic developer. Even when developing using a developer other than the organic processing solution described above, the development method can be carried out in the same manner as the development method described in step (3A) above. 【0047】 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. 【0048】 The above organic 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. 【0049】 Furthermore, the pattern formation method of the present invention 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. 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). 【0050】 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. 【0051】 In the pattern forming method of the present invention, the organic processing solution, resist composition, and various other materials (e.g., solvent, developer, rinse solution, anti-reflective film forming composition, top coat forming composition, etc.) used are preferably free of 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. 【0052】 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. 【0053】 Furthermore, 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 raw materials constituting various materials, and performing distillation under conditions that suppress contamination as much as possible, such as by lining the inside of the apparatus with Teflon®. 【0054】 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. 【0055】 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 piping coated with antistatic treated polyethylene, polypropylene, or fluororesin (polytetrafluoroethylene or perfluoroalkoxy resin, etc.). Similarly, for filters and O-rings, antistatic treated polyethylene, polypropylene, or fluororesin (polytetrafluoroethylene or perfluoroalkoxy resin, etc.) can be used. 【0056】 [Actinic ray-sensitive or radiation-sensitive resin composition] The photosensitive or radiation-sensitive resin compositions used in the present invention will now be described. The photosensitive or radiation-sensitive resin composition used in the present invention (also referred to as the "resist composition") comprises a resin (A) that decomposes and increases in polarity upon the action of an acid (also referred to as the "acid-degradable resin" or "resin (A)") and a compound (B) that generates acid upon irradiation with active light or radiation (also referred to as the "photoacid generator" or "compound (B)"). 【0057】 The resist composition is preferably a negative-type resist composition. Furthermore, the resist composition is preferably a resist composition for organic solvent development. The resist composition is typically a chemically amplified resist composition. 【0058】 [Acid-degradable resin (Resin (A))] The resist composition contains resin (A). In the pattern forming method of the present invention, typically, when an organic developer is used as the developer, a negative-type pattern is suitably formed. Resin (A) typically contains groups that decompose and increase in polarity due to the action of acid (also called "acid-degradable groups"), and preferably contains repeating units having acid-degradable groups. In addition to the repeating units having acid-degradable groups described later, repeating units having acid-degradable groups that include unsaturated bonds are also preferred as repeating units having acid-degradable groups. 【0059】 <Repeating unit with acid-degradable group> (Repeating unit with acid-degradable group) The acid-degradable group is preferably a group that decomposes under the action of an acid to produce a polar group. The acid-degradable group preferably has a structure in which the polar group is protected by a leaving group that is removed by the action of an acid. In other words, the resin (A) preferably has repeating units having a group that decomposes by the action of an acid and generates a polar group. The resin having these repeating units becomes more polar by the action of an acid, increasing its solubility in alkaline developers and decreasing its solubility in organic solvents. The above polar groups are preferably alkali-soluble groups, and examples include acidic 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. The polar groups mentioned above are preferably carboxyl groups, phenolic hydroxyl groups, fluorinated alcohol groups (preferably hexafluoroisopropanol groups), or sulfonic acid groups. 【0060】 Examples of leaving groups that are removed by the action of an acid include the groups 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) 【0061】 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. Preferred alkyl groups for Rx1 to Rx3 are 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. Preferred cycloalkyl groups for Rx1 to Rx3 are 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 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 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. If the resist composition is, for example, an EUV lithography resist composition, 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. 【0062】 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. Also, 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 resist composition is, for example, a resist composition for EUV lithography, 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. 【0063】 The group represented by formula (Y3-1) below is preferred for formula (Y3). 【0064】 [ka] 【0065】 Here, L1 and L2 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, or norbornyl groups, and examples of tertiary alkyl groups include tert-butyl or adamantane groups. In these embodiments, the Tg (glass transition temperature) and activation energy are increased, which ensures film strength and suppresses fogging. 【0066】 If the resist composition is, for example, an EUV lithography resist composition, it is also preferable that the alkyl groups, cycloalkyl groups, aryl groups, and combinations thereof represented by L1 and L2 further have a fluorine atom or an iodine atom as a substituent. Furthermore, it is also preferable that the alkyl groups, cycloalkyl groups, aryl groups, and aralkyl groups contain heteroatoms such as oxygen atoms in addition to fluorine atoms and iodine atoms (that is, in the alkyl groups, cycloalkyl groups, aryl groups, and aralkyl groups, for example, one of the methylene groups is replaced with a heteroatom such as an oxygen atom, or a group containing a heteroatom such as a carbonyl group). Furthermore, if the resist composition is, for example, an EUV lithography 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 which may contain a heteroatom. 【0067】 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. If the resist composition is, for example, an EUV lithography resist composition, it is also preferable that the aromatic ring group represented by Ar, and the alkyl, cycloalkyl, and aryl groups represented by Rn, have fluorine and iodine atoms as substituents. 【0068】 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. 【0069】 Other leaving groups that are removed by the action of an acid may 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. 【0070】 The resin (A) preferably contains at least one selected from the group consisting of a group in which a hydrogen atom of a carboxyl group is replaced by a leaving group that is removed by the action of an acid, a group in which a hydrogen atom of an alcoholic hydroxyl group is replaced by a leaving group that is removed by the action of an acid, and a group in which a hydrogen atom of a phenolic hydroxyl group is replaced by a leaving group that is removed by the action of an acid. 【0071】 As a repeating unit having an acid-degradable group, the repeating unit represented by formula (A) is also preferred. 【0072】 [ka] 【0073】 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. L1 represents a divalent linking group which may have a fluorine atom or an iodine atom. Examples of divalent linking groups 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, arylene groups, etc.), and linking groups formed by linking multiple of these. In particular, 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. 【0074】 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. The alkyl group 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 contained in an alkyl group having a fluorine atom or an iodine atom is not particularly limited, but it is preferably 1 or more, more preferably 1 to 5, and even more preferably 1 to 3. The alkyl group described above may also contain heteroatoms other than halogen atoms, such as oxygen atoms. 【0075】 R2 represents a leaving group that is eliminated by the action of an acid and may contain a fluorine atom or an iodine atom. Examples of leaving groups that may contain a fluorine atom or an iodine atom include those represented by the above formulas (Y1) to (Y4) and that contain a fluorine atom or an iodine atom. 【0076】 As a repeating unit having an acid-degradable group, a repeating unit represented by the following general formula (AI) is also preferred. 【0077】 [ka] 【0078】 In the general formula (AI), Xa1 represents a hydrogen atom or an alkyl group. T represents a single bond or a divalent linking group. Rx1 to Rx3 each independently represent an alkyl group, a cycloalkyl group, an alkenyl group, or an aryl group. Two of the Rx1 to Rx3 elements may combine to form a ring. 【0079】 The alkyl group represented by Xa1 may be linear or branched. Furthermore, the alkyl group may have substituents. Examples of the alkyl group include a methyl group or a -CH2-R 11 The group represented by R is an example. 11 Xa1 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. Xa1 is preferably a hydrogen atom, a methyl group, a trifluoromethyl group, or a hydroxymethyl group. 【0080】 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, and more preferably a single bond. 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. 【0081】 The alkyl groups Rx1 to Rx3 may be linear or branched. Furthermore, these alkyl groups may have substituents. Preferred alkyl groups include C1 to C4 groups such as methyl, ethyl, n-propyl, isopropyl, n-butyl, isobutyl, and t-butyl groups. The cycloalkyl groups Rx1 to Rx3 may be monocyclic or polycyclic cycloalkyl groups. Furthermore, these cycloalkyl groups may have substituents. Preferred cycloalkyl groups are monocyclic cycloalkyl groups such as cyclopentyl and cyclohexyl groups, or polycyclic cycloalkyl groups such as norbornyl, tetracyclodecanyl, tetracyclododecanyl, and adamantyl groups. In these cycloalkyl groups, for example, one of the methylene groups constituting the ring may be replaced with a heteroatom such as an oxygen atom or a sulfur 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 with vinylene groups. The aryl groups Rx1 to Rx3 may be monocyclic or polycyclic. Furthermore, the aryl groups may have substituents. Preferably, the aryl groups have 6 to 10 carbon atoms, such as phenyl, naphthyl, and anthryl groups. The alkenyl groups Rx1 to Rx3 may be linear or branched. Furthermore, the alkenyl groups may have substituents. Vinyl groups are preferred as the alkenyl groups. When two Rx1 to Rx3 bond to form a ring, the formed ring may be monocyclic or polycyclic. The formed ring is preferably a cycloalkyl group. As the above cycloalkyl group, monocyclic cycloalkyl groups such as cyclopentyl and cyclohexyl groups are preferred. Also, polycyclic cycloalkyl groups such as norbornyl, tetracyclodecanyl, tetracyclododecanyl, and adamantyl groups are preferred. Among these, monocyclic cycloalkyl groups having 5 to 6 carbon atoms are preferred. The cycloalkyl group formed by the bonding of two Rx1 to Rx3 may have, for example, one of the methylene groups constituting the ring replaced by a heteroatom such as an oxygen atom or a sulfur 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. 【0082】 When each of the above groups has substituents, the substituents are not particularly limited, but examples include alkyl groups (1 to 4 carbon atoms, etc.), halogen atoms, hydroxyl groups, alkoxy groups (1 to 4 carbon atoms, etc.), alkylthio groups (1 to 4 carbon atoms, etc.), carboxyl groups, and alkoxycarbonyl groups (2 to 6 carbon atoms, etc.). The number of carbon atoms in the substituent is preferably 8 or less. 【0083】 The repeating unit represented by the general formula (AI) is preferably the repeating unit represented by the general formula (AX) shown below. 【0084】 [ka] 【0085】 In the general formula (AX), Xa1 represents a hydrogen atom or an alkyl group. Rx1 to Rx3 each independently represent an alkyl group, a cycloalkyl group, an alkenyl group, or an aryl group. Two of the Rx1 to Rx3 elements may combine to form a ring. 【0086】 In general formula (AX), Xa1 has the same meaning as Xa1 in general formula (AI) mentioned above, and the specific examples and preferred ranges are also the same. In general formula (AX), Rx1 to Rx3 have the same meaning as Rx1 to Rx3 in general formula (AI) mentioned above, and the specific examples and preferred ranges are also the same. 【0087】 As a repeating unit having an acid-degradable group, a repeating unit represented by the following general formula (AX2) is also preferred. 【0088】 [ka] 【0089】 In the general formula (AX2), Xa1 represents a hydrogen atom or an alkyl group. Rx1 to Rx3 each independently represent an alkyl group, a cycloalkyl group, an alkenyl group, or an aryl group. Two of the Rx1 to Rx3 elements may combine to form a ring. Ar represents a divalent aromatic hydrocarbon group. 【0090】 In general formula (AX2), Xa1 has the same meaning as Xa1 in general formula (AI) mentioned above, and the specific examples and preferred ranges are also the same. In general formula (AX2), Rx1 to Rx3 have the same meaning as Rx1 to Rx3 in the aforementioned general formula (AI), and the specific examples and preferred ranges are also the same. In the general formula (AX2), Ar is preferably an arylene group, more preferably an arylene group having 6 to 20 carbon atoms, even more preferably an arylene group having 6 to 10 carbon atoms, and particularly preferably a phenylene group. Ar may have substituents, and 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), with those having 8 carbon atoms or less being preferred. 【0091】 If resin (A) contains a group in which a hydrogen atom of a phenolic hydroxyl group is replaced by a leaving group that removes the hydrogen atom by the action of an acid, it is preferable that resin (A) has repeating units having a structure in which the hydrogen atom of the phenolic hydroxyl group is protected by a group represented by formulas (Y1) to (Y4). 【0092】 As a repeating unit containing a group in which a hydrogen atom of a phenolic hydroxyl group is replaced by a leaving group that removes the hydrogen atom by the action of an acid, the repeating unit represented by the following general formula (AII) is preferred. 【0093】 [ka] 【0094】 In the general formula (AII), R 61 , R 62 and R 63 Each of these independently represents a hydrogen atom, an alkyl group, a cycloalkyl group, a halogen atom, a cyano group, or an alkoxycarbonyl group. However, R 62 It may also bond with Ar6 to form a ring, in which case R 62 represents a single bond or an alkylene group. X6 is a single bond, -COO-, or -CONR 64 - represents R 64 represents a hydrogen atom or an alkyl group. L6 represents a single bond or an alkylene group. Ar6 represents an (n+1) valent aromatic hydrocarbon group, R 62 When bonded to form a ring, it represents an (n+2) valent aromatic hydrocarbon group. For n≧2, each Y2 independently represents a group that is eliminated by the action of a hydrogen atom or an acid. However, at least one of the Y2 groups represents a group that is eliminated by the action of an acid. The group that is eliminated by the action of the acid as Y2 is preferably the group represented by the above formulas (Y1) to (Y4). n represents an integer between 1 and 4. Each of the above groups may have substituents, and 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), with those having 8 carbon atoms or less being preferred. 【0095】 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). 【0096】 Specific examples of repeating units having acid-degradable groups are shown below, but the present invention is not limited thereto. In the formula, Xa1 is any of H, CH3, CF3, and CH2OH, and Rxa and Rxb each represent a linear or branched alkyl group having 1 to 5 carbon atoms. 【0097】 [ka] 【0098】 [ka] 【0099】 [ka] 【0100】 [ka] 【0101】 [ka] 【0102】 [ka] 【0103】 (A repeating unit containing an unsaturated bond and an acid-degradable group) The resin (A) may have 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. Formula (B): 【0104】 [ka] 【0105】 In equation (B), Xb represents a hydrogen atom, a halogen atom, or an alkyl group which may have substituents. L represents a single bond or a divalent linking group which may have substituents. Each of Ry1 to Ry3 independently represents 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). 【0106】 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. 11Xb 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. 【0107】 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. An aromatic group is preferred. 【0108】 Preferred alkyl groups for Ry1 to Ry3 are 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. The cycloalkenyl groups of Ry1 to Ry3 are preferably cyclopentyl groups and monocyclic cycloalkyl groups that include a double bond in part. The cycloalkyl group formed by the bonding of two Ry1-Ry3 groups 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 5-6 carbon atoms are 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 a heteroatom such as a -SO2- group or -SO3- group, or 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 aforementioned cycloalkyl group or cycloalkenyl group. 【0109】 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. 【0110】 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)). 【0111】 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 particularly preferably 60 mol% or less, relative to the total repeating units in resin (A). 【0112】 Specific examples of repeating units having an acid-degradable group containing an unsaturated bond are shown below, but the present invention is 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, 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 or -SO3- group, or a vinylidene group, or a combination thereof, and l, n, and m represent integers of 0 or more. 【0113】 [ka] 【0114】 [ka] 【0115】 [ka] 【0116】 [ka] 【0117】 (Repeating units with polar groups) The resin (A) may have repeating units having polar groups. Examples of polar groups include hydroxyl groups, cyano groups, and carboxyl groups. The repeating unit having a polar group is preferably a repeating unit having an alicyclic hydrocarbon structure substituted with a polar group. Furthermore, it is preferable that the repeating unit having a polar group does not have an acid-degradable group. In the alicyclic hydrocarbon structure substituted with a polar group, an adamantyl group or a norbornyl group is preferred as the alicyclic hydrocarbon structure. 【0118】 The following are specific examples of monomers corresponding to repeating units having polar groups, but the present invention is not limited to these examples. Furthermore, although the following examples are described as methacrylic acid ester compounds, they may also be acrylic acid ester compounds. 【0119】 [ka] 【0120】 In addition, specific examples of repeating units having polar groups include the constituent units disclosed in paragraphs 0415-0433 of U.S. Patent Application Publication No. 2016 / 0070167. Resin (A) may contain only one type of repeating unit having a polar group, or it may contain two or more types in combination. If resin (A) contains repeating units having polar groups, the content is preferably 0.1 mol% to 40 mol%, and more preferably 1 to 30 mol%, relative to the total repeating units in resin (A). 【0121】 The resin (A) may contain repeating units other than those described above. For example, resin (A) may include 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 (29). (20) Repeating units having an acid group, as described later (21) Repeating units having a fluorine atom or an iodine atom, as described later (22) Repeating units having a lactone group, a sultone group, or a carbonate group, as described later (23) Repeating units having photoacid generators, as described later (24) Repeating units represented by formula (V-1) or formula (V-2) below, as described later. (25) Repeating units represented by formula (A), which will be described later (26) Repeating units represented by formula (B), which will be described later (27) Repeating units represented by formula (C), as described later (28) Repeating units represented by formula (D), which will be described later (29) Repeating units represented by formula (E), which will be described later 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. 【0122】 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 repeating units having acidic groups. When resin (A) has acidic groups, the interaction between resin (A) and the acid generated from compound (B) is improved. As a result, acid diffusion is further suppressed, and the cross-sectional shape of the formed pattern can become more rectangular. 【0123】 When the resist composition is used as an EUV-sensitive photosensitive or radiation-sensitive resin composition, it is preferable that the resin (A) has at least one repeating unit selected from the group consisting of group A. Furthermore, when the resist composition is used as an EUV-sensitive photosensitive or radiation-sensitive resin composition, 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. Furthermore, when the resist composition is used as an EUV-sensitive photosensitive or radiation-sensitive resin composition, it is also preferable that the resin (A) has repeating units having aromatic groups. When the resist composition is used as an active photosensitive or radiation-sensitive resin composition for ArF, it is preferable that the resin (A) has at least one repeating unit selected from the group consisting of group B described above. Furthermore, when the resist composition is used as an activated photosensitive or radiation-sensitive resin composition for ArF, it is preferable that resin (A) does not contain either fluorine atoms or silicon atoms. Furthermore, when the resist composition is used as a photosensitive or radiation-sensitive resin composition for ArF, it is preferable that resin (A) does not have aromatic groups. 【0124】 Resin (A) preferably has at least one selected from the group consisting of lactone groups, carbonate groups, sultone groups, and cyclic groups having hydroxyl groups. Lactone groups, carbonate groups, and sultone groups will be described later. The cyclic group having hydroxyl groups is preferably an alicyclic group having hydroxyl groups, and specific examples include those exemplified in the repeating units having acid groups described later. 【0125】 <Repeating unit with acidic group> Resin (A) preferably has 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. Furthermore, one or more fluorine atoms (preferably 1 to 2) of the hexafluoroisopropanol group may be 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 a polar group is protected by a leaving 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. 【0126】 The repeating unit having an acidic group may also have a fluorine atom or an iodine atom. 【0127】 Examples of repeating units having an acidic group include the following: 【0128】 [ka] 【0129】 As a repeating unit having an acid group, the repeating unit represented by the following formula (Y) is preferred. The resin (A) preferably has repeating units represented by the following general formula (Y). 【0130】 [ka] 【0131】 In general formula (Y), A represents a hydrogen atom, alkyl group, cycloalkyl group, halogen atom, or cyano group. L represents a single bond or a divalent linking group containing an oxygen atom. R represents a halogen atom, alkyl group, cycloalkyl group, aryl group, alkenyl group, aralkyl group, alkoxy group, alkylcarbonyloxy group, alkylsulfonyloxy group, alkyloxycarbonyl group, or 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 between 1 and 3. b represents an integer between 0 and (5-a). 【0132】 In the general formula (Y), R is preferably a hydrogen atom. L is preferably a single bond. 【0133】 The following are examples of repeating units having an acid group. In the formulas, a represents 1 or 2. 【0134】 [ka] 【0135】 [ka] 【0136】 [ka] 【0137】 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. 【0138】 [ka] 【0139】 [ka] 【0140】 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). 【0141】 <Repeating units containing fluorine, bromine, or iodine atoms> Resin (A) may have repeating units having fluorine atoms, bromine atoms, or iodine atoms, in addition to the <repeating units having acid-degradable groups> and <repeating units having acid groups> described above. Furthermore, it is preferable that the <repeating units having fluorine atoms, bromine atoms, or iodine atoms> referred to here are different from other types of repeating units belonging to group A, such as the <repeating units having lactone groups, sultone groups, or carbonate groups> and <repeating units having photoacid-generating groups> described later. 【0142】 As a repeating unit having a fluorine atom, a bromine atom, or an iodine atom, the repeating unit represented by formula (C) is preferred. 【0143】 [ka] 【0144】 L5 represents a single bond or an ester group. R9 represents an alkyl group which may have a hydrogen atom, or a fluorine atom, a bromine atom, or an iodine atom. R 10 This represents an alkyl group which may have a hydrogen atom, a fluorine atom, a bromine atom, or an iodine atom, a cycloalkyl group which may have a fluorine atom, a bromine atom, or an iodine atom, an aryl group which may have a fluorine atom, a bromine atom, or an iodine atom, or a group which is a combination thereof. 【0145】 Examples of repeating units having fluorine or iodine atoms are shown below. 【0146】 [ka] 【0147】 The content of repeating units having fluorine atoms, bromine atoms, or iodine atoms 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). As mentioned above, the repeating units having fluorine atoms, bromine atoms, or iodine atoms do not include <repeating units having acid-degradable groups> and <repeating units having acidic groups>. Therefore, the content of the repeating units having fluorine atoms, bromine atoms, or iodine atoms mentioned above refers to the content of repeating units having fluorine atoms, bromine atoms, or iodine atoms excluding <repeating units having acid-degradable groups> and <repeating units having acidic groups>. 【0148】 The total content of repeating units in resin (A) that contain at least one of fluorine atoms, bromine atoms, 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. 【0149】 <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. First, we will explain repeating units having at least one selected from the group consisting of lactone groups, sultone groups, and carbonate groups (hereinafter collectively referred to as "repeating units having lactone groups, sultone groups, or carbonate groups"). It is also preferable that the repeating units having a lactone group, a sultone group, or a carbonate group do not have acidic groups such as a hydroxyl group or a hexafluoropropanol group. 【0150】 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). Furthermore, lactone groups or sultone groups may be directly bonded to the main chain. For example, ring member atoms of lactone groups or sultone groups may constitute the main chain of resin (A). 【0151】 [ka] 【0152】 The 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 greater, the multiple Rb2 groups may be different, and the multiple Rb2 groups may bond to each other to form a ring. 【0153】 Examples of repeating units having a group containing 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). 【0154】 [ka] 【0155】 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 group combining these. Among these, a single bond or a linking group represented by -Ab1-CO2- is preferred. Ab1 is a linear or branched alkylene group, or a monocyclic or polycyclic cycloalkylene group, and a methylene group, ethylene group, cyclohexylene group, adamantylene group, or norbornylene group is preferred. 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). 【0156】 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. 【0157】 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. 【0158】 [ka] 【0159】 In formula (A-1), R A 1 This represents a hydrogen atom, a halogen atom, or a monovalent organic group (preferably a methyl group). n represents a non-negative integer. R 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 groups that are combinations thereof. Z represents an atomic group that forms a monocyclic or polycyclic ring with the group represented by -O-CO-O- in the formula. 【0160】 Examples of repeating units having a lactone group, a sultone group, or a carbonate group are shown below. 【0161】 [ka] 【0162】 [ka] 【0163】 [ka] 【0164】 Next, we will describe repeating units having a hydroxyl group or a cyano group. 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. 2014-98921. 【0165】 Next, we will describe repeating units having alkali-soluble groups. The resin (A) may have repeating units having alkali-soluble groups. Examples of alkali-soluble groups include carboxyl groups, sulfonamide groups, sulfonylimide groups, bisulfonylimide groups, and aliphatic alcohols substituted at the α-position with an electron-withdrawing group (e.g., hexafluoroisopropanol 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. 2014-98921. 【0166】 The content of repeating units having at least one group selected from lactone groups, sultone groups, carbonate groups, hydroxyl groups, cyano groups, and alkali-soluble groups 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). 【0167】 <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 (hereinafter also referred to as a "photoacid generating group"). In this case, the repeating unit having this photoacid generating group can be considered to be the photoacid generating agent (B) described above. Examples of such repeating units include the repeating unit represented by the following equation (4). 【0168】 [ka] 【0169】 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. 40This 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. 【0170】 [ka] 【0171】 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. 【0172】 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). 【0173】 <Repeating unit 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). It is preferable that the repeating units represented by the following formulas (V-1) and (V-2) are different from the repeating units described above. 【0174】 [ka] 【0175】 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 unit described in paragraph

[0100] of International Publication No. 2018 / 193954. 【0176】 <Repeating units to reduce the mobility of the main chain> Resin (A) is preferable to have a high glass transition temperature (Tg) from the viewpoint of suppressing 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. However, excessively high Tg leads to a decrease in the dissolution rate in the developer, so 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). Furthermore, the calculation of Tg using the Bicerano method can be performed using the polymer property estimation software MDL Polymer (MDL Information Systems, Inc.). 【0177】 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. 【0178】 (The repeating unit represented by formula (A)) One example of a specific means of achieving (a) above is to introduce repeating units represented by formula (A) into resin (A). 【0179】 [ka] 【0180】 Formula (A), R AR 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. 【0181】 (The repeating unit represented by formula (B)) One example of a specific means of achieving (b) above is to introduce repeating units represented by formula (B) into resin (A). 【0182】 [ka] 【0183】 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. Furthermore, 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. 【0184】 (The repeating unit represented by formula (C)) One example of a specific means of achieving (c) above is to introduce repeating units represented by formula (C) into resin (A). 【0185】 [ka] 【0186】 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. 【0187】 (The repeating unit represented by formula (D)) One example of a specific means of achieving (d) above is to introduce repeating units represented by formula (D) into resin (A). 【0188】 [ka] 【0189】 In formula (D), "cylic" 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. 【0190】 (The repeating unit represented by formula (E)) One example of a specific means of achieving (e) above is to introduce repeating units represented by formula (E) into resin (A). 【0191】 [ka] 【0192】 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 substitution mechanisms. A "cylic" is a cyclic group that contains carbon atoms in the 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. 【0193】 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 solution during immersion exposure. Examples of such repeating units include repeating units derived from 1-adamantyl (meth)acrylate, diamantyl (meth)acrylate, tricyclodecanyl (meth)acrylate, or cyclohexyl (meth)acrylate. 【0194】 <A repeating unit represented by formula (III) that does not contain 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. 【0195】 [ka] 【0196】 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. 2014-98921. 【0197】 <Other repeating units> Furthermore, resin (A) may have repeating units other than 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. Examples of such repeating units are shown below. 【0198】 [ka] 【0199】 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. 【0200】 As for resin (A), (especially when the composition is used as an active 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. In this case, 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 composed of methacrylate repeating units and acrylate repeating units, and it is preferable that the acrylate repeating units make up 50 mol% or less of the total repeating units. 【0201】 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, preferably 1,000 to 30,000, more preferably 3,000 to 30,000, and even more preferably 5,000 to 15,000. The degree of dispersion (molecular weight distribution) of resin (A) is usually 1 to 5, preferably 1 to 3, more preferably 1.2 to 3.0, and even more 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. 【0202】 In the resist 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, based on the total solid content of the composition. Resin (A) may be used alone or in combination of multiple types. 【0203】 [Solvent (F)] The resist composition preferably contains a solvent (preferably an organic 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). 【0204】 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. 【0205】 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. 【0206】 The solvent content in the resist 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 resist composition. Note that "solids" refers to all components other than the solvent. 【0207】 [Compounds that generate acid upon irradiation with active light or radiation (B) (Photoacid generators)] The resist composition contains compound (B) (photoacid generator) that generates acid upon irradiation with active light or radiation. 【0208】 Compound (B) may be in the form of a low molecular weight compound, or it may be incorporated into a polymer (for example, the resin (A) described above). Alternatively, both the form of a low molecular weight compound and the form incorporated into a polymer (for example, the resin (A)) may be used in combination. If compound (B) is in the form of a low molecular weight compound, the molecular weight of compound (B) 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 compound (B) is incorporated into a polymer, it may be incorporated into a resin (A) or into a resin different from resin (A). Compound (B) is preferably a low-molecular-weight compound. 【0209】 For example, compound (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. 【0210】 The molecular weight of the acid generated from compound (B) is preferably 240 or more, more preferably 250 or more, still more preferably 260 or more, particularly preferably 270 or more, and most preferably 280 or more. 【0211】 <Organic cation> 「M + X - 」, in the compound represented by, M + represents an organic cation. The structure of the above organic cation is not particularly limited. Also, the valence of the organic cation may be 1 or 2 or more. As the above organic cation, a cation represented by the following general formula (ZaI) (hereinafter also referred to as "cation (ZaI)"), or a cation represented by the following general formula (ZaII) (hereinafter also referred to as "cation (ZaII)") is preferable. 【0212】 【Chemical formula】 【0213】 In general formula (ZaI), R 201 , R 202 , and R 203 each independently represent an organic group. In general formula (ZaII), R 204 and R 205 each independently represent an organic group. Although general formulas (ZaI) and (ZaII) will be described in detail below, at least one of R 201 , R 202 , and R 203 in general formula (ZaI) is an aryl group, or at least one of R 204 and R 205 in general formula (ZaII) is preferably an aryl group. The above aryl group may have a substituent, and as the substituent, a halogen atom (preferably a fluorine atom or an iodine atom) or an organic group is preferable. Also, R 201 , R 202, and R 203 At least one of them has an acid-decomposable group, or R in the general formula (ZaII) 204 and R 205 It is also preferable that at least one of them has an acid-decomposable group. The acid-decomposable group is the same as that in the resin (A). R in the general formula (ZaI) 201 , R 202 , and R 203 In the form that at least one of them has an acid-decomposable group, R 201 , R 202 , and R 203 It is preferably an aryl group substituted with an organic group containing at least one acid-decomposable group. R in the general formula (ZaII) 204 and R 205 In the form that at least one of them has an acid-decomposable group, R 204 and R 205 It is preferably an aryl group substituted with an organic group containing at least one acid-decomposable group. 【0214】 The cation (ZaI) will be described. R 201 , R 202 , and R 203 The number of carbon atoms of the organic group as is usually 1 to 30, preferably 1 to 20. Also, two of R 201 ~R 203 may be bonded 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. R 201 ~R 203 Examples of the group formed by bonding two of them include an alkylene group (e.g., butylene group and pentylene group), and -CH2-CH2-O-CH2-CH2-. 【0215】 Preferable embodiments of the organic cation in the formula (ZaI) include the cation (ZaI-1), the cation (ZaI-2), the organic cation represented by the formula (ZaI-3b) (cation (ZaI-3b)), and the organic cation represented by the formula (ZaI-4b) (cation (ZaI-4b)) described later. 【0216】 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. Also, 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, 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 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. 【0217】 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. 【0218】 R 201 ~R 203 The substituents that the aryl group, alkyl group, and cycloalkyl group may have are, independently, preferably 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, and 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. Furthermore, it is preferable that the above substituents 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 leaving group that is removed upon the action of an acid. The polar group and leaving group are as described above. 【0219】 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 Organic groups that do not have an aromatic ring generally have 1 to 30 carbon atoms, with 1 to 20 carbon atoms being preferred. R 201 ~R 203 Each of these is preferably an alkyl group, a cycloalkyl group, an allyl group, or a vinyl group, more preferably a linear or branched 2-oxoalkyl group, a 2-oxocycloalkyl group, or an alkoxycarbonylmethyl group, and even more preferably a linear or branched 2-oxoalkyl group. 【0220】 R 201 ~R 203 Examples 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. Also, R 201 ~R 203 It is also preferable that each substituent independently forms an acid-degradable group in any combination of substituents. 【0221】 Next, we will explain the cation (ZaI-3b). The cation (ZaI-3b) is a cation represented by the following formula (ZaI-3b). 【0222】 [ka] 【0223】 In the 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. Also, 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. 【0224】 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. 【0225】 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. 【0226】 R 1c ~R 5c , R 6c , R 7c , R x , R y , 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. 【0227】 Next, we will explain the cation (ZaI-4b). The cation (ZaI-4b) is a cation represented by the following formula (ZaI-4b). 【0228】 [ka] 【0229】 In the formula (ZaI-4b), l represents an integer between 0 and 2. 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 that partially contains a cycloalkyl group). 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 15 Each 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. 【0230】 In equation (ZaI-4b), R 13 , R 14 , and R 15The alkyl group may be linear or branched. The alkyl group preferably has 1 to 10 carbon atoms. The alkyl group is more preferably a methyl group, ethyl group, n-butyl group, or t-butyl group. Also, 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. 【0231】 Next, we will explain equation (ZaII). In formula (ZaII), R 204 and R 205 Each of these independently represents an organic group, preferably 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 a 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. R 204 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). 【0232】 R 204 and R 205 The aryl group, alkyl group, and cycloalkyl group may each independently have substituents. 204 and R 205Examples 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. 【0233】 M + Specific examples of organic cations represented by are shown below, but the present invention is not limited to these. 【0234】 [ka] 【0235】 [ka] 【0236】 [ka] 【0237】 [ka] 【0238】 <Organic Anions> "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. 【0239】 Examples of non-nucleophilic anions include sulfonic acid anions (aliphatic sulfonic acid anions, aromatic sulfonic acid anions, and camphor sulfonic acid 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. 【0240】 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). 【0241】 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. 【0242】 The alkyl, cycloalkyl, and aryl groups listed above may have substituents. While the substituents are not particularly limited, specific examples include nitro groups, halogen atoms such as fluorine or 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). 【0243】 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. 【0244】 An example of a sulfonylimid anion is the saccharin anion. 【0245】 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. 【0246】 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. 【0247】 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. 【0248】 A preferred example of a non-nucleophilic anion is the anion represented by the following formula (AN4). 【0249】 [ka] 【0250】 In formula (AN4), R 1 ~R 3 Each of these independently represents an organic group or a hydrogen atom. L represents a divalent linking group. 【0251】 In formula (AN4), 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-. 【0252】 L is preferably a group represented by the following formula (AN4-2). * a -(CR 2a 2) X -Q-(CR 2b 2) Y -* b (AN4-2) 【0253】 In formula (AN4-2), * a R in equation (AN4) 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 (AN4) 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 (AN4-2) is 1 or greater, and R in equation (AN4-2) 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 (AN4) 3 This indicates the connection position on the side, * B -SO3 in equation (AN4) - This indicates the connection point on the side. 【0254】 In formula (AN4), R 1 ~R 3 Each of these independently represents an organic group. The above organic group is not 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 atoms, sulfur atoms, and / or nitrogen atoms, etc.). Examples of the above organic groups include substituents that are not electron-withdrawing groups. Examples of substituents that are not electron-withdrawing groups include hydrocarbon groups, hydroxyl groups, oxyhydrocarbon groups, oxycarbonyl hydrocarbon groups, amino groups, hydrocarbon-substituted amino groups, and hydrocarbon-substituted amide groups. Furthermore, preferred substituents that are not electron-withdrawing groups are, independently, -R', -OH, -OR', -OCOR', -NH2, -NR'2, -NHR', or -NHCOR'. R' is a monovalent hydrocarbon group. 【0255】 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. 【0256】 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 (AN4). 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. 【0257】 As a non-nucleophilic anion, the anion represented by the following formula (AN1) is also preferred. 【0258】 [ka] 【0259】 In equation (AN1), o represents an integer between 1 and 3. p represents an integer between 0 and 10. q represents an integer between 0 and 10. 【0260】 Xf represents a fluorine atom or an organic group. The organic group may be an organic group substituted with at least one fluorine atom, or it may be an organic group that does not have a fluorine atom. The number of carbon atoms in the organic group (preferably an alkyl group) is preferably 1 to 10, and more preferably 1 to 4. Furthermore, as the organic group substituted with at least one fluorine atom (preferably an alkyl group), a perfluoroalkyl group is preferred. At least one 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. 【0261】 R4 and R5 each independently represent a hydrogen atom, a fluorine atom, an alkyl group, or an alkyl group substituted with at least one fluorine atom. If there are multiple R4 and R5, they may be the same or different. The alkyl groups represented by R4 and R5 preferably have 1 to 4 carbon atoms. The alkyl groups may have substituents. Hydrogen atoms are preferred for R4 and R5. Specific examples and preferred embodiments of alkyl groups substituted with at least one fluorine atom are the same as the specific examples and preferred embodiments of Xf in formula (AN1). 【0262】 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-. 【0263】 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. 【0264】 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. Furthermore, 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. 【0265】 The above 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. Furthermore, two or more substituents may bond to each other to form a ring. For example, two alkoxy groups, or a hydroxyl group and an alkoxy group, may bond to each other to form a ring having a cyclic acetal structure. This ring may have substituents. Examples of substituents include alkyl groups (1 to 4 carbon atoms), halogen atoms, hydroxyl groups, alkoxy groups (1 to 4 carbon atoms), carboxyl groups, and alkoxycarbonyl groups (2 to 6 carbon atoms). 【0266】 The anion represented by formula (AN1) 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 (AN1). q' represents an integer from 0 to 10. 【0267】 The following embodiments (AN2) and (AN3) are also preferred as anions represented by formula (AN1). Appearance (AN2): In formula (AN1), o represents 2, p represents 0, and -SO3 - The two Xf atoms bonded to the carbon atom directly bonded to (hereinafter, this carbon atom will also be called "carbon atom Z1") each independently represent an organic group that does not contain a hydrogen atom or a fluorine atom, and the two Xf atoms bonded to the carbon atom adjacent to the above carbon atom (hereinafter, this carbon atom will also be called "carbon atom Z2") each independently represent a hydrogen atom or an organic group. Preferred embodiments of q, L, and W are the same as those described above. The two Xf atoms bonded to carbon atom Z1 are preferably hydrogen atoms. Preferably, at least one of the two Xf atoms bonded to carbon atom Z2 is a fluorine atom or an organic group having a fluorine atom; more preferably, both are a fluorine atom or an organic group having a fluorine atom; and even more preferably, both are fluorine-substituted alkyl groups. 【0268】 Embodiment (AN3): In formula (AN1), one of the two Xfs independently represents a fluorine atom or an alkyl group substituted with at least one fluorine atom, and the other independently represents a hydrogen atom or an organic group without a fluorine atom. Preferred embodiments of o, p, q, R4, R5, L, and W are the same as those described above. 【0269】 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. 【0270】 As a non-nucleophilic anion, an aromatic sulfonic acid anion represented by the following formula (AN5) is also preferred. 【0271】 [ka] 【0272】 In formula (AN5), 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. 【0273】 n represents a non-negative integer. n is preferably between 1 and 4, more preferably between 2 and 3, and even more preferably 3. 【0274】 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. 【0275】 B represents a hydrocarbon group. 【0276】 B is preferably an aliphatic hydrocarbon structure. B is more preferably an isopropyl group, a cyclohexyl group, or an optionally substituted aryl group (such as a tricyclohexylphenyl group). Furthermore, B is also "-(L) q The substituent may be represented by "-W". L, q, and W have the same meanings as L, q, and W in formula (AN1) above, and the specific examples and preferred ranges are also the same. 【0277】 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, Rq 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. 【0278】 Furthermore, non-nucleophilic anions include those represented by the following formulas (d1-1) to (d1-4). 【0279】 [ka] 【0280】 [ka] 【0281】 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). 【0282】 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. Also, in equation (d1-2) "Z 2c-SO3 - It is preferable that the anion is different from the anion represented by the above formulas (AN4), (AN1), or (AN5). For example, Z 2c It is preferable that it is not an aryl group. Also, 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. 【0283】 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. 【0284】 In formula (d1-4), R 53 ~R 54 R represents an organic group (preferably a hydrocarbon group having a fluorine atom). 53 ~R 54 They may be joined to each other to form a ring. 【0285】 Organic anions may be used individually or in combination of two or more. 【0286】 The resist composition preferably contains two or more compounds (B), or compound (B) may be at least one selected from the group consisting of the following compounds (I) and (II). 【0287】 <Compound (I) and Compound (II)> Compound (B) is also preferably at least one selected from the group consisting of the following compounds (I) and (II). 【0288】 (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. Cation site M1 + and cation site M2 + Each of these preferably represents an organic cation independently, and specific examples and preferred ranges are as described above in M + This is similar to the organic cation represented by [formula]. Furthermore, the above compound (I) satisfies the following condition I. 【0289】 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. 【0290】 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". To explain 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. 【0291】 Furthermore, 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 such 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 forming a compound having "and one HA2" corresponds to the above-mentioned acid dissociation constant a1. Also, "two A1 - 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 such a compound PI, the above-mentioned cation site M1 in the above-mentioned structural site X + to H + When a compound PI has multiple acid dissociation constants derived from the acidic site represented by HA1, the value of acid dissociation constant a2 is greater than the largest of the multiple acid dissociation constants a1. -Let the acid dissociation constant when it becomes "a compound having one HA1 and one HA2" be aa, and "one A1" - Let the acid dissociation constant when the "compound having one HA1 and one HA2" becomes "a compound having two A1s" - and the acid dissociation constant when it becomes "a compound having one HA2" be ab. The relationship between aa and ab satisfies aa < ab. 【0292】 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 A1s - , and two or more of the above M1s + may be the same or different from each other. Also, in the compound (I), the above A1 - and the above A2 - , as well as 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. 【0293】 In the above compound PI, the difference (absolute value) between the acid dissociation constant a1 (the maximum value when there are multiple acid dissociation constants a1) 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 (the maximum value when there are multiple acid dissociation constants a1) and the acid dissociation constant a2 is not particularly limited, but for example, it is 16 or less. 【0294】 In the above compound PI, the acid dissociation constant a2 is, for example, 20 or less, and preferably 15 or less. The lower limit value of the acid dissociation constant a2 is preferably -4.0 or more. 【0295】 Furthermore, 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. 【0296】 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 Each of these independently represents a monovalent organic group. 【0297】 [ka] 【0298】 [ka] 【0299】 The specific structure of compound (I) is not particularly limited, but examples include compounds represented by formulas (Ia-1) to (Ia-5) described later. 【0300】 - Compound represented by formula (Ia-1) - In the following, we will first discuss the compound represented by formula (Ia-1). 【0301】 M 11 + A 11 - -L1-A 12 - M 12 + (Ia-1) 【0302】 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. 【0303】 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 elements 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 11It 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. Furthermore, 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. 【0304】 In formula (Ia-1), M 11 + and M 12 + For the organic cation represented by the above M + It is the same as this. 【0305】 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 they be monovalent anionic functional groups 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. 【0306】 [ka] 【0307】 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. 【0308】 R A1 Examples of monovalent organic groups represented by include cyano groups, trifluoromethyl groups, and methanesulfonyl groups. 【0309】 R A2 The monovalent organic group represented 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. 【0310】 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, and perfluoroalkyl groups being more preferred. 【0311】 In equations (BX-1) to (BX-4) and (BX-6), RB represents a monovalent organic group. * represents a bond position. R B The monovalent organic group represented 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. In addition, the carbon atoms that become the bonding positions in the alkyl group (for example, in the cases of formulas (BX-1) and (BX-4), the carbon atoms directly bonded to the -CO- explicitly stated in the formula of the alkyl group; in the cases of formulas (BX-2) and (BX-3), the carbon atoms directly bonded to the -SO2- explicitly stated in the formula of the alkyl group; and in the case of formula (BX-6), the carbon atoms explicitly stated in the formula of the alkyl group) - This refers to the carbon atom that is directly bonded to it. If the atom has substituents, it is also preferable that the substituents are other than a fluorine atom or a cyano group. Furthermore, the alkyl group may have carbon atoms substituted with carbonyl carbons. 【0312】 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. 【0313】 In formula (Ia-1), the divalent linking group represented by L1 is not particularly limited and may be -CO-, -NR-, -CO-, -O-, -S-, -SO-, -SO2-, alkylene group (preferably having 1 to 6 carbon atoms; may be linear or branched), cycloalkylene group (preferably having 3 to 15 carbon atoms), alkenylene group (preferably having 2 to 6 carbon atoms), or a divalent aliphatic heterocyclic group (having at least one N, O, S, or Se atom in the ring structure). Examples include 5-10 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. Furthermore, 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). 【0314】 In particular, the divalent linking group represented by L1 is preferably the divalent linking group represented by formula (L1). 【0315】 [ka] 【0316】 In formula (L1), L 111 This represents a single bond or a divalent linking group. L 111The 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 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. Furthermore, 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 to combine it with this. 【0317】 - Compounds represented by formulas (Ia-2) to (Ia-4) - Next, we will explain the compounds represented by formulas (Ia-2) to (Ia-4). 【0318】 [ka] 【0319】 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 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). 【0320】 [ka] 【0321】 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. 【0322】 Furthermore, 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 21a Acid 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. Also, M 21a + M 21b + , and M 22 + They may be the same or different from one another. Also, 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. 【0323】 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 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). 【0324】 [ka] 【0325】 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. 【0326】 Furthermore, 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. 31b It 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. Also, 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. 【0327】 In equation (Ia-4), A 41a - , A 41b - , and A42 - 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. 【0328】 Furthermore, 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. Also, 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. 【0329】 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 not particularly limited and includes, for example, -CO-, -NR-, -O-, -S-, -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), 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. The above 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. Furthermore, 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). 【0330】 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). 【0331】 [ka] 【0332】 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. Furthermore, 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. 【0333】 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. Furthermore, 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). 【0334】 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 substituents are 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 to combine it with this. Also, 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 to combine it with this. 【0335】 - Compound represented by formula (Ia-5) - Next, let's explain equation (Ia-5). 【0336】 [ka] 【0337】 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, but examples include monovalent anionic functional groups selected from the group consisting of the above formulas (AX-1) to (AX-3). A 52a - and A 52b - A represents a divalent anionic functional group. Here, A 52a - and A 52b - The divalent anionic functional group represented by is the anionic moiety A2 mentioned above. - This refers to a divalent group containing A. 52a - and A 52b - Examples of divalent anionic functional groups represented by the above formulas (BX-8) to (BX-11) include divalent anionic functional groups selected from the group. 【0338】 M 51a + M 51b + M 51c + M 52a + , and M 52b + Each of these independently represents an organic cation. 51a + M 51b + M 51c + M 52a+ , and M 52b + The organic cation represented by the above M1 + This is synonymous with the same thing, and the preferred embodiment is also the same. L 51 and L 53 Each of these independently represents a divalent organic group. 51 and L 53 As a divalent organic group represented by the above formula (Ia-2), L 21 and L 22 This is synonymous with the same thing, and the preferred embodiment is also the same. L 52 L represents a trivalent organic group. 52 As 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. 【0339】 Furthermore, 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. Also, M 51a + M 51b + M 51c + M 52a + , and M 52b + They may be the same or different from one another. Also, 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 these may have an acid-degradable group as a substituent. 【0340】 (Compound (II)) Compound (II) is a compound having two or more of the above-mentioned structural sites X and one or more of the following structural sites Z, which generates an acid containing two or more of the above-mentioned first acidic sites derived from the above-mentioned structural sites X and the above-mentioned structural sites Z upon irradiation with active light or radiation. Structural site Z: A nonionic site capable of neutralizing acids. 【0341】 Definition of structural site X in compound (II), and A1 - and M1 + The definition is the definition of structural site X in compound (I) described above, and A1 - and M1 + This is synonymous with the definition of [the specified term], and the preferred embodiment is also the same. 【0342】 In the above compound (II), the above cation moiety M1 in the above structural moiety X + to H + In compound PII obtained by replacing with the above structural site X, the above cation site M1 + to H + The preferred range for the acid dissociation constant a1 derived from the acidic moiety represented by HA1, which is obtained by replacing it with the above compound PI, is the same as the acid dissociation constant a1 in the above compound PI. Furthermore, if compound (II) is, for example, a compound that generates an acid having two of the first acidic sites derived from the above structural site X and the above structural site Z, then compound PII corresponds to "a compound having two HA1s". When the acid dissociation constant of this compound PII is determined, compound PII corresponds to "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. 【0343】 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. Also, two or more of the above A1 - , and two or more of the above M1 + These may be the same or different. 【0344】 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. 【0345】 [ka] 【0346】 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. 【0347】 Compound (II) is not particularly limited, but examples include compounds represented by the following formulas (IIa-1) and (IIa-2). 【0348】 [ka] 【0349】 In the above equation (IIa-1), A 61a - and A 61b - These are A in equation (Ia-1) described 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. 【0350】 In formula (IIa-1), R 2X R represents a monovalent organic group. 2X The monovalent organic group represented by is not particularly limited, and examples include alkyl groups (preferably having 1 to 10 carbon atoms; may be linear or branched), cycloalkyl groups (preferably having 3 to 15 carbon atoms), or alkenyl groups (preferably having 2 to 6 carbon atoms), in which -CH2- may be substituted with one or more selected from the group consisting of -CO-, -NH-, -O-, -S-, -SO-, and -SO2-. Furthermore, the alkylene group, the cycloalkylene group, and the alkenylene group may have substituents. The substituents are not particularly limited, but examples include halogen atoms (preferably fluorine atoms). 【0351】 Furthermore, 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. Also, M 61a + M 61b + , A61a - , A 61b - , L 61 , L 62 , and R 2X At least one of these may have an acid-degradable group as a substituent. 【0352】 In the above equation (IIa-2), A 71a - , A 71b - , and A 71c - These are A in equation (Ia-1) described above. 11 - It is synonymous with the same as the preferred embodiment. Also, M 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. 【0353】 Furthermore, 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. Also, M 71a + M 71b + M 71c + , A 71a - , A 71b - , A 71c - , L 71 , L 72 , and L 73 At least one of these may have an acid-degradable group as a substituent. 【0354】 The anionic moieties that compound (I) and compound (II) may have are exemplified, but the present invention is not limited to these. 【0355】 [ka] 【0356】 [ka] 【0357】 As compound (B), it is also preferable to use the photoacid generators disclosed in paragraphs

[0135] to

[0171] of International Publication No. 2018 / 193954, paragraphs

[0077] to

[0116] of International Publication No. 2020 / 066824, paragraphs

[0018] to

[0075] and

[0334] to

[0335] of International Publication No. 2017 / 154345. 【0358】 The content of compound (B) in the resist composition is not particularly limited, but in order to make the cross-sectional shape of the formed pattern more rectangular, it is preferably 1% by mass or more, more preferably 5% by mass or more, and even more preferably 10% by mass or more, relative to the total solid content of the resist composition. Furthermore, the content of compound (B) is preferably 80% by mass or less, more preferably 70% by mass or less, and even more preferably 60% by mass or less, relative to the total solid content of the resist composition. Compound (B) may be used alone or in combination of two or more types. 【0359】 Furthermore, compound (B) may also be compound (X) as described below. 【0360】 <Compound (X)> Compound (X) is a salt containing a cation (specific cation) represented by the following formula (X). 【0361】 [ka] 【0362】 In formula (X), Ar X This represents an aryl group substituted with a group containing a halogen atom. Ar x The aryl group represented by may be monocyclic or polycyclic. Furthermore, the aryl group may be a heterocyclic ring containing an oxygen atom, a nitrogen atom, or a sulfur atom, etc. Examples of the above heterocycles include pyrrole rings, furan rings, thiophene rings, indole rings, benzofuran rings, and benzothiophene rings. The number of carbon atoms in the above aryl group (Ar X The number of carbon atoms is preferably 6 to 20, more preferably 6 to 15, and even more preferably 6 to 10. 【0363】 A group containing a halogen atom refers to a group that contains a halogen atom either as an atom itself or as part of a substituent. Examples of halogen atoms include fluorine atoms, chlorine atoms, bromine atoms, and iodine atoms, with fluorine atoms or iodine atoms being preferred. Examples of groups containing halogen atoms include halogen atoms, alkyl halides, alkoxy halides, and aryl halides. The number of halogen atoms in the above aryl group is preferably 1 to 20, more preferably 1 to 15, and even more preferably 1 to 10. The number of halogen-containing groups in the above aryl group is preferably 1 to 10, more preferably 1 to 5, and even more preferably 1 to 3. The above aryl group may be substituted with a group that does not contain a halogen atom, in addition to a group that contains a halogen atom. The halogen-free group is preferably an alkyl group (preferably having 1 to 6 carbon atoms), an alkoxy group, or an alkoxycarbonyl group, and more preferably an alkyl group (preferably having 1 to 6 carbon atoms) or an alkoxy group (preferably having 1 to 6 carbon atoms). The aryl group is preferably a phenyl group or a naphthyl group, and more preferably a phenyl group. 【0364】 R X11 ~R X16 Each of these independently represents either a hydrogen atom or a hydrocarbon group. R X11 ~R X12 At least one of them is preferably a hydrocarbon group. X13 ~R X16 It is preferable that this represents a hydrogen atom. The hydrocarbon group described above may be linear, branched, or cyclic. Examples of the hydrocarbon groups mentioned above include alkyl groups, cycloalkyl groups, alkenyl groups, and aryl groups, with alkyl groups being preferred. The number of carbon atoms in the hydrocarbon group is preferably 1 to 20, more preferably 1 to 10, and even more preferably 1 to 5. R X11 and R X12 This means that they may be bonded to each other to form a ring, R X11 and R X13~R X16 at least one of them, or R X12 and R X13 ~R X16 at least one of them may be bonded to each other to form a ring. 【0365】 n and m each independently represent an integer of 1 or more. As n and m, 1 to 10 are preferable, 1 to 5 are more preferable, 1 to 3 are still more preferable, and 2 is particularly preferable. Further, n and m preferably represent the same integer. When n represents an integer of 2 or more, two or more R X13 each other, and two or more R X14 each other may be the same or different. Also, when m represents an integer of 2 or more, two or more R X15 each other, and two or more R X16 each other may be the same or different. 【0366】 L X represents a divalent linking group. Examples of the divalent linking group include, for example, -CO-, -NR A -, -O-, -S-, -SO-, -SO2-, -N(SO2-R A ), an alkylene group, a cycloalkylene group, an alkenylene group, and a divalent linking group formed by combining a plurality of these, and a divalent linking group containing an oxygen atom is preferable. Examples of the divalent linking group containing an oxygen atom include, for example, -CO-, -O-, -SO-, -SO2-, -N(SO2-R A ), and a divalent linking group formed by combining a plurality of these. As R A , a hydrogen atom or an alkyl group having 1 to 6 carbon atoms can be mentioned. Among them, as the divalent linking group containing an oxygen atom, -O-, -CO-, or -N(SO2-R A )- is preferable, and -O- or -CO- is more preferable. The divalent linking group containing an oxygen atom means an oxygen atom itself and a divalent linking group containing an oxygen atom as a part of the divalent linking group. The number of oxygen atoms in a divalent linking group containing oxygen atoms is preferably 1 to 3, more preferably 1 to 2, and even more preferably 1. 【0367】 As the specific cation, the cation represented by formula (X-1) is preferred. 【0368】 [ka] 【0369】 In formula (X-1), X1 represents a group containing a halogen atom. In the above equation (X), X1 is Ar x This is synonymous with the halogen-containing group that the other group possesses, and the preferred range is also the same. 【0370】 Y1 represents a group that does not contain a halogen atom. The halogen-free group is preferably an alkyl group (preferably having 1 to 6 carbon atoms), an alkoxy group, or an alkoxycarbonyl group, and more preferably an alkyl group (preferably having 1 to 6 carbon atoms) or an alkoxy group. A group that does not contain a halogen atom refers to a group that does not contain a halogen atom as part of its substituent. In other words, Y1 represents a group other than the halogen atom represented by X1. 【0371】 a represents an integer from 1 to 5, b represents an integer from 0 to 4, and a + b is from 1 to 5. For a, 1 to 4 is preferred. For b, 1 to 4 is preferred. 【0372】 R X20 ~R X29 Each of these independently represents either a hydrogen atom or a hydrocarbon group. R X20 ~R X21 In the above equation (X), R X11 ~R X12 This is synonymous with the same thing, and the preferred range is also the same. R X22 ~R X29The hydrocarbon group represented by may be linear, branched, or cyclic. R X22 ~R X29 Examples of hydrocarbon groups represented by include alkyl groups, cycloalkyl groups, alkenyl groups, and aryl groups, with alkyl groups being preferred. R X22 ~R X29 The number of carbon atoms in the hydrocarbon group represented is preferably 1 to 20, more preferably 1 to 10, and even more preferably 1 to 5. R X20 and R X21 This means that they may be bonded to each other to form a ring, R 20 and R X22 ~R X25 At least one of the following, or R X21 and R X26 ~R X29 At least one of them may be joined to each other to form a ring. 【0373】 The specific cation may be used individually or in combination of two or more types. 【0374】 The molecular weight of compound (X) is preferably 100 to 10000, more preferably 100 to 2500, and even more preferably 100 to 1500. 【0375】 The preferred range for the content of compound (X) is the same as the preferred range for the content of compound (B) described above. Compound (X) may be used alone or in combination of two or more types. When using two or more types, it is preferable that their total content is within the range of the preferred content described above. 【0376】 Specific examples of compound (X) are shown below, but the present invention is not limited to these. 【0377】 [ka] 【0378】 [ka] 【0379】 [Acid diffusion control agent] The resist composition may contain an acid diffusion control agent. The acid diffusion control agent traps the acid generated from photoacid generators during exposure and acts as a quencher to suppress the reaction of acid-degradable resins in unexposed areas due to excess generated acid. Examples of acid diffusion control agents include basic compounds (CA), low-molecular-weight compounds (CB) that have a nitrogen atom and a group that is eliminated by the action of an acid, and compounds (CC) whose acid diffusion control ability is reduced or lost by irradiation with active light or radiation. Examples of the above-mentioned compounds (CC) include onium salt compounds (CD) that are relatively weak acids with respect to the photoacid generator, and basic compounds (CE) whose basicity decreases or disappears upon irradiation with active light or radiation. As an acid diffusion control agent, any known acid diffusion control agent can be used as appropriate. For example, 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. Furthermore, for example, specific examples of basic compounds (CA) include those described in paragraphs

[0132] to

[0136] of International Publication No. 2020 / 066824; specific examples of basic compounds (CD) 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 (CB) 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 (CE) having a nitrogen atom in the cation portion include those described in paragraph

[0164] of International Publication No. 2020 / 066824. Furthermore, specific examples of onium salt compounds (CDs) that are relatively weak acids with respect to photoacid generators are those described in paragraphs

[0305] to

[0314] of International Publication No. 2020 / 158337, paragraphs

[0455] to

[0464] of International Publication No. 2020 / 158467, paragraphs

[0298] to

[0307] of International Publication No. 2020 / 158366, and paragraphs

[0357] to

[0366] of International Publication No. 2020 / 158417. 【0380】 If the resist composition contains an acid diffusion control agent, the content of the acid diffusion control agent (total if there are multiple types) is preferably 0.1 to 15.0% by mass, and more preferably 1.0 to 15.0% by mass, relative to the total solid content of the composition. In the resist composition, one acid diffusion control agent may be used alone, or two or more may be used in combination. 【0381】 [Hydrophobic resin (D)] The resist composition may further contain a hydrophobic resin different from 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. 【0382】 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. Furthermore, 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. 【0383】 If the resist 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 resist composition. 【0384】 [Surfactants (E)] The resist composition may contain a surfactant. The inclusion of a surfactant improves adhesion and allows for the formation of patterns with fewer development defects. 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. 【0385】 These surfactants may be used individually or in combination of two or more types. 【0386】 If the resist 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 composition. 【0387】 [Other additives] The resist 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 the developer (for example, a phenol compound with a molecular weight of 1000 or less, or an alicyclic or aliphatic compound containing a carboxyl group). 【0388】 The resist composition may further contain a dissolution-inhibiting compound. Here, a "dissolution-inhibiting compound" is a compound with a molecular weight of 3000 or less that decomposes due to the action of an acid, thereby reducing its solubility in an organic developer. 【0389】 The resist composition of the present invention is suitably used as a photosensitive composition for EUV light. 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. 【0390】 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. 【0391】 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 a resist composition contains a resin whose polarity increases due to the action of an acid (an acid-degradable resin), a photoacid generator, an acid diffusion control agent, and a solvent, then the 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 correspond 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 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 resin, the total atoms derived from the photoacid generator, and the total atoms derived from the acid diffusion control agent. 【0392】 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. 【0393】 [Manufacturing methods for electronic devices] Furthermore, the present invention relates to a method for manufacturing an electronic device, including the pattern formation method described above, and to an electronic device manufactured by this manufacturing method. Preferred embodiments of the electronic device of the present invention include those mounted on electrical and electronic equipment (such as home appliances, office automation equipment, media-related equipment, optical equipment, and communication equipment). [Examples] 【0394】 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. 【0395】 [Various components of the resist composition] 〔resin〕 Resins Pol-1 to Pol-32 were synthesized according to known methods. Tables 1 and 2 show the ratio (molarity), weight-average molecular weight (Mw), and dispersion (Mw / Mn) of each repeating unit. The weight-average molecular weight (Mw) and dispersion (Mw / Mn) of resins Pol-01 to Pol-32 were measured by GPC (carrier: tetrahydrofuran (THF)) (polystyrene equivalent). The ratio of each unit was also determined as follows: 13 The measurement was performed using 1C-NMR (nuclear magnetic resonance). 【0396】 [Table 1] 【0397】 [Table 2] 【0398】 The structural formulas of the repeating units shown in Tables 1 and 2 are shown below. 【0399】 [ka] 【0400】 [ka] 【0401】 [Photoacid generator] The structures of the photoacid generators used (PAG-1 to PAG-27) are shown below. 【0402】 [ka] 【0403】 [ka] 【0404】 [ka] 【0405】 [ka] 【0406】 Tables 3 and 4 below show the molecular weight of the acid generated by the photoacid generator. 【0407】 [Table 3] 【0408】 [Table 4] 【0409】 [Acid diffusion control agents, other additives] The structures of the acid diffusion control agents used (PQ-01 to PQ-08, Q-01 to Q-04) and other additives (CL-1) are shown below. E-3 is PF656 (manufactured by OMNOVA, a fluorine-based surfactant). 【0410】 [ka] 【0411】 [ka] 【0412】 [Hydrophobic resin] Hydrophobic resins D-1 to D-3 were synthesized according to known methods. Table 5 shows the ratio (mol %), weight-average molecular weight (Mw), and degree of dispersion (Mw / Mn) of each repeating unit. The weight-average molecular weight (Mw) and dispersion (Mw / Mn) of hydrophobic resins D-1 to D-3 were measured by GPC (carrier: tetrahydrofuran (THF)) (in polystyrene equivalent). The composition ratio (molar ratio) of the resins was also determined. 13 The measurement was performed using 1C-NMR (nuclear magnetic resonance). 【0413】 [Table 5] 【0414】 The structural formulas of the repeating units shown in Table 5 are shown below. 【0415】 [ka] 【0416】 〔solvent〕 The solvents used are listed below. F-1: Propylene glycol monomethyl ether acetate (PGMEA) F-2: Propylene glycol monomethyl ether (PGME) F-3: Propylene glycol monoethyl ether (PGEE) F-4: Cyclohexanone F-5: Cyclopentanone F-6:2-heptanone F-7: Ethyl lactate F-8: γ-Butyrolactone F-9: Propylene Carbonate 【0417】 [Preparation of resist composition] The components shown in Tables 6, 7, and 8 were dissolved in the solvents shown in Tables 6, 7, and 8, and filtered through a polyethylene filter with a pore size of 0.03 μm to prepare resist compositions (Res-01 to Res-52). The content (parts by mass) of each component and solvent in the resist compositions is shown in Tables 6, 7, and 8. 【0418】 [Table 6] 【0419】 [Table 7] 【0420】 [Table 8] 【0421】 [Preparation of organic treatment solution] Organic treatment solutions (R-01 to R-19) were prepared by mixing the organic solvents listed in Table 9 to the concentrations shown in Table 9. The resulting organic treatment solutions were used as developer or rinse solutions as described later. 【0422】 [Table 9] 【0423】 [Formation, pattern formation, and development of resist film] An organic film AL412 (manufactured by Brewer Science) was coated onto a silicon wafer and baked at 205°C for 60 seconds to form a film with a thickness of 5 nm. On top of that, each of the prepared resist compositions described in Tables 10 and 11 was coated and baked (PB) at the temperatures described in Tables 10 and 11 for 60 seconds to form a resist film with a thickness of 40 nm. Using an EUV lithography system (Exitech Micro Exposure Tool, NA 0.3, Quadrupol, outer sigma 0.68, inner sigma 0.36), a silicon wafer with the obtained resist film was pattern-irradiated across the entire wafer with the same exposure dose. A mask with a line size of 20 nm and a line-to-space ratio of 1:1 was used as the rectil. After irradiation, the wafer was baked (PEB) on a hot plate for 60 seconds at the temperatures listed in Tables 10 and 11. Then, the wafer was developed for 30 seconds using the developer solutions listed in Tables 10 and 11, rinsed with the rinse solutions listed in Tables 10 and 11, rotated, and baked again at 100°C for 60 seconds to obtain a 1:1 line-and-space pattern with a line width of 20 nm. 【0424】 [Evaluation of in-plane uniformity of line width] The line widths of the obtained line and space patterns were measured using a length-measuring scanning electron microscope (SEM, Hitachi S-9380II). 3σ, which is three times the standard deviation (σ) of the measured line widths, was calculated and used as an indicator of in-plane uniformity of line width. Specifically, one shot consisted of 3.5 mm in the vertical (y-axis direction) and 6.5 mm in the horizontal (x-axis direction). A total of 232 exposures were performed on the wafer, with 8 columns in the x-direction and 29 rows in the y-direction. Ten length-measuring photographs (5 lines per photograph) were taken for each shot, and the average of these 10 length-measuring values ​​was taken as the length-measuring value for that shot. The standard deviation of the length-measuring values ​​for all 232 shots was multiplied by 3 to obtain 3σ. The results are shown in Tables 10 and 11. The unit for in-plane uniformity of line width in Tables 10 and 11 below is "nm". 【0425】 [Table 10] 【0426】 [Table 11] 【0427】 From the evaluation results in Tables 10 and 11, it was found that the pattern formation method of the example exhibits excellent in-plane uniformity of the line width of the resulting pattern. Both Example 5 and Comparative Example 1 are examples developed using the organic processing solution R-05, but Example 5 shows superior in-plane uniformity of line width compared to Comparative Example 1. This is thought to be because Comparative Example 1 uses a negative-type chemically amplified resist composition (Res-46) that becomes negative through a crosslinking reaction, and therefore the organic processing solution R-05 did not wet and spread uniformly on the resist film. Although both Example 27 and Comparative Examples 2-5 were developed using the organic processing solution R-12, Example 27 exhibited superior in-plane uniformity of line width compared to Comparative Examples 2-5. This is likely because the rinsing solutions used in Comparative Examples 2-5 were not the specific organic processing solution of the present invention, and therefore did not spread uniformly across the resist film. [Industrial applicability] 【0428】 According to the present invention, a pattern forming method can be provided that can obtain a pattern with excellent in-plane uniformity of line width, and a method for manufacturing an electronic device including the above pattern forming method. 【0429】 Although the present invention has been described in detail and with reference to specific embodiments, it will be apparent to those skilled in the art that various changes and modifications can be made without departing from the spirit and scope of the invention. This application is based on Japanese Patent Application No. 2021-9169 filed on 22 January 2021 and Japanese Patent Application No. 2021-120391 filed on 21 July 2021, the contents of which are incorporated herein by reference.

Claims

[Claim 1] An organic treatment solution containing butyl acetate and hydrocarbons having 11 or more carbon atoms, The content of butyl acetate in the organic treatment liquid is 65% by mass or more and 95% by mass or less, and the content of hydrocarbons having 11 or more carbon atoms is 5% by mass or more and 35% by mass or less. The hydrocarbon having 11 or more carbon atoms is an alkane having 11 to 15 carbon atoms. The aforementioned organic processing solution is an organic processing solution used for developing or rinsing a resist film. [Claim 2] The organic treatment liquid according to claim 1, wherein the hydrocarbon having 11 or more carbon atoms is undecane or dodecane. [Claim 3] The organic treatment liquid according to claim 1, wherein the organic treatment liquid contains two or more hydrocarbons having 11 or more carbon atoms. [Claim 4] The organic treatment liquid according to claim 1, wherein the content of butyl acetate in the organic treatment liquid is 80% by mass or more and 95% by mass or less, and the content of hydrocarbons having 11 or more carbon atoms is 5% by mass or more and 20% by mass or less. [Claim 5] The organic treatment solution according to claim 1, wherein the organic treatment solution is for rinsing a resist film. [Claim 6] The organic processing solution according to claim 1, wherein the organic processing solution is for developing a resist film. [Claim 7] The organic treatment liquid according to claim 1, wherein the amount of impurities contained in the organic treatment liquid is 1 ppm (parts per million) or less by mass. [Claim 8] The organic treatment solution according to claim 1, wherein the organic treatment solution contains a conductive compound.

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