Actinic-ray-sensitive or radiation-sensitive resin composition, resist film, pattern forming method, and method for manufacturing electronic device

Abstract

Provided is an actinic-ray-sensitive or radiation-sensitive resin composition containing: a resin (A) of which the polarity is increased by the action of an acid; an onium salt (B-1) that generates an acid (ACB1) in response to irradiation with actinic rays or radiation; and an onium salt (B-2) that generates an acid (ACB2) in response to irradiation with actinic rays or radiation. The pKa of the acid (ACB1) is greater than the pKa of the acid (ACB2) by 1.0 or more. If the onium salt (B-1) has a specific structure and does not contain any fluorine atoms or contains fluorine atoms, the fluorine atom content is 3 mass% or less with respect to all atoms contained in the onium salt (B-1). If the onium salt (B-2) has a specific structure and does not contain any fluorine atoms or contains fluorine atoms, the fluorine atom content is 3 mass% or less with respect to all atoms contained in the onium salt (B-2). Also provided are: a resist film; a pattern forming method; and a method for manufacturing an electronic device, said method including the pattern forming method.

Description

Actinic ray-sensitive or radiation-sensitive resin composition, resist film, pattern forming method, and method for manufacturing electronic device

[0001] The present invention relates to an actinic ray-sensitive or radiation-sensitive resin composition, a resist film, a pattern forming method, and a method for manufacturing an electronic device. More specifically, the present invention relates to an actinic ray-sensitive or radiation-sensitive resin composition, a resist film, a pattern forming method, and a method for manufacturing an electronic device that can be suitably used in an ultra-microlithography process applicable to processes for manufacturing VLSI (Large Scale Integration) and high-capacity microchips, processes for creating molds for nanoimprinting, and processes for manufacturing high-density information recording media, as well as other photofabrication processes.

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

[0003] Currently, in addition to excimer laser light, lithography using electron beams (EB), X-rays, extreme ultraviolet rays (EUV), etc. is also being developed. Accordingly, resist compositions that are effectively sensitive to various types of actinic rays or radiation have been developed.

[0004] Patent Document 1 describes a radiation-sensitive resin composition containing a polymer having a structural unit containing an acid-dissociable group and a specific radiation-sensitive acid generator. Patent Document 2 describes a chemically amplified resist composition containing a polymer having a structural unit having a specific acid-dissociable group, a radiation-sensitive acid generator, and a compound having a specific structure, the compound generating an acid that is weaker upon exposure than the acid generated from the radiation-sensitive acid generator upon exposure.

[0005] Japanese Patent Publication No. 2018-49177 Japanese Patent Publication No. 2016-197242

[0006] Recently, the performance required of resist compositions has become increasingly higher. In particular, there is a demand for further improvement in performance in terms of line width roughness (LWR) performance and pattern shape (rectangularity of the cross-sectional shape of the pattern) when forming a pattern. LWR performance refers to the ability to reduce the LWR of the pattern.

[0007] Therefore, an object of the present invention is to provide an actinic ray-sensitive or radiation-sensitive resin composition, a resist film, a pattern formation method, and a method for manufacturing an electronic device including the pattern formation method, which are capable of forming a pattern with excellent LWR performance and pattern shape.

[0008] The present inventors have found that the above problems can be solved by the following configuration.

[0009] [1] A resin (A) whose polarity increases under the action of an acid, and a resin (AC) that changes into an acid under the action of an actinic ray or radiation. Ｂ１ an onium salt (B-1) that generates an acid (AC) upon irradiation with actinic rays or radiation; Ｂ２ and an onium salt (B-2) that generates the acid (AC), Ｂ１ The pKa of the acid (AC Ｂ２), which is at least 1.0 higher than the pKa of the onium salt (B-1), the onium salt (B-1) does not contain any fluorine atoms, or if it contains a fluorine atom, the content of fluorine atoms is 3 mass% or less, based on the total mass of all atoms contained in the onium salt (B-1), the onium salt (B-2) does not contain any fluorine atoms, or if it contains a fluorine atom, the content of fluorine atoms is 3 mass% or less, based on the total mass of all atoms contained in the onium salt (B-2), the onium salt (B-1) is at least one selected from the group consisting of onium salts represented by the following formula (b1-1) and onium salts represented by the following formula (b1-2), and the onium salt (B-2) is an onium salt represented by the following formula (b2-1).

[0010]

[0011] In formula (b1-1) and formula (b1-2), R １１ represents an organic group. １２ represents a single bond or a divalent linking group. １１ － Ha-O － , -COO － , -SO ３ － or -SO ２ N － Y １１ (R １１１ ) ｋ Represents R １１１ represents an alkyl group, a cycloalkyl group, or an aryl group. １１ -CO-, -SO-, -SO ２ - or a single bond. k represents 0 or 1. When k represents 0, R １１１ does not exist, and Y １１ is R １１ When k is 1, R １１１ is R １１ It may be bonded to X １２ － Ha-O － , -COO － , -SO ３ － or -SO ２ N － Y １２ (R １１２) ｈ Represents R １１２ represents an alkyl group, a cycloalkyl group, or an aryl group. １２ -CO-, -SO-, -SO ２ - or a single bond. h represents 0 or 1. When h represents 0, R １１２ does not exist, and Y １２ Is L １２ or Z １２ ＋ When h is 1, R １１２ Is L １２ or Z １２ ＋ Z may be bonded to １１ ＋ represents an organic cation. １２ ＋ represents an organic cation group. １１ -X １１ － does not represent an anion represented by any of the following formulas (i)-1 to (i)-3.

[0012]

[0013]

[0014] In formula (b2-1), R ２ａ represents an electron-withdrawing group. ２ｂ and R ２ｃ R each independently represents a hydrogen atom or an organic group. ２ａ , R ２ｂ and R ２ｃ At least two selected from the group consisting of may be bonded to form a ring. ２ｂ and R ２ｃ and do not both represent hydrogen atoms. ２ ＋ represents an organic cation. [2] R in the above formula (b2-1) ２ａ represents a cyano group, a nitro group, a dicyanomethyl group, or a group represented by the following formula (1A):

[0015]

[0016] In formula (1A), Y１ and Y ３ are each independently —O— or —NR ３ - represents. ３ represents a hydrogen atom or an alkyl group. ２ is -C(=O)- or -SO ２ - represents. ４ represents an alkyl group, a cycloalkyl group, or an aryl group. ３ and R ４ At least two selected from the group consisting of may be bonded to form a ring. p and r each independently represent 0 or 1. q represents 1 or 2. * represents a bonding position. [3] The actinic ray-sensitive or radiation-sensitive resin composition according to [1] or [2], wherein the onium salt (B-1) is at least one selected from the group consisting of onium salts represented by any of the following formulae (b1-2a) to (b1-2e) and onium salts represented by the above formula (b1-2):

[0017]

[0018] In formula (b1-2a), R ２１ａ ~R ２１ｅ each independently represents a hydrogen atom or an organic group. ２１ｃ and R ２１ｄ At least one selected from the group consisting of a cyano group, a nitro group, a group represented by the following formula (2A) and a group represented by the following formula (2B), R ２１ａ and R ２１ｂ does not represent a group selected from the group consisting of a cyano group, a nitro group, a group represented by the following formula (2A), and a group represented by the following formula (2B). ２１ represents a single bond or a divalent linking group. ２１ represents an integer of 1 to 4. ２１ When R represents an integer of 2 or more, a plurality of R ２１ｃ may be the same or different, and multiple R ２１ｄ may be the same or different. ２１ａ , R ２１ｂ , R ２１ｃ , R ２１ｄ and L ２１ At least two selected from the group consisting of may be bonded to form a ring.１１ ＋ represents an organic cation.

[0019]

[0020] In formula (2A), Y ２１ａ and Y ２２ａ are each independently —O— or —NR ３２ａ - represents. ３２ａ represents a hydrogen atom or an alkyl group. ４２ａ represents an alkyl group, a cycloalkyl group, or an aryl group. ２１ａ and r ２１ａ Each independently represents 0 or 1. ２１ａ and r ２１ａ and do not both represent 0. ２１ａ represents 1 or 2. * represents a bonding position. In formula (2B), Y ２１ｂ and Y ２２ｂ are each independently —O— or —NR ３２ｂ - represents. ３２ｂ represents a hydrogen atom or an alkyl group. ４２ｂ represents an alkyl group, a cycloalkyl group, or an aryl group. ２１ｂ and r ２１ｂ Each independently represents 0 or 1. * represents a bonding position. In formula (b1-2b), R ２２ａ represents an organic group other than a halogen atom, a hydroxy group, or a carboxyl group. １２ represents an aromatic group. １２ represents an integer of 0 or more. １２ When R represents an integer of 2 or more, a plurality of R ２２ａ may be the same or different. １１ ＋ represents an organic cation. １３ represents an aromatic group. ２３ａ represents a halogen atom or an organic group. １３ and q １３ Each independently represents an integer of 0 or more. １３ When R represents an integer of 2 or more, a plurality of R ２３ａ may be the same or different, provided that p １３ and q １３ and do not both represent 0.１３ If represents 1, then p １３ represents an integer of 1 or more. １１ ＋ represents an organic cation. ２４ａ represents an organic group. ２４ａ When has an aromatic ring, —COO － The carbon atom of Z is not directly bonded to the aromatic ring. １１ ＋ represents an organic cation. ２５ａ -CO-, -SO-, -SO ２ - or a single bond. ２５ａ and R ２５ｂ R each independently represents an alkyl group, a cycloalkyl group, or an aryl group. ２５ａ and R ２５ｂ may be bonded to form a ring. １１ ＋ represents an organic cation. [4] The actinic ray-sensitive or radiation-sensitive resin composition according to any one of [1] to [3], further comprising a resin (D) different from the resin (A), wherein the resin (D) satisfies the following requirement (i): (i) the SP value of the resin (D) is smaller than the SP value of the resin (A) and is 17.2 or less. [5] The actinic ray-sensitive or radiation-sensitive resin composition according to any one of [1] to [4], wherein the onium salt (B-1) does not contain a fluorine atom. [6] The actinic ray-sensitive or radiation-sensitive resin composition according to any one of [1] to [5], wherein the onium salt (B-2) does not contain a fluorine atom. [7] The actinic ray-sensitive or radiation-sensitive resin composition according to any one of [1] to [6], wherein the resin (A) has a repeating unit represented by the following formula (AP-1):

[0021]

[0022] In formula (AP-1), R Ａ１１ represents a hydrogen atom, a halogen atom or an alkyl group. Ａ１１ represents a single bond or a divalent linking group. Ａ１２ is SO ２[8] The actinic ray-sensitive or radiation-sensitive resin composition according to any one of [1] to [7], wherein the resin (A) has a repeating unit represented by the following formula (AP-2):

[0023]

[0024] In formula (AP-2), R Ａ２１ represents a hydrogen atom, a halogen atom or an alkyl group. Ａ２１ represents a single bond or a divalent linking group. Ａ２２ [9] The actinic ray-sensitive or radiation-sensitive resin composition according to any one of [1] to [8], wherein the resin (A) has a repeating unit represented by the following formula (AP-3):

[0025]

[0026] In formula (AP-3), R Ａ３１ represents a hydrogen atom, a halogen atom or an alkyl group. Ａ３１ represents a single bond or a divalent linking group. Ａ３２ represents an alicyclic hydrocarbon group. Ａ３３ represents a substituent having a double bond.

[10] The actinic ray-sensitive or radiation-sensitive resin composition according to [4], further satisfying both of the following requirements (ii) and (iii): (ii) the sum of the content of repeating units not containing a fluorine atom among the repeating units contained in the resin (D) is 80 mol % or more, based on all repeating units in the resin (D). (iii) the content of the resin (D) is 0.01 to 10 mass % based on the total solid content in the actinic ray-sensitive or radiation-sensitive resin composition.

[11] A resist film formed using the actinic ray-sensitive or radiation-sensitive resin composition according to any one of [1] to

[10] .

[12] A pattern formation method comprising the steps of: forming a resist film on a substrate using the actinic ray-sensitive or radiation-sensitive resin composition according to any one of [1] to

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

[13] A method for manufacturing an electronic device, comprising the pattern forming method according to

[12] .

[0027] The present invention can provide an actinic ray-sensitive or radiation-sensitive resin composition, a resist film, a pattern formation method, and a method for manufacturing an electronic device including the pattern formation method, which are capable of forming a pattern with excellent LWR performance and pattern shape.

[0028] The present invention will be described in detail below. The following description of the components will be based on representative embodiments of the present invention, but the present invention is not limited to such embodiments.

[0029] In this specification, "actinic rays" or "radiation" refers to, for example, the bright line spectrum of a mercury lamp, far ultraviolet rays typified by excimer lasers, extreme ultraviolet rays (EUV), X-rays, soft X-rays, and electron beams (EB). In this specification, "light" refers to actinic rays or radiation. Unless otherwise specified, in this specification, "exposure" includes not only exposure using the bright line spectrum of a mercury lamp, far ultraviolet rays typified by excimer lasers, extreme ultraviolet rays, X-rays, and EUV, but also drawing using particle beams such as electron beams and ion beams. In this specification, the word "to" is used to mean that the numerical values ​​before and after it are included as the lower and upper limits.

[0030] In this specification, (meth)acrylate refers to at least one of acrylate and methacrylate, and (meth)acrylic acid refers to at least one of acrylic acid and methacrylic acid.

[0031] In this specification, the weight average molecular weight (Mw), number average molecular weight (Mn), and dispersity (also referred to as molecular weight distribution) (Mw / Mn) of a resin are defined as polystyrene-equivalent values ​​measured by gel permeation chromatography (GPC) using a GPC apparatus (HLC-8120GPC manufactured by Tosoh Corporation) (solvent: tetrahydrofuran, flow rate (sample injection amount): 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).

[0032] In the description of groups (atomic groups) in this specification, unless contrary to the spirit of the present invention, notations that do not specify whether they are substituted or unsubstituted include groups that contain a substituent as well as groups that do not have a substituent. For example, the term "alkyl group" includes not only alkyl groups that do not have a substituent (unsubstituted alkyl groups) but also alkyl groups that have a substituent (substituted alkyl groups). Furthermore, the term "organic group" in this specification refers to a group containing at least one carbon atom. Unless otherwise specified, a monovalent substituent is preferred as the substituent. Examples of the substituent include monovalent non-metallic atomic groups excluding hydrogen atoms, which can be selected, for example, from the following substituents T:

[0033] (Substituent T) Examples of the substituent T include halogen atoms such as a fluorine atom, a chlorine atom, a bromine atom, and an iodine atom; alkoxy groups such as a methoxy group, an ethoxy group, and a tert-butoxy group; a cycloalkyloxy group; an aryloxy group such as a phenoxy group and a p-tolyloxy group; an alkoxycarbonyl group such as a methoxycarbonyl group and a butoxycarbonyl group; a cycloalkyloxycarbonyl group; an aryloxycarbonyl group such as a phenoxycarbonyl group; an acyloxy group such as an acetoxy group, a propionyloxy group, and a benzoyloxy group; an acetyl group, a benzoyl group, an isobutyryl group, Examples of the substituent T include acyl groups such as acryloyl, methacryloyl, and methoxalyl; sulfanyl groups; alkylsulfanyl groups such as methylsulfanyl and tert-butylsulfanyl; arylsulfanyl groups such as phenylsulfanyl and p-tolylsulfanyl; alkyl groups; alkenyl groups; cycloalkyl groups; aryl groups; aromatic heterocyclic groups; hydroxy groups; carboxyl groups; formyl groups; sulfo groups; cyano groups; alkylaminocarbonyl groups; arylaminocarbonyl groups; sulfonamide groups; silyl groups; amino groups; and carbamoyl groups. In addition, when these substituents can further have one or more substituents, examples of the substituent T also include groups having one or more substituents selected from the above-mentioned substituents as the further substituents (e.g., monoalkylamino groups, dialkylamino groups, arylamino groups, trifluoromethyl groups, etc.). However, the substituents in the onium salts (A) and (B) do not contain a fluorine atom as the substituent T.

[0034] In this specification, the bonding direction of a divalent group is not limited unless otherwise specified. For example, when Y is -COO- in a compound represented by the formula "X-Y-Z", Y may be -CO-O- or -O-CO-. The compound may be either "X-CO-O-Z" or "X-O-CO-Z".

[0035] In this specification, the acid dissociation constant (pKa) refers to the pKa in an aqueous solution, and specifically, is a value determined by calculation using the following software package 1 based on a database of Hammett's substituent constants and known literature values. All pKa values ​​described in this specification are values ​​determined by calculation using this software package. Software package 1: Advanced Chemistry Development (ACD / Labs) Software V8.14 for Solaris (1994-2007 ACD / Labs).

[0036] The pKa can also be calculated by molecular orbital calculation. A specific method for this is to calculate the pKa of H in an aqueous solution based on the thermodynamic cycle. ＋ One method is to calculate the dissociation free energy. ＋ The dissociation free energy can be calculated by, for example, DFT (density functional theory), but various other methods have been reported in the literature, and the method is not limited to these. There are several software programs that can perform DFT, and Gaussian 16 is an example.

[0037] In this specification, pKa refers to a value calculated based on a database of Hammett's substituent constants and publicly known literature values ​​using software package 1, as described above, but if pKa cannot be calculated by this method, a value obtained by Gaussian 16 based on DFT (density functional theory) will be adopted. In this specification, pKa refers to "pKa in aqueous solution" as described above, but if pKa in aqueous solution cannot be calculated, "pKa in dimethyl sulfoxide (DMSO) solution" will be adopted.

[0038] In this specification, the term "solid content" refers to components that form a film (preferably a resist film) formed using the actinic ray-sensitive or radiation-sensitive resin composition, and does not include solvents. Furthermore, any component that forms a film (preferably a resist film) formed using the actinic ray-sensitive or radiation-sensitive resin composition is considered to be a solid content even if it is in a liquid state.

[0039] <Actinic ray-sensitive or radiation-sensitive resin composition> The actinic ray-sensitive or radiation-sensitive resin composition of the present invention (also referred to as "the composition of the present invention") comprises a resin (A) whose polarity increases under the action of an acid, and a resin (A) that reacts with an acid (AC) upon irradiation with actinic rays or radiation. Ｂ１ an onium salt (B-1) that generates an acid (AC) upon irradiation with actinic rays or radiation; Ｂ２ and an onium salt (B-2) that generates an acid (AC Ｂ１ The pKa of the acid (AC Ｂ２ the onium salt (B-1) does not contain any fluorine atoms, or if it contains fluorine atoms, the content of fluorine atoms is 3 mass% or less based on all atoms contained in the onium salt (B-1); the onium salt (B-2) does not contain any fluorine atoms, or if it contains fluorine atoms, the content of fluorine atoms is 3 mass% or less based on all atoms contained in the onium salt (B-2); the onium salt (B-1) is at least one selected from the group consisting of onium salts represented by the following formula (b1-1) and onium salts represented by the following formula (b1-2):

[0040]

[0041] In formula (b1-1) and formula (b1-2), R １１ represents an organic group. １２ represents a single bond or a divalent linking group. １１ － Ha-O － , -COO － , -SO ３ － or -SO２ N － Y １１ (R １１１ ) ｋ Represents R １１１ represents an alkyl group, a cycloalkyl group, or an aryl group. １１ -CO-, -SO-, -SO ２ - or a single bond. k represents 0 or 1. When k represents 0, R １１１ does not exist, and Y １１ is R １１ When k is 1, R １１１ is R １１ It may be bonded to X １２ － Ha-O － , -COO － , -SO ３ － or -SO ２ N － Y １２ (R １１２ ) ｈ Represents R １１２ represents an alkyl group, a cycloalkyl group, or an aryl group. １２ -CO-, -SO-, -SO ２ - or a single bond. h represents 0 or 1. When h represents 0, R １１２ does not exist, and Y １２ Is L １２ or Z １２ ＋ When h is 1, R １１２ Is L １２ or Z １２ ＋ Z may be bonded to １１ ＋ represents an organic cation. １２ ＋ represents an organic cation group. １１ -X １１ － does not represent an anion represented by any of the following formulas (i)-1 to (i)-3.

[0042]

[0043]

[0044] In formula (b2-1), R ２ａ represents an electron-withdrawing group. ２ｂ and R ２ｃ R each independently represents a hydrogen atom or an organic group. ２ａ , R ２ｂ and R ２ｃ At least two selected from the group consisting of may be bonded to form a ring. ２ｂ and R ２ｃ and do not both represent hydrogen atoms. ２ ＋ represents an organic cation.

[0045] The mechanism by which the composition of the present invention can form a pattern with excellent LWR performance and pattern shape is not clear, but the present inventors have speculated as follows. However, the present invention is not limited by the speculated mechanism below. The acid (AC Ｂ１ ) is a compound having a pKa value that is higher than that of the acid (AC) generated from the onium salt (B-2) upon irradiation with actinic rays or radiation. Ｂ２ ), and therefore, in the composition of the present invention, the onium salt (B-2) can act as a compound (photoacid generator) that generates an acid to promote the deprotection reaction of the acid-decomposable group in the resin (A), whose polarity increases under the action of an acid, and the onium salt (B-1) can act as a quencher (acid diffusion controller) that traps the acid generated from the photoacid generator or the like upon exposure and suppresses the reaction of the resin (A) in unexposed areas due to the excess generated acid. Both the onium salt (B-1) and the onium salt (B-2) do not contain fluorine atoms, or, if they contain fluorine atoms, the content of fluorine atoms is 3% by mass or less based on all atoms contained in each compound. Hereinafter, "containing no fluorine atoms, or, if they contain fluorine atoms, the content of fluorine atoms is 3% by mass or less based on all atoms contained in each compound" is also referred to as "low fluorine content" or "low fluorine content." Since the onium salt (B-2) has a low fluorine content, it has high compatibility with the resin (A) and is dispersed uniformly. Ｂ２It is believed that excellent LWR performance can be obtained by suppressing the variation in the concentration of the acid (AC). In addition, since the onium salt (B-1) also has a low fluorine content, the compatibility between the onium salt (B-1) and the onium salt (B-2) is high. Ｂ２ ) concentration variations can be further suppressed, which is thought to further improve LWR performance. Furthermore, the improvement in pattern shape was an unexpected effect, as described below. Normally, the exposure dose is greater near the surface of the resist film, which is less affected by absorption, and in order to obtain an ideal rectangular pattern shape, it is thought that the quencher should be adjusted to be somewhat hydrophobic so that it is unevenly distributed on the surface of the resist film. There was concern that the use of onium salt (B-1) with a low fluorine content would increase the hydrophilicity of the resist film and deteriorate the pattern shape, but the pattern shape was actually improved. This is because the distribution of onium salt (B-1) and onium salt (B-2) was highly uniform, and the generated acid (AC Ｂ２ It is estimated that this is because the effect of efficiently quenching the ion beam (X) outweighs the variation in exposure dose due to slight differences in absorption.

[0046] The composition of the present invention is typically a resist composition, and may be either a positive resist composition or a negative resist composition. The composition of the present invention may be a resist composition for alkali development or a resist composition for organic solvent development. The composition of the present invention may be either a chemically amplified resist composition or a non-chemically amplified resist composition. The composition of the present invention is preferably a chemically amplified resist composition. An actinic ray-sensitive or radiation-sensitive film can be formed using the composition of the present invention. The actinic ray-sensitive or radiation-sensitive film formed using the composition of the present invention is typically a resist film. First, the various components of the composition of the present invention will be described in detail below.

[0047] [Onium Salt (B-1)] The onium salt (B-1) contained in the composition of the present invention will now be described. The onium salt (B-1) is at least one selected from the group consisting of onium salts represented by the following formula (b1-1) and onium salts represented by the following formula (b1-2):

[0048]

[0049] In formula (b1-1) and formula (b1-2), R １１ represents an organic group. １２ represents a single bond or a divalent linking group. １１ － Ha-O － , -COO － , -SO ３ － or -SO ２ N － Y １１ (R １１１ ) ｋ Represents R １１１ represents an alkyl group, a cycloalkyl group, or an aryl group. １１ -CO-, -SO-, -SO ２ - or a single bond. k represents 0 or 1. When k represents 0, R １１１ does not exist, and Y １１ is R １１ When k is 1, R １１１ is R １１ It may be bonded to X １２ － Ha-O － , -COO － , -SO ３ － or -SO ２ N － Y １２ (R １１２ ) ｈ Represents R １１２ represents an alkyl group, a cycloalkyl group, or an aryl group. １２ -CO-, -SO-, -SO ２ - or a single bond. h represents 0 or 1. When h represents 0, R １１２ does not exist, and Y １２ Is L １２ or Z １２ ＋ When h is 1, R １１２ Is L １２ or Z １２ ＋ Z may be bonded to １１ ＋ represents an organic cation. １２ ＋represents an organic cation group. １１ -X １１ － does not represent an anion represented by any of the following formulas (i)-1 to (i)-3.

[0050]

[0051] R in formula (b1-1) １１ represents an organic group. １１ preferably represents a monovalent organic group. １１ and Y １１ When R １１ and R １１１ When R １１ R preferably represents a divalent organic group. １１ The organic group represented by is not particularly limited, and examples thereof include an alkyl group, a cycloalkyl group, an alkenyl group, an alkynyl group, an aryl group, a heteroaryl group, an aralkyl group, an alkoxy group, an aryloxy group, a carboxyl group, an acyl group, an acyloxy group, a formyloxy group, an alkoxycarbonyl group, an alkylsulfoxy group, an arylsulfoxy group, an alkylsulfonyl group, an arylsulfonyl group, —OCO(OR ８ ) or -OCO(NR ９ R １０ ) is preferable. ８ , R ９ and R １０ each independently represents a hydrogen atom, an alkyl group, a cycloalkyl group, an alkenyl group, an alkynyl group, an aryl group, a heteroaryl group, or an aralkyl group.

[0052] R １１ The alkyl group, cycloalkyl group, alkenyl group, alkynyl group, aryl group, heteroaryl group, aralkyl group, alkoxy group, aryloxy group, carboxyl group, acyloxy group, formyloxy group, alkoxycarbonyl group, alkylsulfoxy group, and arylsulfoxy group represented by may further have one or more substituents. For example, the alkyl group may be substituted with a hydroxy group. Furthermore, the hydrogen atom of the carboxyl group may be substituted with a substituent.

[0053] R １１Each group represented by is described below. The number of carbon atoms in the alkyl group is not particularly limited, but may be, for example, 1 to 20, 1 to 10, or 1 to 6. The alkyl group may be either linear or branched. Examples of the alkyl group include a methyl group, an ethyl group, an n-propyl group, an i-propyl group, an n-butyl group, a t-butyl group, and an n-hexyl group. The same applies to the alkyl group portion in an alkoxy group, the alkyl group portion in an aralkyl group, the alkyl group portion in an alkoxycarbonyl group, the alkyl group portion in an alkylsulfonyl group, the alkyl group portion in an alkylsulfoxy group, the alkyl group portion in an acyl group when the acyl group is an alkylcarbonyl group, and the alkyl group portion in an acyloxy group when the acyloxy group is an alkylcarbonyloxy group. The cycloalkyl group may be 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. The number of carbon atoms in the cycloalkyl group is not particularly limited, but may be, for example, 5 to 20 or 5 to 15. The alkenyl group may be either linear or branched. The number of carbon atoms in the alkenyl group is not particularly limited, but may be, for example, 2 to 20, 2 to 10, or 2 to 6. The alkynyl group may be either linear or branched. The number of carbon atoms in the alkynyl group is not particularly limited, but may be, for example, 2 to 20, 2 to 10, or 2 to 6. The aryl group may be either monocyclic or polycyclic (e.g., 2 to 6 rings, etc.). The number of ring atoms in the aryl group is not particularly limited, but may be, for example, 6 to 20, 6 to 15, or 6 to 10. The aryl group is preferably a phenyl group, a naphthyl group, or an anthryl group, and more preferably a phenyl group.The same applies to the aryl group portion of an aralkyl group, the aryl group portion of an aryloxy group, the aryl group portion of an arylsulfonyl group, the aryl group portion of an arylsulfoxy group, the aryl group portion when the acyl group is an arylcarbonyl group, and the aryl group portion when the acyloxy group is an arylcarbonyloxy group. The heteroaryl group may be either monocyclic or polycyclic (e.g., 2 to 6 rings). The number of heteroatoms contained in the heteroaryl group as ring members is not particularly limited, but may be, for example, 1 to 10. Examples of heteroatoms include nitrogen atoms, sulfur atoms, oxygen atoms, selenium atoms, tellurium atoms, phosphorus atoms, silicon atoms, and boron atoms. The number of ring members of the heteroaryl group is not particularly limited, but may be, for example, 5 to 15.

[0054] R ８ , R ９ and R １０ R each independently represents a hydrogen atom, an alkyl group, a cycloalkyl group, an alkenyl group, an alkynyl group, an aryl group, a heteroaryl group, or an aralkyl group. ８ , R ９ and R １０ The explanations, specific examples and preferred ranges of the alkyl group, cycloalkyl group, alkenyl group, alkynyl group, aryl group, heteroaryl group and aralkyl group represented by R are as described above. １１ It is similar to that in

[0055] X in formula (b1-1) １１ － Ha-O － , -COO － , -SO ３ － or -SO ２ N － Y １１ (R １１１ ) ｋ Represents R １１１ represents an alkyl group, a cycloalkyl group, or an aryl group. １１ -CO-, -SO-, -SO ２ - or a single bond. k represents 0 or 1. When k represents 0, R １１１ does not exist, and Y１１ is R １１ When k is 1, R １１１ is R １１ may be bonded to R １１１ The number of carbon atoms in the alkyl group represented by is not particularly limited, but may be, for example, 1 to 20, 1 to 10, or 1 to 6. The alkyl group may be either linear or branched. Examples of the alkyl group include a methyl group, an ethyl group, an n-propyl group, an i-propyl group, an n-butyl group, a t-butyl group, and an n-hexyl group. R １１１ The cycloalkyl group represented by may be a monocyclic cycloalkyl group such as a cyclopentyl group or a cyclohexyl group, or may be a polycyclic cycloalkyl group such as a norbornyl group, a tetracyclodecanyl group, a tetracyclododecanyl group, or an adamantyl group. The number of carbon atoms in the cycloalkyl group is not particularly limited, but may be, for example, 5 to 20 or 5 to 15. １１１ The aryl group represented by may be either a monocyclic or polycyclic (for example, 2 to 6 rings). The number of ring atoms of the aryl group is not particularly limited, but may be, for example, 6 to 20, 6 to 15, or 6 to 10. The aryl group is preferably a phenyl group, a naphthyl group, or an anthryl group, and more preferably a phenyl group. X １１ － Ha-COO － , -SO ３ － or -SO ２ N － Y １１ (R １１１ ) ｋ Preferably, -COO － or -SO ３ － It is more preferable that:

[0056] Z in formula (b1-1) １１ ＋ represents an organic cation. １１ ＋ is preferably a sulfonium cation or an iodonium cation. １１ ＋The cation represented by formula (ZaI) is not particularly limited. The valence of the cation may be monovalent or divalent or higher. As the cation, a cation represented by formula (ZaI) below (hereinafter also referred to as "cation (ZaI)") or a cation represented by formula (ZaII) below (hereinafter also referred to as "cation (ZaII)") is preferred.

[0057]

[0058] In the above formula (ZaI), R ２０１ , R ２０２ and R ２０３ R each independently represents an organic group. ２０１ , R ２０２ and R ２０３ The number of carbon atoms in the organic group represented by R is preferably 1 to 30, and more preferably 1 to 20. ２０１ ~R ２０３ Two of these 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. ２０１ ~R ２０３ Examples of groups formed by combining two of these include alkylene groups (e.g., butylene and pentylene groups) and —CH ２ -CH ２ -O-CH ２ -CH ２ - are some examples.

[0059] Suitable embodiments of the organic cation in formula (ZaI) include cation (ZaI-1), cation (ZaI-2), cation (ZaI-3b), and cation (ZaI-4b) described below.

[0060] First, the cation (ZaI-1) will be described. The cation (ZaI-1) is R in the above formula (ZaI). ２０１ ~R ２０３ is an arylsulfonium cation, in which at least one of R is an aryl group. ２０１ ~R ２０３ may all be aryl groups, or R ２０１ ~R ２０３ A part of R may be an aryl group, and the rest may be an alkyl group or a cycloalkyl group.２０１ ~R ２０３ is an aryl group, and R ２０１ ~R ２０３ The remaining two of R 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. ２０１ ~R ２０３ Examples of groups formed by combining two of the above include alkylene groups 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 (e.g., butylene group, pentylene group, and —CH ２ -CH ２ -O-CH ２ -CH ２ The arylsulfonium cations include triarylsulfonium cations, diarylalkylsulfonium cations, aryldialkylsulfonium cations, diarylcycloalkylsulfonium cations, and aryldicycloalkylsulfonium cations.

[0061] The aryl group contained in the arylsulfonium cation is preferably a phenyl group or a naphthyl group, and more preferably a phenyl group. The aryl group may be an aryl group having a heterocyclic structure containing an oxygen atom, a nitrogen atom, or a sulfur atom. 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 group or cycloalkyl group optionally contained in the arylsulfonium cation 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, an ethyl group, a propyl group, an n-butyl group, a sec-butyl group, a t-butyl group, a cyclopropyl group, a cyclobutyl group, or a cyclohexyl group.

[0062] R ２０１ ~R ２０３Preferred substituents that the aryl group, alkyl group, and cycloalkyl group may have include alkyl groups (e.g., having 1 to 15 carbon atoms), cycloalkyl groups (e.g., having 3 to 15 carbon atoms), aryl groups (e.g., having 6 to 14 carbon atoms), alkoxy groups (e.g., having 1 to 15 carbon atoms), cycloalkylalkoxy groups (e.g., having 1 to 15 carbon atoms), halogen atoms other than fluorine atoms (e.g., chlorine atoms, bromine atoms, iodine atoms), hydroxyl groups, carboxyl groups, ester groups, sulfinyl groups, sulfonyl groups, alkylthio groups, and phenylthio groups. The above substituents may further have substituents, if possible. It is also preferred that the above substituents form an acid-decomposable group in any combination.

[0063] Next, the cation (ZaI-2) will be described. The cation (ZaI-2) is a cation represented by the formula (ZaI) R ２０１ ~R ２０３ are each independently a cation representing an organic group that does not have an aromatic ring. The aromatic ring also includes an aromatic ring containing a heteroatom. ２０１ ~R ２０３ The number of carbon atoms of the organic group not having an aromatic ring as R is preferably 1 to 30, and more preferably 1 to 20. ２０１ ~R ２０３ are each independently 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 still more preferably a linear or branched 2-oxoalkyl group.

[0064] R ２０１ ~R ２０３ Examples of the alkyl group and cycloalkyl group in R include linear alkyl groups having 1 to 10 carbon atoms or branched alkyl groups having 3 to 10 carbon atoms (e.g., methyl, ethyl, propyl, butyl, and pentyl groups), and cycloalkyl groups having 3 to 10 carbon atoms (e.g., cyclopentyl, cyclohexyl, and norbornyl groups). ２０１ ~R ２０３may be further substituted with a halogen atom other than a fluorine atom, an alkoxy group (for example, having 1 to 5 carbon atoms), a hydroxyl group, a cyano group, or a nitro group. ２０１ ~R ２０３ It is also preferred that the substituents independently form an acid-decomposable group by any combination of the substituents.

[0065] Next, the cation (ZaI-3b) will be described. The cation (ZaI-3b) is a cation represented by the following formula (ZaI-3b).

[0066]

[0067] In formula (ZaI-3b), R １ｃ ~R ５ｃ R each 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 other than a fluorine atom, a hydroxyl group, a nitro group, an alkylthio group, or an arylthio group. ６ｃ and R ７ｃ R each independently represents a hydrogen atom, an alkyl group (for example, a t-butyl group), a cycloalkyl group, a halogen atom other than a fluorine atom, a cyano group, or an aryl group. ｘ and R ｙ R each 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. １ｃ ~R ７ｃ , and R ｘ and R ｙ It is also preferred that the substituents independently form an acid-decomposable group by any combination of the substituents.

[0068] 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 Rｙ may be bonded 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 ring include aromatic or non-aromatic hydrocarbon rings, aromatic or non-aromatic heterocycles, and polycyclic fused rings formed by combining two or more of these rings. Examples of the ring include 3- to 10-membered rings, preferably 4- to 8-membered rings, and more preferably 5- or 6-membered rings.

[0069] R １ｃ ~R ５ｃ Two or more of the following, R ６ｃ and R ７ｃ , and R ｘ and R ｙ Examples of the group formed by bonding of R include alkylene groups such as butylene and pentylene. A methylene group in this alkylene group may be substituted with a heteroatom such as an oxygen atom. ５ｃ and R ６ｃ , and R ５ｃ and R ｘ The group formed by bonding is preferably a single bond or an alkylene group. Examples of the alkylene group include a methylene group and an ethylene group.

[0070] 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 ring formed by bonding together may have a substituent.

[0071] Next, the cation (ZaI-4b) will be described. The cation (ZaI-4b) is a cation represented by the following formula (ZaI-4b).

[0072]

[0073] In formula (ZaI-4b), l represents an integer of 0 to 2, and r represents an integer of 0 to 8. １３ represents a hydrogen atom, a halogen atom other than a fluorine atom (for example, a chlorine atom, a bromine atom, or an iodine atom), a hydroxyl group, an alkyl group, a halogenated alkyl group other than a fluorine atom, an alkoxy group, a carboxyl group, an alkoxycarbonyl group, or a group containing a cycloalkyl group (which may be a cycloalkyl group itself or a group containing a cycloalkyl group as a part). These groups may have a substituent. R １４ represents a hydroxyl group, a halogen atom other than a fluorine atom (for example, a chlorine atom, a bromine atom, or an iodine atom), an alkyl group, a halogenated alkyl group other than a fluorine atom, 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 as a part). These groups may have a substituent. R １４ When a plurality of R are present, each independently represents the above group such as a hydroxyl group. １５ each independently represents an alkyl group, a cycloalkyl group, or a naphthyl group. １５ may be bonded to each other to form a ring. １５ When two R are bonded to each other to form a ring, the ring skeleton may contain a heteroatom such as an oxygen atom or a nitrogen atom. １５ are preferably alkylene groups and bonded to each other to form a ring structure. １５ The ring formed by bonding together may have a substituent.

[0074] In formula (ZaI-4b), R １３ , R １４ , and R １５ The alkyl group in R may be linear or branched. The number of carbon atoms in the alkyl group is preferably 1 to 10. The alkyl group is preferably a methyl group, an ethyl group, an n-butyl group, a t-butyl group, or the like. １３ ~R １５, and R ｘ and R ｙ It is also preferred that each of the substituents independently form an acid-decomposable group by any combination of the substituents.

[0075] Next, formula (ZaII) will be described. In formula (ZaII), R ２０４ and R ２０５ R each independently represents an aryl group, an alkyl group, or a cycloalkyl group. ２０４ and R ２０５ The aryl group in R is preferably a phenyl group or a naphthyl group, and more preferably a phenyl group. ２０４ and R ２０５ The aryl group in R may be an aryl group having a heterocycle containing an oxygen atom, a nitrogen atom, a sulfur atom, or the like. Examples of the skeleton of the aryl group having a heterocycle include pyrrole, furan, thiophene, indole, benzofuran, and benzothiophene. ２０４ and R ２０５ The alkyl group and cycloalkyl group are preferably a linear alkyl group having 1 to 10 carbon atoms or a branched alkyl group having 3 to 10 carbon atoms (e.g., methyl, ethyl, propyl, butyl, or pentyl), or a cycloalkyl group having 3 to 10 carbon atoms (e.g., cyclopentyl, cyclohexyl, or norbornyl).

[0076] R ２０４ and R ２０５ The aryl group, alkyl group, and cycloalkyl group in R may each independently have a substituent. ２０４ and R ２０５ Examples of the substituent that the aryl group, alkyl group, and cycloalkyl group may have include an alkyl group (e.g., having 1 to 15 carbon atoms), a cycloalkyl group (e.g., having 3 to 15 carbon atoms), an aryl group (e.g., having 6 to 15 carbon atoms), an alkoxy group (e.g., having 1 to 15 carbon atoms), a halogen atom other than a fluorine atom, a hydroxyl group, and a phenylthio group. ２０４ and R ２０５ It is also preferred that the substituents independently form an acid-decomposable group by any combination of the substituents.

[0077] Below, Z １１ ＋ Specific examples of the organic cation represented by the formula (I) are shown below, but are not limited to these.

[0078]

[0079]

[0080] However, R in formula (b1-1) １１ -X １１ － does not represent an anion represented by any of the above formulas (i)-1 to (i)-3. That is, R in formula (b1-1) １１ -X １１ － is not an anion represented by the above formula (i)-1, is not an anion represented by the above formula (i)-2, and is not an anion represented by the above formula (i)-3.

[0081] R in formula (b1-1) １１ and Z １１ ＋ It is preferable that the compound does not contain a structure represented by the following formula (Am-1).

[0082]

[0083] In formula (Am-1), Q １ ~Q ３ each independently represents a hydrogen atom or an organic group. １ ~Q ３ At least two of these may be bonded to each other to form a ring.

[0084] Q in formula (Am-1) １ ~Q ３ each independently represents a hydrogen atom or an organic group. １ ~Q ３ The organic group represented by is not particularly limited, and examples thereof include an alkyl group, a cycloalkyl group, an alkenyl group, an alkynyl group, an aryl group, a heteroaryl group, an aralkyl group, an alkoxy group, an aryloxy group, a carboxyl group, an acyl group, an acyloxy group, a formyloxy group, an alkoxycarbonyl group, an alkylsulfoxy group, an arylsulfoxy group, an alkylsulfonyl group, an arylsulfonyl group, —OCO(OR ８) or -OCO(NR ９ R １０ ) is preferable. ８ , R ９ and R １０ each independently represents a hydrogen atom, an alkyl group, a cycloalkyl group, an alkenyl group, an alkynyl group, an aryl group, a heteroaryl group, or an aralkyl group.

[0085] Q １ ~Q ３ The alkyl group, cycloalkyl group, alkenyl group, alkynyl group, aryl group, heteroaryl group, aralkyl group, alkoxy group, aryloxy group, carboxyl group, acyloxy group, formyloxy group, alkoxycarbonyl group, alkylsulfoxy group, and arylsulfoxy group represented by may further have one or more substituents. For example, the alkyl group may be substituted with a hydroxy group. Furthermore, the hydrogen atom of the carboxyl group may be substituted with a substituent.

[0086] Q １ ~Q ３Each group represented by is described below. The number of carbon atoms in the alkyl group is not particularly limited, but may be, for example, 1 to 20, 1 to 10, or 1 to 6. The alkyl group may be either linear or branched. Examples of the alkyl group include a methyl group, an ethyl group, an n-propyl group, an i-propyl group, an n-butyl group, a t-butyl group, and an n-hexyl group. The same applies to the alkyl group portion in an alkoxy group, the alkyl group portion in an aralkyl group, the alkyl group portion in an alkoxycarbonyl group, the alkyl group portion in an alkylsulfonyl group, the alkyl group portion in an alkylsulfoxy group, the alkyl group portion in an acyl group when the acyl group is an alkylcarbonyl group, and the alkyl group portion in an acyloxy group when the acyloxy group is an alkylcarbonyloxy group. The cycloalkyl group may be 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. The number of carbon atoms in the cycloalkyl group is not particularly limited, but may be, for example, 5 to 20 or 5 to 15. The alkenyl group may be either linear or branched. The number of carbon atoms in the alkenyl group is not particularly limited, but may be, for example, 2 to 20, 2 to 10, or 2 to 6. The alkynyl group may be either linear or branched. The number of carbon atoms in the alkynyl group is not particularly limited, but may be, for example, 2 to 20, 2 to 10, or 2 to 6. The aryl group may be either monocyclic or polycyclic (e.g., 2 to 6 rings, etc.). The number of ring atoms in the aryl group is not particularly limited, but may be, for example, 6 to 20, 6 to 15, or 6 to 10. The aryl group is preferably a phenyl group, a naphthyl group, or an anthranyl group, and more preferably a phenyl group.The same applies to the aryl group portion of an aralkyl group, the aryl group portion of an aryloxy group, the aryl group portion of an arylsulfonyl group, the aryl group portion of an arylsulfoxy group, the aryl group portion when the acyl group is an arylcarbonyl group, and the aryl group portion when the acyloxy group is an arylcarbonyloxy group. The heteroaryl group may be either monocyclic or polycyclic (e.g., 2 to 6 rings). The number of heteroatoms contained in the heteroaryl group as ring members is not particularly limited, but may be, for example, 1 to 10. Examples of heteroatoms include nitrogen atoms, sulfur atoms, oxygen atoms, selenium atoms, tellurium atoms, phosphorus atoms, silicon atoms, and boron atoms. The number of ring members of the heteroaryl group is not particularly limited, but may be, for example, 5 to 15.

[0087] R ８ , R ９ and R １０ R each independently represents a hydrogen atom, an alkyl group, a cycloalkyl group, an alkenyl group, an alkynyl group, an aryl group, a heteroaryl group, or an aralkyl group. ８ , R ９ and R １０ The explanations, specific examples and preferred ranges of the alkyl group, cycloalkyl group, alkenyl group, alkynyl group, aryl group, heteroaryl group and aralkyl group represented by Q are respectively described above. １ ~Q ３ It is similar to that in

[0088] Q １ ~Q ３ may contain a cation or anion. １ ~Q ３ The atom or atomic group contained in may release an electron to become a cation, or may accept an electron to become an anion.

[0089] The structure represented by the following formula (XX-1) and the structure represented by the following formula (XX-2) do not fall under the structure represented by formula (Am-1).

[0090]

[0091] In formula (XX-1) and formula (XX-2), Q １ ~Q ４ each independently represents a hydrogen atom or an organic group. １ ~Q ４ At least two of these may be bonded to each other to form a ring. １ ~Q ３ The organic group represented by is as described above. ４ The organic group represented by Q is explained above. １ ~Q ３ It is similar to that in

[0092] L in formula (b1-2) １２ represents a single bond or a divalent linking group. １２ The divalent linking group represented by is not particularly limited, but examples thereof include —O—, —NR １ -, -S-, -SO-, -SO ２ -, an organic group (preferably a divalent organic group), and a group formed by combining two or more of these groups, and -O-, -CO-, -COO-, -OCOO-, -NR １ --, --CONR １ -, -S-, -SO-, -SO ２ -, an alkylene group, a cycloalkylene group, an alkenylene group, an arylene group, or a group formed by combining two or more of these groups is preferred. １ represents a hydrogen atom or an alkyl group. １２ The alkylene group represented by is not particularly limited, but is preferably an alkylene group having 1 to 8 carbon atoms, such as a methylene group, an ethylene group, a propylene group, a butylene group, a hexylene group, or an octylene group. １２The number of carbon atoms in the cycloalkylene group represented by is not particularly limited, but is preferably 3 to 20, and more preferably 4 to 15. The cycloalkylene group may be a monocyclic cycloalkylene group such as a cyclopentylene group or a cyclohexylene group, or a polycyclic cycloalkylene group such as a norbornylene group, a tetracyclodecanylene group, a tetracyclododecanylene group, or an adamantylene group. One of the methylene groups constituting the cycloalkane ring of the cycloalkylene group may be replaced with a heteroatom such as an oxygen atom, a group having a heteroatom such as a carbonyl group or an ester bond, or a vinylidene group. Furthermore, in the cycloalkylene group, one or more of the ethylene groups constituting the cycloalkane ring may be replaced with a vinylene group. １２ The alkenylene group represented by is not particularly limited, but is preferably, for example, an alkenylene group having 2 to 8 carbon atoms. １２ The arylene group represented by is not particularly limited, but examples thereof include arylene groups having 6 to 20 carbon atoms, and preferably arylene groups having 6 to 15 carbon atoms. The arylene group is preferably a phenylene group or a naphthylene group, and particularly preferably a phenylene group. １ When represents an alkyl group, examples of the alkyl group include alkyl groups having 20 or less carbon atoms, such as a methyl group, an ethyl group, a propyl group, an isopropyl group, an n-butyl group, a sec-butyl group, a hexyl group, a 2-ethylhexyl group, an octyl group, and a dodecyl group, and alkyl groups having 8 or less carbon atoms are preferred.

[0093] X in formula (b1-2) １２ － Ha-O － , -COO － , -SO ３ － or -SO ２ N － Y １２ (R １１２ ) ｈ Represents R １１２ represents an alkyl group, a cycloalkyl group, or an aryl group. １２ -CO-, -SO-, -SO ２ - or a single bond. h represents 0 or 1. When h represents 0, R１１２ does not exist, and Y １２ Is L １２ or Z １２ ＋ When h is 1, R １１２ Is L １２ or Z １２ ＋ may be bonded to R １１２ The number of carbon atoms in the alkyl group represented by is not particularly limited, but may be, for example, 1 to 20, 1 to 10, or 1 to 6. The alkyl group may be either linear or branched. Examples of the alkyl group include a methyl group, an ethyl group, an n-propyl group, an i-propyl group, an n-butyl group, a t-butyl group, and an n-hexyl group. R １１２ The cycloalkyl group represented by may be a monocyclic cycloalkyl group such as a cyclopentyl group or a cyclohexyl group, or may be a polycyclic cycloalkyl group such as a norbornyl group, a tetracyclodecanyl group, a tetracyclododecanyl group, or an adamantyl group. The number of carbon atoms in the cycloalkyl group is not particularly limited, but may be, for example, 5 to 20 or 5 to 15. １１２ The aryl group represented by may be either a monocyclic or polycyclic (for example, 2 to 6 rings). The number of ring atoms of the aryl group is not particularly limited, but may be, for example, 6 to 20, 6 to 15, or 6 to 10. The aryl group is preferably a phenyl group, a naphthyl group, or an anthryl group, and more preferably a phenyl group. X １２ － is -COO － , -SO ３ － or -SO ２ N － Y １２ (R １１２ ) ｈ Preferably, -COO － or -SO ３ － It is more preferable that:

[0094] Z in formula (b1-2) １２ ＋ represents an organic cationic group. An organic cationic group is an organic group having a cation. Z１２ ＋ The organic cation group represented by is not particularly limited, but Z in the above formula (b1-1) １１ ＋ It is preferable that the group is a group obtained by removing one arbitrary hydrogen atom from an organic cation represented by the formula:

[0095] The onium salt (B-1) is preferably at least one selected from the group consisting of onium salts represented by any one of the following formulas (b1-2a) to (b1-2e) and onium salts represented by the above formula (b1-2).

[0096]

[0097] In formula (b1-2a), R ２１ａ ~R ２１ｅ each independently represents a hydrogen atom or an organic group. ２１ｃ and R ２１ｄ At least one selected from the group consisting of a cyano group, a nitro group, a group represented by the following formula (2A) and a group represented by the following formula (2B), R ２１ａ and R ２１ｂ does not represent a group selected from the group consisting of a cyano group, a nitro group, a group represented by the following formula (2A), and a group represented by the following formula (2B). ２１ represents a single bond or a divalent linking group. ２１ represents an integer of 1 to 4. ２１ When R represents an integer of 2 or more, a plurality of R ２１ｃ may be the same or different, and multiple R ２１ｄ may be the same or different. ２１ａ , R ２１ｂ , R ２１ｃ , R ２１ｄ and L ２１ At least two selected from the group consisting of may be bonded to form a ring. １１ ＋ represents an organic cation.

[0098]

[0099] In formula (2A), Y ２１ａ and Y ２２ａ are each independently —O— or —NR３２ａ - represents. ３２ａ represents a hydrogen atom or an alkyl group. ４２ａ represents an alkyl group, a cycloalkyl group, or an aryl group. ２１ａ and r ２１ａ Each independently represents 0 or 1. ２１ａ and r ２１ａ and do not both represent 0. ２１ａ represents 1 or 2. * represents a bonding position. In formula (2B), Y ２１ｂ and Y ２２ｂ are each independently —O— or —NR ３２ｂ - represents. ３２ｂ represents a hydrogen atom or an alkyl group. ４２ｂ represents an alkyl group, a cycloalkyl group, or an aryl group. ２１ｂ and r ２１ｂ Each independently represents 0 or 1. * represents a bonding position. In formula (b1-2b), R ２２ａ represents an organic group other than a halogen atom, a hydroxy group, or a carboxyl group. １２ represents an aromatic group. １２ represents an integer of 0 or more. １２ When R represents an integer of 2 or more, a plurality of R ２２ａ may be the same or different. １１ ＋ represents an organic cation. １３ represents an aromatic group. ２３ａ represents a halogen atom or an organic group. １３ and q １３ Each independently represents an integer of 0 or more. １３ When R represents an integer of 2 or more, a plurality of R ２３ａ may be the same or different, provided that p １３ and q １３ and do not both represent 0. １３ If represents 1, then p １３ represents an integer of 1 or more. １１ ＋ represents an organic cation. ２４ａ represents an organic group. ２４ａWhen has an aromatic ring, —COO － The carbon atom of Z is not directly bonded to the aromatic ring. １１ ＋ represents an organic cation. ２５ａ -CO-, -SO-, -SO ２ - or a single bond. ２５ａ and R ２５ｂ R each independently represents an alkyl group, a cycloalkyl group, or an aryl group. ２５ａ and R ２５ｂ may be bonded to form a ring. １１ ＋ represents an organic cation.

[0100] R in formula (b1-2a) ２１ｃ and R ２１ｄ each independently represents a hydrogen atom or an organic group. ２１ｃ and R ２１ｄ At least one selected from the group consisting of represents a cyano group, a nitro group, a group represented by formula (2A), and a group represented by formula (2B). ２１ｃ and R ２１ｄ The organic group represented by is not particularly limited, but is preferably an alkyl group, a cycloalkyl group, an alkenyl group, an alkynyl group, an aryl group, a heteroaryl group, an alkoxy group, an aryloxy group, a cyano group, a group represented by formula (2A), or a group represented by formula (2B).

[0101] R ２１ｃ and R ２１ｄ The alkyl group, cycloalkyl group, alkenyl group, alkynyl group, aryl group, heteroaryl group, alkoxy group, and aryloxy group represented by may further have one or more substituents. For example, the alkyl group may be substituted with a hydroxy group.

[0102] R ２１ｃ and R ２１ｄEach group represented by is described below. The number of carbon atoms in the alkyl group is not particularly limited, but may be, for example, 1 to 20, 1 to 10, or 1 to 6. The alkyl group may be either linear or branched. Examples of the alkyl group include a methyl group, an ethyl group, an n-propyl group, an i-propyl group, an n-butyl group, a t-butyl group, and an n-hexyl group. The same applies to the alkyl group portion in the alkoxy group. The cycloalkyl group may be 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. The number of carbon atoms in the cycloalkyl group is not particularly limited, but may be, for example, 5 to 20 or 5 to 15. The alkenyl group may be either linear or branched. The number of carbon atoms in the alkenyl group is not particularly limited, but may be, for example, 2 to 20, 2 to 10, or 2 to 6. The alkynyl group may be either linear or branched. The number of carbon atoms in the alkynyl group is not particularly limited, but may be, for example, 2 to 20, 2 to 10, or 2 to 6. The aryl group may be either monocyclic or polycyclic (e.g., 2 to 6 rings). The number of ring atoms in the aryl group is not particularly limited, but may be, for example, 6 to 20, 6 to 15, or 6 to 10. The aryl group is preferably a phenyl group, a naphthyl group, or an anthryl group, and more preferably a phenyl group. The same applies to the aryl group moiety in the aryloxy group. The heteroaryl group may be either monocyclic or polycyclic (e.g., 2 to 6 rings). The number of heteroatoms contained in the heteroaryl group as ring atoms is not particularly limited, but may be, for example, 1 to 10. Examples of heteroatoms include a nitrogen atom, a sulfur atom, an oxygen atom, a selenium atom, a tellurium atom, a phosphorus atom, a silicon atom, and a boron atom. The number of ring atoms in the heteroaryl group is not particularly limited, but may be, for example, 5 to 15.

[0103] n in formula (b1-2a) ２１ represents an integer of 1 to 4. ２１When R represents an integer of 2 or more, a plurality of R ２１ｃ may be the same or different, and multiple R ２１ｄ may be the same or different. ２１ａ , R ２１ｂ , R ２１ｃ , R ２１ｄ and L ２１ At least two selected from the group consisting of may be bonded to form a ring. ２１ Preferably, R represents 1 or 2. ２１ａ , R ２１ｂ , R ２１ｃ , R ２１ｄ and L ２１ The ring formed by bonding at least two selected from the group consisting of is not particularly limited, but a cycloalkane ring is preferred. The cycloalkane ring may be a monocyclic cycloalkane ring or a polycyclic cycloalkane ring. The cycloalkane ring is preferably a monocyclic or polycyclic cycloalkane ring having 5 to 20 ring carbon atoms. In the cycloalkane ring, one or more of the methylene groups constituting the ring may be replaced with a heteroatom such as an oxygen atom, a group having a heteroatom such as a carbonyl group, or a vinylidene group. Furthermore, one or more of the ethylene groups constituting the cycloalkane ring may be replaced with a vinylene group.

[0104] Y in formula (2A) ２１ａ and Y ２２ａ are each independently —O— or —NR ３２ａ - represents. ３２ａ represents a hydrogen atom or an alkyl group. ３２ａ The number of carbon atoms in the alkyl group represented by is not particularly limited, but may be, for example, 1 to 20, 1 to 10, or 1 to 6. The alkyl group may be either linear or branched. Examples of the alkyl group include a methyl group, an ethyl group, an n-propyl group, an i-propyl group, an n-butyl group, a t-butyl group, and an n-hexyl group. Y ２１ａ and Y ２２ａ Preferably represents —O—.

[0105] R in formula (2A) ４２ａrepresents an alkyl group, a cycloalkyl group, or an aryl group, and preferably represents an alkyl group or a cycloalkyl group. ４２ａ The alkyl group represented by R may be linear or branched, and is preferably an alkyl group having 1 to 12 carbon atoms, more preferably an alkyl group having 1 to 6 carbon atoms, and even more preferably an alkyl group having 1 to 3 carbon atoms. ４２ａ Examples of the alkyl group represented by the formula (I) include a methyl group, an ethyl group, an n-propyl group, an isopropyl group, an n-butyl group, an isobutyl group, a sec-butyl group, and a t-butyl group. The alkyl group may further have a substituent. ４２ａ The cycloalkyl group represented by R may be monocyclic or polycyclic, and is preferably a cycloalkyl group having 3 to 20 carbon atoms, more preferably a cycloalkyl group having 4 to 15 carbon atoms, and even more preferably a cycloalkyl group having 5 to 10 carbon atoms. ４２ａ Examples of the cycloalkyl group represented by the formula (I) include a cyclopentyl group, a 1-methylcyclopentyl group, a cyclohexyl group, an adamantyl group, a 1-ethyladamantyl group, a norbornyl group, a tetracyclodecanyl group, and a tetracyclododecanyl group. One of the methylene groups constituting the cycloalkane ring of the cycloalkyl group may be replaced with a heteroatom such as an oxygen atom, a group having a heteroatom such as a carbonyl group or an ester bond, or a vinylidene group. Furthermore, in the cycloalkyl group, one or more of the ethylene groups constituting the cycloalkane ring may be replaced with a vinylene group. The cycloalkyl group may further have a substituent. R ４２ａ The aryl group represented by the formula (I) is preferably an aryl group having 6 to 20 carbon atoms, more preferably an aryl group having 6 to 15 carbon atoms, still more preferably an aryl group having 6 to 10 carbon atoms, particularly preferably a phenyl group or a naphthyl group, and most preferably a phenyl group. The aryl group may further have a substituent.

[0106] p in formula (2A) ２１ａ and r ２１ａ Each independently represents 0 or 1. ２１ａ and r ２１ａ and do not both represent 0. ２１ａ and r ２１ａIt is preferred that one of q represents 1 and the other represents 0. ２１ａ represents 1 or 2, and preferably represents 1.

[0107] Y in formula (2B) ２１ｂ and Y ２２ｂ are each independently —O— or —NR ３２ｂ - represents. ３２ｂ represents a hydrogen atom or an alkyl group. ３２ｂ The number of carbon atoms in the alkyl group represented by is not particularly limited, but may be, for example, 1 to 20, 1 to 10, or 1 to 6. The alkyl group may be either linear or branched. Examples of the alkyl group include a methyl group, an ethyl group, an n-propyl group, an i-propyl group, an n-butyl group, a t-butyl group, and an n-hexyl group. Y ２１ｂ and Y ２２ｂ Preferably represents —O—.

[0108] R in formula (2B) ４２ｂ represents an alkyl group, a cycloalkyl group, or an aryl group, and preferably represents an alkyl group or a cycloalkyl group. ４２ｂ The alkyl group represented by R may be linear or branched, and is preferably an alkyl group having 1 to 12 carbon atoms, more preferably an alkyl group having 1 to 6 carbon atoms, and even more preferably an alkyl group having 1 to 3 carbon atoms. ４２ｂ Examples of the alkyl group represented by R include a methyl group, an ethyl group, an n-propyl group, an isopropyl group, an n-butyl group, an isobutyl group, a sec-butyl group, and a t-butyl group. ４２ｂ The cycloalkyl group represented by R may be monocyclic or polycyclic, and is preferably a cycloalkyl group having 3 to 20 carbon atoms, more preferably a cycloalkyl group having 4 to 15 carbon atoms, and even more preferably a cycloalkyl group having 5 to 10 carbon atoms. ４２ｂExamples of the cycloalkyl group represented by the formula (I) include a cyclopentyl group, a 1-methylcyclopentyl group, a cyclohexyl group, an adamantyl group, a 1-ethyladamantyl group, a norbornyl group, a tetracyclodecanyl group, and a tetracyclododecanyl group. One of the methylene groups constituting the cycloalkane ring of the cycloalkyl group may be replaced with a heteroatom such as an oxygen atom, a group having a heteroatom such as a carbonyl group or an ester bond, or a vinylidene group. Furthermore, in the cycloalkyl group, one or more of the ethylene groups constituting the cycloalkane ring may be replaced with a vinylene group. R ４２ｂ The aryl group represented by the formula (I) is preferably an aryl group having 6 to 20 carbon atoms, more preferably an aryl group having 6 to 15 carbon atoms, still more preferably an aryl group having 6 to 10 carbon atoms, particularly preferably a phenyl group or a naphthyl group, and most preferably a phenyl group.

[0109] p in formula (2B) ２１ｂ and r ２１ｂ Each independently represents 0 or 1. ２１ｂ and r ２１ｂ It is preferable that at least one of p represents 0, ２１ｂ and r ２１ｂ More preferably, represents 0.

[0110] R in formula (b1-2a) ２１ａ and R ２１ｂ each independently represents a hydrogen atom or an organic group. ２１ａ and R ２１ｂ does not represent a group selected from the group consisting of a cyano group, a nitro group, a group represented by formula (2A), and a group represented by formula (2B). The group represented by formula (2A) and the group represented by formula (2B) are as described above. ２１ａ and R ２１ｂ The organic group represented by is not particularly limited as long as it is other than a cyano group, a group represented by formula (2A) and a group represented by formula (2B), but is preferably an alkyl group, a cycloalkyl group, an alkenyl group, an alkynyl group, an aryl group, a heteroaryl group, an alkoxy group or an aryloxy group.

[0111] R ２１ａ and R ２１ｂThe explanation, specific examples and preferred ranges of the alkyl group, cycloalkyl group, alkenyl group, alkynyl group, aryl group, heteroaryl group, alkoxy group and aryloxy group represented by R ２１ｃ and R ２１ｄ It is the same as in

[0112] R in formula (b1-2a) ２１ｅ represents a hydrogen atom or an organic group. ２１ｅ The organic group represented by is not particularly limited, but is preferably an alkyl group, a cycloalkyl group, an alkenyl group, an alkynyl group, an aryl group, a heteroaryl group, an alkoxy group, an aryloxy group, a cyano group, a group represented by formula (2A) or a group represented by formula (2B). The explanation, specific examples and preferred ranges of these groups are described in the above section on R ２１ｃ and R ２１ｄ It is the same as in

[0113] L in formula (b1-2a) ２１ represents a single bond or a divalent linking group; ２１ The divalent linking group represented by is not particularly limited, but examples thereof include —O—, —NR １ -, -S-, -SO-, -SO ２ -, an organic group (preferably a divalent organic group), and a group formed by combining two or more of these groups, and -O-, -CO-, -COO-, -OCOO-, -NR １ --, --CONR １ -, -S-, -SO-, -SO ２ -, an alkylene group, a cycloalkylene group, an alkenylene group, an arylene group, or a group formed by combining two or more of these groups is preferred. １ represents a hydrogen atom or an alkyl group. ２１ The alkylene group represented by is not particularly limited, but is preferably an alkylene group having 1 to 8 carbon atoms, such as a methylene group, an ethylene group, a propylene group, a butylene group, a hexylene group, or an octylene group. ２１The number of carbon atoms in the cycloalkylene group represented by is not particularly limited, but is preferably 3 to 20, and more preferably 4 to 15. The cycloalkylene group may be a monocyclic cycloalkylene group such as a cyclopentylene group or a cyclohexylene group, or a polycyclic cycloalkylene group such as a norbornylene group, a tetracyclodecanylene group, a tetracyclododecanylene group, or an adamantylene group. One of the methylene groups constituting the cycloalkane ring of the cycloalkylene group may be replaced with a heteroatom such as an oxygen atom, a group having a heteroatom such as a carbonyl group or an ester bond, or a vinylidene group. Furthermore, in the cycloalkylene group, one or more of the ethylene groups constituting the cycloalkane ring may be replaced with a vinylene group. ２１ The alkenylene group represented by is not particularly limited, but is preferably, for example, an alkenylene group having 2 to 8 carbon atoms. ２１ The arylene group represented by is not particularly limited, but examples thereof include arylene groups having 6 to 20 carbon atoms, and preferably arylene groups having 6 to 15 carbon atoms. The arylene group is preferably a phenylene group or a naphthylene group, and particularly preferably a phenylene group. １ When represents an alkyl group, examples of the alkyl group include alkyl groups having 20 or less carbon atoms, such as a methyl group, an ethyl group, a propyl group, an isopropyl group, an n-butyl group, a sec-butyl group, a hexyl group, a 2-ethylhexyl group, an octyl group, and a dodecyl group, and alkyl groups having 8 or less carbon atoms are preferred.

[0114] Z in formula (b1-2a) １１ ＋ represents an organic cation. １１ ＋ The explanation, specific examples and preferred ranges for Z in the above formula (b1-1) are １１ ＋ It is the same as in

[0115] R in formula (b1-2b) ２２ａ represents an organic group other than a halogen atom, a hydroxy group, or a carboxyl group. ２２ａThe halogen atom represented by R is preferably a chlorine atom, a bromine atom, or an iodine atom. ２２ａ The organic group represented by is not particularly limited as long as it is a carboxyl group, but is preferably an alkyl group, a cycloalkyl group, an alkenyl group, an alkynyl group, an aryl group, a heteroaryl group, an alkoxy group, or an aryloxy group. ２２ａ The alkyl group, cycloalkyl group, alkenyl group, alkynyl group, aryl group, heteroaryl group, alkoxy group, and aryloxy group represented by may further have one or more substituents. For example, the alkyl group may be substituted with a hydroxy group.

[0116] R ２２ａEach group represented by is described below. The number of carbon atoms in the alkyl group is not particularly limited, but may be, for example, 1 to 20, 1 to 10, or 1 to 6. The alkyl group may be either linear or branched. Examples of the alkyl group include a methyl group, an ethyl group, an n-propyl group, an i-propyl group, an n-butyl group, a t-butyl group, and an n-hexyl group. The same applies to the alkyl group portion in the alkoxy group. The cycloalkyl group may be 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. The number of carbon atoms in the cycloalkyl group is not particularly limited, but may be, for example, 5 to 20 or 5 to 15. The alkenyl group may be either linear or branched. The number of carbon atoms in the alkenyl group is not particularly limited, but may be, for example, 2 to 20, 2 to 10, or 2 to 6. The alkynyl group may be either linear or branched. The number of carbon atoms in the alkynyl group is not particularly limited, but may be, for example, 2 to 20, 2 to 10, or 2 to 6. The aryl group may be either monocyclic or polycyclic (e.g., 2 to 6 rings). The number of ring atoms in the aryl group is not particularly limited, but may be, for example, 6 to 20, 6 to 15, or 6 to 10. The aryl group is preferably a phenyl group, a naphthyl group, or an anthryl group, and more preferably a phenyl group. The same applies to the aryl group moiety in the aryloxy group. The heteroaryl group may be either monocyclic or polycyclic (e.g., 2 to 6 rings). The number of heteroatoms contained in the heteroaryl group as ring atoms is not particularly limited, but may be, for example, 1 to 10. Examples of heteroatoms include a nitrogen atom, a sulfur atom, an oxygen atom, a selenium atom, a tellurium atom, a phosphorus atom, a silicon atom, and a boron atom. The number of ring atoms in the heteroaryl group is not particularly limited, but may be, for example, 5 to 15.

[0117] Ar in formula (b1-2b) １２ is an aromatic group (more specifically, p１２ + monovalent aromatic group). １２ The aromatic group represented by Ar may be an aromatic hydrocarbon group or an aromatic heterocyclic group. １２ When the aromatic group represented by is an aromatic hydrocarbon group, the aromatic hydrocarbon group may be either monocyclic or polycyclic. The number of carbon atoms in the aromatic hydrocarbon group is not particularly limited, but is preferably 6 to 20, more preferably 6 to 14. The aromatic hydrocarbon group may be any p-condensed ring compound having a structure in which an aromatic hydrocarbon (e.g., benzene, naphthalene, etc.) is condensed with a cycloalkane (e.g., cyclopentane, cyclohexane, etc.). １２ +It may also be a group obtained by removing one hydrogen atom.

[0118] Ar １２ When the aromatic group represented by is an aromatic heterocyclic group, the aromatic heterocyclic group may be either monocyclic or polycyclic. The aromatic heterocyclic group preferably contains at least one heteroatom selected from the group consisting of a nitrogen atom, an oxygen atom, and a sulfur atom as a ring member. The number of carbon atoms in the aromatic heterocyclic group is not particularly limited, but for example, 2 to 18 is preferred, 3 to 12 is more preferred, and 4 to 12 is even more preferred. The number of ring atoms in the aromatic heterocyclic group is not particularly limited, but for example, 5 to 20 is preferred, and 6 to 15 is more preferred. Examples of the aromatic heterocyclic group include five-membered ring aromatic heterocyclic compounds such as pyrrole, imidazole, pyrazole, oxazole, isoxazole, thiazole, isothiazole, triazole, thiophene, and furan, and six-membered ring aromatic heterocyclic compounds such as pyridine, pyrazine, pyrimidine, pyridazine, triazine, thiazine, and oxazine. １２The aromatic heterocyclic group may be any p-substituted fused ring compound (e.g., indole, quinoline, isoquinoline, etc.) having a structure in which the five-membered aromatic heterocyclic compound or the six-membered aromatic heterocyclic compound is fused with at least one selected from the group consisting of the five-membered aromatic heterocyclic compound, the six-membered aromatic heterocyclic compound, aromatic hydrocarbons (e.g., benzene, naphthalene, etc.), cycloalkanes (e.g., cyclopentane, cyclohexane, etc.), and non-aromatic heterocyclic compounds (e.g., five-membered non-aromatic heterocyclic compounds such as pyrrolidine, pyrroline, 2-oxazolidone, tetrahydrofuran, tetrahydrothiophene, and six-membered non-aromatic heterocyclic compounds such as morpholine, piperidine, piperazine, tetrahydropyran, etc.). １２ +It may also be a group obtained by removing one hydrogen atom.

[0119] p in formula (b1-2b) １２ represents an integer of 0 or more. １２ When R represents an integer of 2 or more, a plurality of R ２２ａ may be the same or different. １２ Preferably, represents 1 or 2.

[0120] Z in formula (b1-2b) １１ ＋ represents an organic cation. １１ ＋ The explanation, specific examples and preferred ranges for Z in the above formula (b1-1) are １１ ＋ It is the same as in

[0121] Ar in formula (b1-2c) １３ is an aromatic group (more specifically, p １３ +q １３ + monovalent aromatic group). １３ The aromatic group represented by Ar may be an aromatic hydrocarbon group or an aromatic heterocyclic group. １３When the aromatic group represented by is an aromatic hydrocarbon group, the aromatic hydrocarbon group may be either monocyclic or polycyclic. The number of carbon atoms in the aromatic hydrocarbon group is not particularly limited, but is preferably 6 to 20, more preferably 6 to 14. The aromatic hydrocarbon group may be any p-condensed ring compound having a structure in which an aromatic hydrocarbon (e.g., benzene, naphthalene, etc.) is condensed with a cycloalkane (e.g., cyclopentane, cyclohexane, etc.). １３ +q １３ +It may also be a group obtained by removing one hydrogen atom.

[0122] Ar １３ When the aromatic group represented by is an aromatic heterocyclic group, the aromatic heterocyclic group may be either monocyclic or polycyclic. The aromatic heterocyclic group preferably contains at least one heteroatom selected from the group consisting of a nitrogen atom, an oxygen atom, and a sulfur atom as a ring member. The number of carbon atoms in the aromatic heterocyclic group is not particularly limited, but for example, 2 to 18 is preferred, 3 to 12 is more preferred, and 4 to 12 is even more preferred. The number of ring atoms in the aromatic heterocyclic group is not particularly limited, but for example, 5 to 20 is preferred, and 6 to 15 is more preferred. Examples of the aromatic heterocyclic group include five-membered ring aromatic heterocyclic compounds such as pyrrole, imidazole, pyrazole, oxazole, isoxazole, thiazole, isothiazole, triazole, thiophene, and furan, and six-membered ring aromatic heterocyclic compounds such as pyridine, pyrazine, pyrimidine, pyridazine, triazine, thiazine, and oxazine. １３ +q １３The aromatic heterocyclic group may be any p-substituted fused ring compound (e.g., indole, quinoline, isoquinoline, etc.) having a structure in which the five-membered aromatic heterocyclic compound or the six-membered aromatic heterocyclic compound is fused with at least one selected from the group consisting of the five-membered aromatic heterocyclic compound, the six-membered aromatic heterocyclic compound, aromatic hydrocarbons (e.g., benzene, naphthalene, etc.), cycloalkanes (e.g., cyclopentane, cyclohexane, etc.), and non-aromatic heterocyclic compounds (e.g., five-membered non-aromatic heterocyclic compounds such as pyrrolidine, pyrroline, 2-oxazolidone, tetrahydrofuran, tetrahydrothiophene, and six-membered non-aromatic heterocyclic compounds such as morpholine, piperidine, piperazine, tetrahydropyran, etc.). １３ +q １３ +It may also be a group obtained by removing one hydrogen atom.

[0123] R in formula (b1-2c) ２３ａ represents a halogen atom or an organic group. ２３ａ The halogen atom represented by R is preferably a chlorine atom, a bromine atom, or an iodine atom. ２３ａ The organic group represented by is not particularly limited, but is preferably a carboxyl group, an alkyl group, a cycloalkyl group, an alkenyl group, an alkynyl group, an aryl group, a heteroaryl group, an alkoxy group, or an aryloxy group. ２３ａ The carboxyl group, alkyl group, cycloalkyl group, alkenyl group, alkynyl group, aryl group, heteroaryl group, alkoxy group, and aryloxy group represented by may further have one or more substituents. For example, the alkyl group may be substituted with a hydroxy group.

[0124] R ２３ａEach group represented by is described below. The number of carbon atoms in the alkyl group is not particularly limited, but may be, for example, 1 to 20, 1 to 10, or 1 to 6. The alkyl group may be either linear or branched. Examples of the alkyl group include a methyl group, an ethyl group, an n-propyl group, an i-propyl group, an n-butyl group, a t-butyl group, and an n-hexyl group. The same applies to the alkyl group portion in the alkoxy group. The cycloalkyl group may be 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. The number of carbon atoms in the cycloalkyl group is not particularly limited, but may be, for example, 5 to 20 or 5 to 15. The alkenyl group may be either linear or branched. The number of carbon atoms in the alkenyl group is not particularly limited, but may be, for example, 2 to 20, 2 to 10, or 2 to 6. The alkynyl group may be either linear or branched. The number of carbon atoms in the alkynyl group is not particularly limited, but may be, for example, 2 to 20, 2 to 10, or 2 to 6. The aryl group may be either monocyclic or polycyclic (e.g., 2 to 6 rings). The number of ring atoms in the aryl group is not particularly limited, but may be, for example, 6 to 20, 6 to 15, or 6 to 10. The aryl group is preferably a phenyl group, a naphthyl group, or an anthryl group, and more preferably a phenyl group. The same applies to the aryl group moiety in the aryloxy group. The heteroaryl group may be either monocyclic or polycyclic (e.g., 2 to 6 rings). The number of heteroatoms contained in the heteroaryl group as ring atoms is not particularly limited, but may be, for example, 1 to 10. Examples of heteroatoms include a nitrogen atom, a sulfur atom, an oxygen atom, a selenium atom, a tellurium atom, a phosphorus atom, a silicon atom, and a boron atom. The number of ring atoms in the heteroaryl group is not particularly limited, but may be, for example, 5 to 15.

[0125] p in formula (b1-2c) １３ and q １３Each independently represents an integer of 0 or more. １３ When R represents an integer of 2 or more, a plurality of R ２３ａ may be the same or different, provided that p １３ and q １３ and do not both represent 0. １３ If represents 1, then p １３ represents an integer of 1 or more. １３ Preferably, q represents 1 or 2. １３ Preferably, represents 1 or 2.

[0126] Z in formula (b1-2c) １１ ＋ represents an organic cation. １１ ＋ The explanation, specific examples and preferred ranges for Z in the above formula (b1-1) are １１ ＋ It is the same as in

[0127] R in formula (b1-2d) ２４ａ represents an organic group. ２４ａ The organic group represented by is not particularly limited, but is preferably an alkyl group, a cycloalkyl group, an alkenyl group, an alkynyl group, or an alkoxy group. ２４ａ The alkyl group, cycloalkyl group, alkenyl group, alkynyl group and alkoxy group represented by may further have one or more substituents. For example, the alkyl group may be substituted with a hydroxy group.

[0128] R ２４ａEach group represented by is described below. The number of carbon atoms in the alkyl group is not particularly limited, but may be, for example, 1 to 20, 1 to 10, or 1 to 6. The alkyl group may be either linear or branched. Examples of the alkyl group include a methyl group, an ethyl group, an n-propyl group, an i-propyl group, an n-butyl group, a t-butyl group, and an n-hexyl group. The same applies to the alkyl group portion in the alkoxy group. The cycloalkyl group may be 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. The number of carbon atoms in the cycloalkyl group is not particularly limited, but may be, for example, 5 to 20 or 5 to 15. The alkenyl group may be either linear or branched. The number of carbon atoms in the alkenyl group is not particularly limited, but may be, for example, 2 to 20, 2 to 10, or 2 to 6. The alkynyl group may be either linear or branched. The number of carbon atoms in the alkynyl group is not particularly limited, but may be, for example, 2 to 20, 2 to 10, or 2 to 6.

[0129] R ２４ａ The organic group represented by may have an aromatic ring, but R ２４ａ When has an aromatic ring, —COO － The carbon atom of the formula (I) is not directly bonded to the aromatic ring.

[0130] Z in formula (b1-2d) １１ ＋ represents an organic cation. １１ ＋ The explanation, specific examples and preferred ranges for Z in the above formula (b1-1) are １１ ＋ It is the same as in

[0131] Y in formula (b1-2e) ２５ａ -CO-, -SO-, -SO ２ - or a single bond.

[0132] R in formula (b1-2e) ２５ａ and R ２５ｂ R each independently represents an alkyl group, a cycloalkyl group, or an aryl group. ２５ａ and R ２５ｂ may be bonded to form a ring. ２５ａ and R ２５ｂ The number of carbon atoms in the alkyl group represented by is not particularly limited, but may be, for example, 1 to 20, 1 to 10, or 1 to 6. The alkyl group may be either linear or branched. Examples of the alkyl group include a methyl group, an ethyl group, an n-propyl group, an i-propyl group, an n-butyl group, a t-butyl group, and an n-hexyl group. R ２５ａ and R ２５ｂ The cycloalkyl group represented by may be a monocyclic cycloalkyl group such as a cyclopentyl group or a cyclohexyl group, or may be a polycyclic cycloalkyl group such as a norbornyl group, a tetracyclodecanyl group, a tetracyclododecanyl group, or an adamantyl group. The number of carbon atoms in the cycloalkyl group is not particularly limited, but may be, for example, 5 to 20 or 5 to 15. ２５ａ and R ２５ｂ The aryl group represented by may be either a monocyclic or polycyclic (for example, 2 to 6 rings). The number of ring atoms of the aryl group is not particularly limited, but may be, for example, 6 to 20, 6 to 15, or 6 to 10. The aryl group is preferably a phenyl group, a naphthyl group, or an anthryl group, and more preferably a phenyl group.

[0133] Z in formula (b1-2e) １１ ＋ represents an organic cation. １１ ＋ The explanation, specific examples and preferred ranges for Z in the above formula (b1-1) are １１ ＋ It is the same as in

[0134] (Molecular Weight of Onium Salt (B-1)) The onium salt (B-1) may be in the form of a low molecular weight compound or a polymer. Furthermore, the low molecular weight compound and the polymer may be used in combination. When the onium salt (B-1) is in the form of a low molecular weight compound, the molecular weight of the onium salt (B-1) is not particularly limited, but is preferably 5,000 or less, more preferably 3,000 or less, and particularly preferably 2,000 or less. Furthermore, the molecular weight of the onium salt (B-1) is preferably 100 or more, more preferably 200 or more. When the onium salt (B-1) is in the form of a polymer, it may be incorporated into a part of the resin (A) whose polarity increases under the action of an acid, or it may be incorporated into a resin different from the resin (A) whose polarity increases under the action of an acid. When the onium salt (B-1) is incorporated into a part of the resin (A), the resin (A) also serves as the onium salt (B-1). Therefore, the composition of the present invention may or may not contain a separate onium salt (B-1). The onium salt (B-1) is preferably in the form of a low molecular weight compound.

[0135] (Fluorine Content of Onium Salt (B-1)) The onium salt (B-1) does not contain fluorine atoms, or if it contains fluorine atoms, the content of fluorine atoms (fluorine content) is 3 mass% or less relative to all atoms contained in the onium salt (B-1). If the onium salt (B-1) contains fluorine atoms, the content of fluorine atoms is preferably 2 mass% or less, and more preferably 1 mass% or less, relative to all atoms contained in the onium salt (B-1). It is particularly preferable that the onium salt (B-1) does not contain fluorine atoms (i.e., the fluorine content is 0 mass%). The fluorine content of the onium salt (B-1) represents the mass ratio of fluorine atoms to all atoms in the onium salt (B-1). The fluorine content (mass%) can be calculated using the following formula (1): 100×19×F Ｂ１ / MW Ｂ１ (1) In formula (1), F Ｂ１ is the number of fluorine atoms contained in the onium salt (B-1), MW Ｂ１represents the molecular weight of the onium salt (B-1). In this specification, the fluorine content of the onium salt (B-1) refers to the value determined by the above method, but when the fluorine content cannot be determined by the above method, the value used is calculated by an analytical method such as elemental analysis of a film obtained by evaporating the solvent component of the composition.

[0136] (Content of Onium Salt (B-1)) The content of the onium salt (B-1) in the composition of the present invention is not particularly limited, but is preferably 0.1 to 30.0 mass%, more preferably 0.5 to 20.0 mass%, and even more preferably 1.0 to 15.0 mass%, relative to the total solids content of the composition of the present invention. The onium salt (B-1) may be used alone, or two or more types may be used. When two or more types are used, it is preferable that the total content thereof is within the above-mentioned suitable content range.

[0137] The onium salt (B-1) can be synthesized by referring to a known method.

[0138] Specific examples of the onium salt (B-1) include, but are not limited to, B1-1 to B1-18 used in the examples described below.

[0139] [Onium Salt (B-2)] The onium salt (B-2) contained in the composition of the present invention will be explained below. The onium salt (B-2) is an onium salt represented by the following formula (b2-1).

[0140]

[0141] In formula (b2-1), R ２ａ represents an electron-withdrawing group. ２ｂ and R ２ｃ R each independently represents a hydrogen atom or an organic group. ２ａ , R ２ｂ and R ２ｃ At least two selected from the group consisting of may be bonded to form a ring. ２ｂ and R ２ｃ and do not both represent hydrogen atoms. ２ ＋ represents an organic cation.

[0142] The onium salt (B-2) is a compound different from the above-mentioned onium salt (B-1).

[0143] R in formula (b2-1) ２ａ represents an electron-withdrawing group. The electron-withdrawing group is preferably a group having a Hammett's substituent constant σp value of greater than 0, more preferably a group having a σp value of 0.1 or more, and even more preferably a group having a σp value of 0.2 or more. For Hammett's substituent constant σp value, see, for example, Chemical Reviews, 1991, Vol. 91, pp. 165-195. Examples of the electron-withdrawing group include halogen atoms (e.g., fluorine atom, chlorine atom, bromine atom, iodine atom), halogenated alkyl groups (e.g., -CF ３ group), formyl group, carboxyl group, cyano group, nitro group, dicyanomethyl group (-(CH)CN ２ ), and a group represented by the following formula (1A). ２ａ represents preferably a cyano group, a nitro group, a dicyanomethyl group, or a group represented by the following formula (1A), and more preferably represents a cyano group, a dicyanomethyl group, or a group represented by the following formula (1A).

[0144]

[0145] In formula (1A), Y １ and Y ３ are each independently —O— or —NR ３ - represents. ３ represents a hydrogen atom or an alkyl group. ２ is -C(=O)- or -SO ２ - represents. ４ represents an alkyl group, a cycloalkyl group, or an aryl group. ３ and R ４ At least two selected from the group consisting of may be bonded to form a ring. p and r each independently represent 0 or 1. q represents 1 or 2. * represents the bonding position.

[0146] Y in formula (1A) １ and Y ３ are each independently —O— or —NR ３ - represents. ３represents a hydrogen atom or an alkyl group. ３ The number of carbon atoms in the alkyl group represented by is not particularly limited, but may be, for example, 1 to 20, 1 to 10, or 1 to 6. The alkyl group may be either linear or branched. Examples of the alkyl group include a methyl group, an ethyl group, an n-propyl group, an i-propyl group, an n-butyl group, a t-butyl group, and an n-hexyl group. Y １ and Y ３ Preferably represents —O—.

[0147] R in formula (1A) ４ represents an alkyl group, a cycloalkyl group, or an aryl group, and preferably represents an alkyl group or a cycloalkyl group. ４ The alkyl group represented by R may be linear or branched, and is preferably an alkyl group having 1 to 12 carbon atoms, more preferably an alkyl group having 1 to 6 carbon atoms, and even more preferably an alkyl group having 1 to 3 carbon atoms. ４ Examples of the alkyl group represented by the formula (I) include a methyl group, an ethyl group, an n-propyl group, an isopropyl group, an n-butyl group, an isobutyl group, a sec-butyl group, and a t-butyl group. The alkyl group may further have a substituent. ４ The cycloalkyl group represented by R may be monocyclic or polycyclic, and is preferably a cycloalkyl group having 3 to 20 carbon atoms, more preferably a cycloalkyl group having 4 to 15 carbon atoms, and even more preferably a cycloalkyl group having 5 to 10 carbon atoms. ４ Examples of the cycloalkyl group represented by the formula (I) include a cyclopentyl group, a 1-methylcyclopentyl group, a cyclohexyl group, an adamantyl group, a 1-ethyladamantyl group, a norbornyl group, a tetracyclodecanyl group, and a tetracyclododecanyl group. One of the methylene groups constituting the cycloalkane ring of the cycloalkyl group may be replaced with a heteroatom such as an oxygen atom, a group having a heteroatom such as a carbonyl group or an ester bond, or a vinylidene group. Furthermore, in the cycloalkyl group, one or more of the ethylene groups constituting the cycloalkane ring may be replaced with a vinylene group. The cycloalkyl group may further have a substituent. R ４The aryl group represented by the formula (I) is preferably an aryl group having 6 to 20 carbon atoms, more preferably an aryl group having 6 to 15 carbon atoms, still more preferably an aryl group having 6 to 10 carbon atoms, particularly preferably a phenyl group or a naphthyl group, and most preferably a phenyl group. The aryl group may further have a substituent.

[0148] Y in formula (1A) ２ is -C(=O)- or -SO ２ In formula (1A), p and r each independently represent 0 or 1. In formula (1A), q represents 1 or 2, and preferably represents 1.

[0149] The group represented by formula (1A) is —O(C═O)R ４ , -(C=O)OR ４ , -O(SO ２ ) R ４ , -(SO ２ ) OR ４ or -(SO ２ ) R ４ is preferably —O(C═O)R ４ , -(C=O)OR ４ or -(SO ２ ) R ４ It is more preferable that:

[0150] R in formula (b2-1) ２ｂ and R ２ｃ each independently represents a hydrogen atom or an organic group. ２ｂ and R ２ｃ and R do not both represent hydrogen atoms. ２ｂ and R ２ｃ The organic group represented by is not particularly limited, but is preferably an alkyl group, a cycloalkyl group, an alkenyl group, an alkynyl group, an aryl group, a heteroaryl group, an alkoxy group, an aryloxy group, a cyano group, a dicyanomethyl group, or a group represented by formula (1A).

[0151] R ２ｂ and R ２ｃThe alkyl group, cycloalkyl group, alkenyl group, alkynyl group, aryl group, heteroaryl group, alkoxy group, and aryloxy group represented by may further have one or more substituents. For example, the alkyl group may be substituted with a hydroxy group.

[0152] R ２ｂ and R ２ｃEach group represented by is described below. The number of carbon atoms in the alkyl group is not particularly limited, but may be, for example, 1 to 20, 1 to 10, or 1 to 6. The alkyl group may be either linear or branched. Examples of the alkyl group include a methyl group, an ethyl group, an n-propyl group, an i-propyl group, an n-butyl group, a t-butyl group, and an n-hexyl group. The same applies to the alkyl group portion in the alkoxy group. The cycloalkyl group may be 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. The number of carbon atoms in the cycloalkyl group is not particularly limited, but may be, for example, 5 to 20 or 5 to 15. The alkenyl group may be either linear or branched. The number of carbon atoms in the alkenyl group is not particularly limited, but may be, for example, 2 to 20, 2 to 10, or 2 to 6. The alkynyl group may be either linear or branched. The number of carbon atoms in the alkynyl group is not particularly limited, but may be, for example, 2 to 20, 2 to 10, or 2 to 6. The aryl group may be either monocyclic or polycyclic (e.g., 2 to 6 rings). The number of ring atoms in the aryl group is not particularly limited, but may be, for example, 6 to 20, 6 to 15, or 6 to 10. The aryl group is preferably a phenyl group, a naphthyl group, or an anthryl group, and more preferably a phenyl group. The same applies to the aryl group moiety in the aryloxy group. The heteroaryl group may be either monocyclic or polycyclic (e.g., 2 to 6 rings). The number of heteroatoms contained in the heteroaryl group as ring atoms is not particularly limited, but may be, for example, 1 to 10. Examples of heteroatoms include a nitrogen atom, a sulfur atom, an oxygen atom, a selenium atom, a tellurium atom, a phosphorus atom, a silicon atom, and a boron atom. The number of ring atoms in the heteroaryl group is not particularly limited, but may be, for example, 5 to 15.

[0153] R ２ａ , R ２ｂ and R ２ｃAt least two selected from the group consisting of may be bonded to form a ring. ２ａ , R ２ｂ and R ２ｃ The ring formed by bonding at least two selected from the group consisting of is not particularly limited, but a cycloalkane ring is preferred. The cycloalkane ring may be a monocyclic cycloalkane ring or a polycyclic cycloalkane ring. The cycloalkane ring is preferably a monocyclic or polycyclic cycloalkane ring having 5 to 20 ring carbon atoms. In the cycloalkane ring, one or more of the methylene groups constituting the ring may be replaced with a heteroatom such as an oxygen atom, a group having a heteroatom such as a sulfonyl group or a carbonyl group, or a vinylidene group. Furthermore, one or more of the ethylene groups constituting the cycloalkane ring may be replaced with a vinylene group.

[0154] Z in formula (b2-1) ２ ＋ represents an organic cation. ２ ＋ The explanation, specific examples and preferred ranges for Z in the above formula (b1-1) are １１ ＋ It is the same as in

[0155] (Molecular Weight of Onium Salt (B-2)) The onium salt (B-2) may be in the form of a low molecular weight compound or a polymer. Furthermore, the low molecular weight compound and the polymer may be used in combination. When the onium salt (B-2) is in the form of a low molecular weight compound, the molecular weight of the onium salt (B-2) is not particularly limited, but is preferably 5,000 or less, more preferably 3,000 or less, and particularly preferably 2,000 or less. Furthermore, the molecular weight of the onium salt (B-2) is preferably 100 or more, more preferably 200 or more. When the onium salt (B-2) is in the form of a polymer, it may be incorporated into a part of the resin (A) whose polarity increases under the action of an acid, or it may be incorporated into a resin different from the resin (A) whose polarity increases under the action of an acid. When the onium salt (B-2) is incorporated into a part of the resin (A), the resin (A) also serves as the onium salt (B-2). Therefore, the composition of the present invention may or may not contain a separate onium salt (B-2). The onium salt (B-2) is preferably in the form of a low molecular weight compound.

[0156] (Fluorine Content of Onium Salt (B-2)) The onium salt (B-2) does not contain fluorine atoms, or if it contains fluorine atoms, the content of fluorine atoms (fluorine content) is 3 mass% or less relative to all atoms contained in the onium salt (B-2). If the onium salt (B-2) contains fluorine atoms, the content of fluorine atoms is preferably 2 mass% or less, and more preferably 1 mass% or less, relative to all atoms contained in the onium salt (B-2). It is particularly preferable that the onium salt (B-2) does not contain fluorine atoms (i.e., the fluorine content is 0 mass%). The fluorine content of the onium salt (B-2) represents the mass ratio of fluorine atoms to all atoms in the onium salt (B-2). The fluorine content (mass%) can be calculated using the following formula (2): 100×19×F Ｂ２ / MW Ｂ２ (2) In formula (2), F Ｂ２ is the number of fluorine atoms contained in the onium salt (B-2), MW Ｂ２represents the molecular weight of the onium salt (B-2). In this specification, the fluorine content of the onium salt (B-2) refers to the value determined by the above method, but when the fluorine content cannot be determined by the above method, the value used is calculated by an analytical method such as elemental analysis of a film obtained by evaporating the solvent component of the composition.

[0157] (Content of Onium Salt (B-2)) The content of the onium salt (B-2) in the composition of the present invention is not particularly limited, but is preferably 1.0 to 50.0 mass% relative to the total solids content of the composition of the present invention, more preferably 3.0 to 45.0 mass%, and even more preferably 5.0 to 40.0 mass%. The onium salt (B-2) may be used alone, or two or more types may be used. When two or more types are used, it is preferable that the total content thereof is within the above-mentioned suitable content range.

[0158] The onium salt (B-2) can be synthesized, for example, by the method described in the Examples.

[0159] Specific examples of the onium salt (B-2) include, but are not limited to, B2-1 to B2-30 used in the examples described later and the compounds shown below.

[0160]

[0161] (Acid (AC Ｂ１ ) and acid (AC Ｂ２ The onium salt (B-1) is converted into an acid (AC) by irradiation with actinic rays or radiation. Ｂ１ ) is generated. Ｂ１ ) pKa ("pKa Ｂ１ ") is an acid (AC) generated by the onium salt (B-2) upon irradiation with actinic rays or radiation. Ｂ２ ) pKa ("pKa Ｂ２ It is also called "pKa.") It is 1.0 or more larger than Ｂ１ -pKa Ｂ２(also referred to as "ΔpKa") is 1.0 or more, preferably 1.3 or more, more preferably 1.5 or more, and even more preferably 2.0 or more. ΔpKa is preferably 15.0 or less, more preferably 13.0 or less, and even more preferably 10.0 or less. pKa Ｂ１ is preferably −2.0 to 12.0, more preferably −1.0 to 11.0, and even more preferably 0.0 to 10.0. Ｂ２ is preferably −8.0 to 1.0, more preferably −7.0 to 0.5, and even more preferably −6.0 to 0.0. Ｂ１ and pKa Ｂ２ The specific method for determining is as follows: The anion moiety of each onium salt is protonated (for example, the anion moiety is SO ３ － If so, SO ３ H), calculations are performed using software (Advanced Chemistry Development (ACD / Labs) Software V8.14 for Solaris (1994-2007 ACD / Labs)). If the pKa cannot be calculated by this method, the value obtained by Gaussian 16 based on DFT (density functional theory) is adopted. When multiple onium salts are contained as onium salt (B-1), the calculated value of the onium salt species with the lowest pKa is used to calculate ΔpKa (pKa Ｂ１ -pKa Ｂ２ When the onium salt (B-2) contains a plurality of onium salts, the calculated value of the onium salt species with the highest pKa is used to calculate ΔpKa (pKa Ｂ１ -pKa Ｂ２ ) is calculated.

[0162] The mass ratio (B-2) / (B-1) of the content of the onium salt (B-2) to the content of the onium salt (B-1) contained in the composition of the present invention is preferably 1 to 25, more preferably 1 to 20, and even more preferably 1 to 15.

[0163] [Resin (A) whose polarity increases under the action of acid] The composition of the present invention contains a resin (A) (also simply referred to as "resin (A)") whose polarity increases under the action of acid. The resin (A) preferably contains a group that decomposes under the action of acid and increases its polarity (also referred to as an "acid-decomposable group"), and contains a repeating unit having an acid-decomposable group. When the resin (A) has an acid-decomposable group, in a pattern formation method using the composition of the present invention, typically, a positive pattern is preferably formed when an alkaline developer is used as the developer, and a negative pattern is preferably formed when an organic developer is used as the developer. As the repeating unit having an acid-decomposable group, in addition to a repeating unit having an acid-decomposable group, a repeating unit having an acid-decomposable group containing an unsaturated bond is preferred.

[0164] (Repeating unit having an acid-decomposable group) The acid-decomposable group refers to a group that decomposes under the action of an acid to generate a polar group. The acid-decomposable group preferably has a structure in which a polar group is protected with a group (leaving group) that is released under the action of an acid. In other words, the resin (A) has a repeating unit that decomposes under the action of an acid to generate a polar group. The polarity of a resin having this repeating unit increases under the action of an acid, increasing its solubility in an alkaline developer and decreasing its solubility in an organic solvent. The polar group is preferably an alkali-soluble group, such as a carboxyl group, a phenolic hydroxyl group, a fluorinated alcohol group, a sulfonic acid group, a phosphate group, a sulfonamide group, a sulfonylimide group, a (alkylsulfonyl) (alkylcarbonyl) methylene group, a (alkylsulfonyl) (alkylcarbonyl) imide group, a bis(alkylcarbonyl) methylene group, a bis(alkylcarbonyl) imide group, a bis(alkylsulfonyl) methylene group, a bis(alkylsulfonyl) imide group, a tris(alkylcarbonyl) methylene group, and an acidic group such as a tris(alkylsulfonyl) methylene group, and an alcoholic hydroxyl group. Among these, the polar group is preferably a carboxyl group, a phenolic hydroxyl group, a fluorinated alcohol group (preferably a hexafluoroisopropanol group), or a sulfonic acid group.

[0165] Examples of the group that is eliminated by the action of an acid include groups represented by formulae (Y1) to (Y4). Formula (Y1): —C(Rx １ ) (Rx ２ ) (Rx ３ ) Formula (Y2): -C(=O)OC(Rx １ ) (Rx ２ ) (Rx ３ ) Formula (Y3): -C(R ３６ ) (R ３７ ) (OR ３８ ) Formula (Y4): -C(Rn)(H)(Ar)

[0166] In formula (Y1) and formula (Y2), Rx １ ~Rx ３ Rx each independently represents 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). １ ~Rx ３ When all of Rx are alkyl groups (linear or branched), １ ~Rx ３ At least two of Rx are preferably methyl groups. １ ~Rx ３ each independently preferably represents a linear or branched alkyl group, and Rx １ ~Rx ３ More preferably, Rx each independently represents a linear alkyl group. １ ~Rx ３ may be bonded to form a monocyclic or polycyclic ring. １ ~Rx ３ The alkyl group of Rx is preferably an alkyl group having 1 to 5 carbon atoms, such as a methyl group, an ethyl group, an n-propyl group, an isopropyl group, an n-butyl group, an isobutyl group, or a t-butyl group. １ ~Rx ３ The cycloalkyl group of Rx 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. １ ~Rx３ The aryl group in Rx is preferably an aryl group having 6 to 10 carbon atoms, and examples thereof include a phenyl group, a naphthyl group, and an anthryl group. １ ~Rx ３ The alkenyl group of Rx is preferably a vinyl group. １ ~Rx ３ The ring formed by combining the two is preferably a cycloalkyl group. １ ~Rx ３ The cycloalkyl group formed by bonding the two 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. １ ~Rx ３ In the cycloalkyl group formed by bonding these two, one of the methylene groups constituting the ring may be replaced with a heteroatom such as an oxygen atom, a group containing a heteroatom such as a carbonyl group, or a vinylidene group. In these cycloalkyl groups, one or more of the ethylene groups constituting the cycloalkane ring may be replaced with a vinylene group. The group represented by formula (Y1) or formula (Y2) can be, for example, Rx １ is a methyl group or an ethyl group, and Rx ２ and Rx ３ and Rx are preferably bonded to form the above-mentioned cycloalkyl group. When the actinic ray-sensitive or radiation-sensitive resin composition is, for example, a resist composition for EUV exposure, １ ~Rx ３ an alkyl group, a cycloalkyl group, an alkenyl group, an aryl group, and Rx １ ~Rx ３ The ring formed by bonding these two groups preferably further has a fluorine atom or an iodine atom as a substituent.

[0167] In formula (Y3), R ３６ ~R ３８ R each independently represents a hydrogen atom or a monovalent organic group. ３７ and R ３８may be bonded to each other to form a ring. Examples of the monovalent organic group include an alkyl group, a cycloalkyl group, an aryl group, an aralkyl group, and an alkenyl group. ３６ is also preferably a hydrogen atom. The alkyl group, cycloalkyl group, aryl group, and aralkyl group may contain a heteroatom such as an oxygen atom and / or a group containing a heteroatom such as a carbonyl group. For example, in the alkyl group, cycloalkyl group, aryl group, and aralkyl group, one or more methylene groups may be replaced with a heteroatom such as an oxygen atom and / or a group containing a heteroatom such as a carbonyl group. R ３８ may bond with another substituent on the main chain of the repeating unit to form a ring. ３８ The group formed by bonding together R and another substituent on the main chain of the repeating unit is preferably an alkylene group such as a methylene group. ３６ ~R ３８ and a monovalent organic group represented by R ３７ and R ３８ It is also preferable that the ring formed by bonding these groups together further has a fluorine atom or an iodine atom as a substituent.

[0168] Formula (Y3) is preferably a group represented by the following formula (Y3-1).

[0169]

[0170] Here, L １ and L ２Each independently represents 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 that may contain a heteroatom, a cycloalkyl group that may contain a heteroatom, an aryl group that may contain a heteroatom, an amino group, an ammonium group, a mercapto group, a cyano group, an aldehyde group, or a group combining these (for example, a group combining an alkyl group and a cycloalkyl group). In the alkyl group and the cycloalkyl group, for example, one of the methylene groups may be replaced with a heteroatom such as an oxygen atom, or a group containing a heteroatom such as a carbonyl group. In addition, L １ and L ２ It is preferred that one of Q, M, and L is a hydrogen atom, and the other is an alkyl group, a cycloalkyl group, an aryl group, or a group in which an alkylene group and an aryl group are combined. １ At least two of the groups may be bonded to form a ring (preferably a 5- or 6-membered ring). ２ is preferably a secondary or tertiary alkyl group, and more preferably a tertiary alkyl group. Examples of secondary alkyl groups include an isopropyl group, a cyclohexyl group, and a norbornyl group, and examples of tertiary alkyl groups include a tert-butyl group and an adamantane group. In these embodiments, the Tg (glass transition temperature) and activation energy are increased, thereby ensuring film strength and suppressing fogging.

[0171] When the actinic ray-sensitive or radiation-sensitive resin composition is, for example, a resist composition for EUV exposure, L １ and L ２It is also preferable that the alkyl group, cycloalkyl group, aryl group, and combinations thereof represented by the formula (I) further have a fluorine atom or an iodine atom as a substituent. The alkyl group, cycloalkyl group, aryl group, and aralkyl group preferably contain a heteroatom such as an oxygen atom in addition to the fluorine atom and iodine atom. Specifically, in the alkyl group, cycloalkyl group, aryl group, and aralkyl group, for example, one of the methylene groups may be replaced with a heteroatom such as an oxygen atom, or a group containing a heteroatom such as a carbonyl group. When the actinic ray-sensitive or radiation-sensitive resin composition is, for example, a resist composition for EUV exposure, in the alkyl group which may contain a heteroatom, cycloalkyl group which may contain a heteroatom, aryl group which may contain a heteroatom, amino group, ammonium group, mercapto group, cyano group, aldehyde group, and combinations thereof represented by Q, the heteroatom is preferably selected from the group consisting of a fluorine atom, an iodine atom, and an oxygen atom.

[0172] 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 be bonded to each other to form a non-aromatic ring. Ar is preferably an aryl group. When the actinic ray-sensitive or radiation-sensitive resin composition is, for example, a resist composition for EUV exposure, it is also preferable that the aromatic ring group represented by Ar and the alkyl group, cycloalkyl group, and aryl group represented by Rn have a fluorine atom or an iodine atom as a substituent.

[0173] In terms of excellent acid decomposition properties of the repeating unit, when a non-aromatic ring is directly bonded to the polar group (or a residue thereof) in the leaving group protecting the polar group, it is also preferable that the ring atom in the non-aromatic ring adjacent to the ring atom directly bonded to the polar group (or a residue thereof) does not have a halogen atom such as a fluorine atom as a substituent.

[0174] The group that is eliminated by the action of an acid may also be a 2-cyclopentenyl group having a substituent (such as an alkyl group), such as a 3-methyl-2-cyclopentenyl group, or a cyclohexyl group having a substituent (such as an alkyl group), such as a 1,1,4,4-tetramethylcyclohexyl group.

[0175] The repeating unit having an acid-decomposable group is also preferably a repeating unit represented by formula (A).

[0176]

[0177] L １ represents a divalent linking group which may have a fluorine atom or an iodine atom, R １ 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; R ２ represents a leaving group which is eliminated by the action of an acid and may have a fluorine atom or an iodine atom. １ , R １ , and R ２ At least one of L has a fluorine atom or an iodine atom. １ Examples of the divalent linking group which may have a fluorine atom or an iodine atom and is represented by the formula: ２ -, hydrocarbon groups which may have a fluorine atom or an iodine atom (for example, alkylene groups, cycloalkylene groups, alkenylene groups, arylene groups, etc.), and linking groups in which a plurality of these groups are linked together. １As the alkylene group, -CO-, an arylene group, or -arylene group-alkylene group having a fluorine atom or an iodine atom- is preferred, and -CO- or -arylene group-alkylene group having a fluorine atom or an iodine atom- is more preferred. As the arylene group, a phenylene group is preferred. The alkylene group may be linear or branched. The number of carbon atoms in the alkylene group is not particularly limited, but is preferably 1 to 10, and more preferably 1 to 3. The total number of fluorine atoms and iodine atoms contained in the 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.

[0178] R １ The alkyl group represented by R may be linear or branched. The number of carbon atoms in the alkyl group is not particularly limited, but is preferably 1 to 10, and more preferably 1 to 3. １ The total number of fluorine atoms and iodine atoms contained in the alkyl group having a fluorine atom or an iodine atom, represented by the formula (I), is not particularly limited, but is preferably 1 or more, more preferably 1 to 5, and even more preferably 1 to 3. １ The alkyl group represented by the formula (I) may contain a heteroatom other than a halogen atom, such as an oxygen atom.

[0179] R ２ Examples of the leaving group represented by the formulae (Y1) to (Y4) above, which may have a fluorine atom or an iodine atom, include leaving groups represented by the formulae (Y1) to (Y4) above, which have a fluorine atom or an iodine atom.

[0180] The repeating unit having an acid-decomposable group is also preferably a repeating unit represented by formula (AI).

[0181]

[0182] In formula (AI), Xa １ represents a hydrogen atom or an alkyl group which may have a substituent. T represents a single bond or a divalent linking group. Rx １ ~Rx ３each independently represents 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). １ ~Rx ３ When all of Rx are alkyl groups (linear or branched), １ ~Rx ３ Preferably, at least two of Rx are methyl groups. １ ~Rx ３ may be bonded to form a monocyclic or polycyclic ring (such as a monocyclic or polycyclic cycloalkyl group).

[0183] Xa １ Examples of the alkyl group represented by the formula (I) which may have a substituent include a methyl group or —CH ２ -R １１ Examples of the group include a group represented by R １１ represents a halogen atom (such as a fluorine atom), a hydroxyl group, or a monovalent organic group. １１ Examples of the monovalent organic group represented by the formula (I) include an alkyl group having 5 or less carbon atoms which may be substituted with a halogen atom, an acyl group having 5 or less carbon atoms which may be substituted with a halogen atom, and an alkoxy group having 5 or less carbon atoms which may be substituted with a halogen atom, and an alkyl group having 3 or less carbon atoms is preferred, and a methyl group is more preferred. １ is preferably a hydrogen atom, a methyl group, a trifluoromethyl group, or a hydroxymethyl group.

[0184] Examples of the divalent linking group for T include an alkylene group, an aromatic ring group, a -COO-Rt- group, and a -O-Rt- group. In the formula, Rt represents an alkylene group or a cycloalkylene group. T is preferably a single bond or a -COO-Rt- group. When T represents a -COO-Rt- group, Rt is preferably an alkylene group having 1 to 5 carbon atoms, and is preferably a -CH ２ - group, -(CH ２ ) ２ - group, or -(CH ２ ) ３ The - group is more preferred.

[0185] Rx １ ~Rx ３The alkyl group of Rx is preferably an alkyl group having 1 to 4 carbon atoms, such as a methyl group, an ethyl group, an n-propyl group, an isopropyl group, an n-butyl group, an isobutyl group, or a t-butyl group. １ ~Rx ３ The cycloalkyl group of Rx 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. １ ~Rx ３ The aryl group in Rx is preferably an aryl group having 6 to 10 carbon atoms, and examples thereof include a phenyl group, a naphthyl group, and an anthryl group. １ ~Rx ３ The alkenyl group of Rx is preferably a vinyl group. １ ~Rx ３ As the cycloalkyl group formed by combining the above two, a monocyclic cycloalkyl group such as a cyclopentyl group or a cyclohexyl group is preferred. Polycyclic cycloalkyl groups such as a norbornyl group, a tetracyclodecanyl group, a tetracyclododecanyl group, and an adamantyl group are also preferred. Among these, a monocyclic cycloalkyl group having 5 to 6 carbon atoms is preferred. Rx １ ~Rx ３ The cycloalkyl group formed by bonding these two may have, for example, one of the methylene groups constituting the ring replaced with 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 with a vinylene group. The repeating unit represented by formula (AI) can be, for example, Rx １ is a methyl group or an ethyl group, and Rx ２ and Rx ３ and are preferably bonded to form the above-mentioned cycloalkyl group.

[0186] When each of the above groups has a substituent, examples of the substituent include an alkyl group (having 1 to 4 carbon atoms), a halogen atom, a hydroxyl group, an alkoxy group (having 1 to 4 carbon atoms), a carboxyl group, and an alkoxycarbonyl group (having 2 to 6 carbon atoms). The number of carbon atoms in the substituent is preferably 8 or less.

[0187] The repeating unit represented by formula (AI) may be an acid-decomposable (meth)acrylic acid tertiary alkyl ester repeating unit (Xa １ represents a hydrogen atom or a methyl group, and T represents a single bond).

[0188] Specific examples of the repeating unit having an acid-decomposable group are shown below, but the invention is not limited thereto. １ is H, CH ３ , C.F. ３ , or CH ２ Rxa and Rxb each independently represent a linear or branched alkyl group having 1 to 5 carbon atoms.

[0189]

[0190] The resin (A) may have a repeating unit having an acid-decomposable group containing an unsaturated bond as a repeating unit having an acid-decomposable group. As the repeating unit having an acid-decomposable group containing an unsaturated bond, a repeating unit represented by formula (B) is preferred.

[0191]

[0192] In formula (B), Xb represents a hydrogen atom, a halogen atom, or an alkyl group which may have a substituent. L represents a single bond or a divalent linking group which may have a substituent. Ry １ ~Ry ３ each 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, provided that Ry １ ~Ry ３ At least one of R represents an alkenyl group, an alkynyl group, a monocyclic or polycyclic cycloalkenyl group, or a monocyclic or polycyclic aryl group.１ ~Ry ３ may be bonded to form a monocyclic or polycyclic ring (such as a monocyclic or polycyclic cycloalkyl group or cycloalkenyl group).

[0193] The alkyl group represented by Xb, which may have a substituent, is, for example, a methyl group or —CH ２ -R １１ Examples of the group include a group represented by R １１ represents a halogen atom (such as a fluorine atom), a hydroxyl group, or a monovalent organic group, and examples thereof include an alkyl group having 5 or less carbon atoms which may be substituted with a halogen atom, an acyl group having 5 or less carbon atoms which may be substituted with a halogen atom, and an alkoxy group having 5 or less carbon atoms which may be substituted with a halogen atom, preferably an alkyl group having 3 or less carbon atoms, and more preferably a methyl group. Xb is preferably a hydrogen atom, a fluorine atom, a methyl group, a trifluoromethyl group, or a hydroxymethyl group.

[0194] Examples of the divalent linking group for L include a -Rt- group, a -CO- group, a -COO-Rt- group, a -COO-Rt-CO- group, a -Rt-CO- group, and a -O-Rt- group. In the formula, Rt represents an alkylene group, a cycloalkylene group, or an aromatic ring group, and an aromatic ring group is preferable. L is preferably a -Rt- group, a -CO- group, a -COO-Rt-CO- group, or a -Rt-CO- group. Rt may have a substituent such as a halogen atom, a hydroxyl group, or an alkoxy group.

[0195] Ry １ ~Ry ３ The alkyl group of Ry is preferably an alkyl group having 1 to 4 carbon atoms, such as a methyl group, an ethyl group, an n-propyl group, an isopropyl group, an n-butyl group, an isobutyl group, or a t-butyl group. １ ~Ry ３ The cycloalkyl group of Ry 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. １ ~Ry ３The aryl group in Ry is preferably an aryl group having 6 to 10 carbon atoms, and examples thereof include a phenyl group, a naphthyl group, and an anthryl group. １ ~Ry ３ The alkenyl group in Ry is preferably a vinyl group. １ ~Ry ３ The alkynyl group in Ry is preferably an ethynyl group. １ ~Ry ３ The cycloalkenyl group of Ry is preferably a monocyclic cycloalkyl group such as a cyclopentyl group or a cyclohexyl group, which has a double bond in part thereof. １ ~Ry ３ The cycloalkyl group formed by combining the above two groups is preferably a monocyclic cycloalkyl group such as a cyclopentyl group or a cyclohexyl group, or a polycyclic cycloalkyl group such as a norbornyl group, a tetracyclodecanyl group, a tetracyclododecanyl group, or an adamantyl group. Among these, a monocyclic cycloalkyl group having 5 to 6 carbon atoms is more preferred. １ ~Ry ３ The cycloalkyl group or cycloalkenyl group formed by bonding two of the above is, for example, a group in which one of the methylene groups constituting the ring is substituted with a heteroatom such as an oxygen atom, a carbonyl group, or —SO ２ - group and -SO ３ The repeating unit represented by formula (B) may be substituted with a group containing a hetero atom such as a - group, a vinylidene group, or a combination thereof. In addition, in these cycloalkyl groups or cycloalkenyl groups, one or more ethylene groups constituting the cycloalkane ring or cycloalkene ring may be substituted with a vinylene group. １ is a methyl group, an ethyl group, a vinyl group, an allyl group, or an aryl group, and Ry ２ and Ry ３ and are bonded to form the above-mentioned cycloalkyl group or cycloalkenyl group.

[0196] When each of the above groups has a substituent, examples of the substituent include an alkyl group (having 1 to 4 carbon atoms), a halogen atom, a hydroxyl group, an alkoxy group (having 1 to 4 carbon atoms), a carboxyl group, and an alkoxycarbonyl group (having 2 to 6 carbon atoms). The number of carbon atoms in the substituent is preferably 8 or less.

[0197] The repeating unit represented by formula (B) is preferably an acid-decomposable (meth)acrylic acid tertiary ester repeating unit (a repeating unit in which Xb represents a hydrogen atom or a methyl group and L represents a —CO— group), an acid-decomposable hydroxystyrene tertiary alkyl ether repeating unit (a repeating unit in which Xb represents a hydrogen atom or a methyl group and L represents a phenyl group), or an acid-decomposable styrene carboxylic acid tertiary ester repeating unit (a repeating unit in which Xb represents a hydrogen atom or a methyl group and L represents a —Rt—CO— group (Rt is an aromatic group)).

[0198] The content of the repeating unit having an acid-decomposable group containing an unsaturated bond is preferably 15 mol% or more, more preferably 20 mol% or more, and even more preferably 30 mol% or more, relative to all repeating units in the resin (A). The upper limit is preferably 80 mol% or less, more preferably 70 mol% or less, and even more preferably 60 mol% or less, relative to all repeating units in the resin (A). Specific examples of repeating units having an acid-decomposable group containing an unsaturated bond include the repeating units described in paragraphs

[0067] to

[0071] of WO 2022 / 024928. The above descriptions are incorporated herein by reference.

[0199] The content of the repeating units having an acid-decomposable group is preferably 15 mol% or more, more preferably 20 mol% or more, and even more preferably 30 mol% or more, based on the total repeating units in the resin (A), and the upper limit thereof 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, based on the total repeating units in the resin (A).

[0200] Resin (A) may contain at least one repeating unit selected from the group consisting of Group A below, and / or at least one repeating unit selected from the group consisting of Group B below. Group A: A group consisting of the following repeating units (20) to (25). (20) A repeating unit having an acid group, as described below. (21) A repeating unit having neither an acid-decomposable group nor an acid group, and having a fluorine atom, a bromine atom, or an iodine atom, as described below. (22) A repeating unit having a lactone group, a sultone group, or a carbonate group, as described below. (23) A repeating unit having a photoacid-generating group, as described below. (24) A repeating unit represented by Formula (V-1) or Formula (V-2) as described below. (25) A repeating unit for reducing main chain mobility. The repeating units represented by Formulas (A) to (E) as described below correspond to (25) A repeating unit for reducing main chain mobility. Group B: A group consisting of the following repeating units (30) to (32). (30) A repeating unit having at least one group selected from a lactone group, a sultone group, a carbonate group, a hydroxyl group, a cyano group, and an alkali-soluble group, as described below. (31) A repeating unit having an alicyclic hydrocarbon structure and not exhibiting acid decomposability, as described below. (32) A repeating unit represented by formula (III), as described below, having neither a hydroxyl group nor a cyano group.

[0201] The resin (A) preferably has an acid group, and as described below, preferably contains a repeating unit having an acid group. The definition of the acid group will be explained later together with preferred embodiments of the repeating unit having an acid group. When the resin (A) has an acid group, the interaction between the resin (A) and the acid generated from the photoacid generator is more excellent. As a result, the diffusion of the acid is further suppressed, and the cross-sectional shape of the formed pattern can be more rectangular.

[0202] Resin (A) may have at least one repeating unit selected from the group consisting of Group A. When the actinic ray-sensitive or radiation-sensitive resin composition is used as an actinic ray-sensitive or radiation-sensitive resin composition for EUV exposure, resin (A) preferably has at least one repeating unit selected from the group consisting of Group A. Resin (A) may contain at least one of a fluorine atom and an iodine atom. When the actinic ray-sensitive or radiation-sensitive resin composition is used as an actinic ray-sensitive or radiation-sensitive resin composition for EUV exposure, resin (A) preferably contains at least one of a fluorine atom and an iodine atom. When 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 repeating units: a repeating unit containing a fluorine atom and a repeating unit containing an iodine atom. Resin (A) may have a repeating unit having an aromatic group. When the actinic ray-sensitive or radiation-sensitive resin composition is used as an actinic ray-sensitive or radiation-sensitive resin composition for EUV exposure, it is also preferable that the resin (A) has a repeating unit having an aromatic group. The resin (A) may have at least one repeating unit selected from the group consisting of Group B above. When the actinic ray-sensitive or radiation-sensitive resin composition is used as an actinic ray-sensitive 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 above. Note that when the actinic ray-sensitive or radiation-sensitive resin composition is used as an actinic ray-sensitive or radiation-sensitive resin composition for ArF, it is preferable that the resin (A) does not contain either a fluorine atom or a silicon atom. When the actinic ray-sensitive or radiation-sensitive resin composition is used as an actinic ray-sensitive or radiation-sensitive resin composition for ArF, it is preferable that the resin (A) does not have an aromatic group.

[0203] (Repeating Unit Having an Acid Group) The resin (A) may have a repeating unit having an acid group. The acid group preferably has a pKa of 13 or less. The acid dissociation constant of the acid group is preferably 13 or less, more preferably 3 to 13, and even more preferably 5 to 10. When the resin (A) has an acid group having a pKa of 13 or less, the content of the acid group in the resin (A) is not particularly limited, but is often 0.2 to 6.0 mmol / g. Of 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. When the content of the acid group is within the above range, development proceeds smoothly, and the formed pattern shape is excellent, and resolution is also excellent. Examples of the acid group that may be preferred include a carboxyl group, a phenolic hydroxyl group, a fluorinated alcohol group (preferably a hexafluoroisopropanol group), a sulfonic acid group, a sulfonamide group, and an isopropanol group. In the hexafluoroisopropanol group, one or more (preferably one to two) fluorine atoms may be substituted with a group other than a fluorine atom (such as an alkoxycarbonyl group). The acid group may be —C(CF ３ )(OH)—CF ２ In addition, one or more fluorine atoms are substituted with a group other than a fluorine atom to form -C(CF ３ )(OH)—CF ２ - may form a ring containing the repeating unit. The repeating unit having an acid group is preferably a repeating unit different from the repeating unit having a structure in which a polar group is protected by a group that is cleaved by the action of an acid described above, and the repeating unit having a lactone group, a sultone group, or a carbonate group described below. The repeating unit having an acid group may have a fluorine atom or an iodine atom. Specific examples of the repeating unit having an acid group include the repeating units described in paragraphs

[0088] to

[0089] and

[0103] to

[0110] of WO 2022 / 024928. The above descriptions are incorporated herein by reference.

[0204] The repeating unit having an acid group is preferably a repeating unit represented by the following formula (b1-1).

[0205]

[0206] In formula (b1-1), A ａ１ represents a hydrogen atom, an alkyl group, a cycloalkyl group, a halogen atom, or a cyano group. ２１ 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 R groups, they may be the same or different. ２１ When R ２１ is preferably a hydrogen atom. a represents an integer of 1 to 3. b represents an integer of 0 to (5-a).

[0207] When the resin (A) contains a repeating unit having an acid group, the content of the repeating unit having an acid group is preferably 10 mol% or more, more preferably 15 mol% or more, based on the total repeating units in the resin (A), and the upper limit thereof is preferably 70 mol% or less, more preferably 65 mol% or less, and even more preferably 60 mol% or less, based on the total repeating units in the resin (A).

[0208] (Repeating units having neither an acid-decomposable group nor an acid group, and having a fluorine atom, a bromine atom, or an iodine atom) In addition to the above-mentioned <repeating units having an acid-decomposable group> and <repeating units having an acid group>, the resin (A) may have a repeating unit having neither an acid-decomposable group nor an acid group, and having a fluorine atom, a bromine atom, or an iodine atom (hereinafter also referred to as unit X). The <repeating units having neither an acid-decomposable group nor an acid group, and having a fluorine atom, a bromine atom, or an iodine atom> referred to here is preferably different from other types of repeating units belonging to Group A, such as the <repeating units having a lactone group, a sultone group, or a carbonate group> and the <repeating units having a photoacid-generating group> described below.

[0209] The unit X is preferably a repeating unit represented by formula (C).

[0210]

[0211] L５ represents a single bond or an ester group. ９ represents a hydrogen atom or an alkyl group which may have a fluorine atom or an iodine atom. １０ represents a hydrogen atom, an alkyl group which may have a fluorine atom or an iodine atom, a cycloalkyl group which may have a fluorine atom or an iodine atom, an aryl group which may have a fluorine atom or an iodine atom, or a group combining these. Specific examples of repeating units having a fluorine atom or an iodine atom include the repeating units described in paragraphs

[0116] to

[0117] of WO 2022 / 024928. The above descriptions are incorporated herein by reference.

[0212] The content of the units X is preferably 0 mol% or more, more preferably 5 mol% or more, and even more preferably 10 mol% or more, based on all repeating units in the resin (A), and the upper limit thereof is preferably 50 mol% or less, more preferably 45 mol% or less, and even more preferably 40 mol% or less, based on all repeating units in the resin (A).

[0213] Among the repeating units of the resin (A), the total content of repeating units containing at least one of a fluorine atom, a bromine atom, and an iodine atom 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, based on the total repeating units of the resin (A). The upper limit is not particularly limited, but is, for example, 100 mol% or less, based on the total repeating units of the resin (A). Examples of repeating units containing at least one of a fluorine atom, a bromine atom, and an iodine atom include repeating units having a fluorine atom, a bromine atom, or an iodine atom and an acid-decomposable group, repeating units having a fluorine atom, a bromine atom, or an iodine atom and an acid group, and repeating units having a fluorine atom, a bromine atom, or an iodine atom.

[0214] (Repeating unit having a lactone group, a sultone group, or a carbonate group) The resin (A) may have a repeating unit (hereinafter also referred to as "unit Y") having at least one selected from the group consisting of a lactone group, a sultone group, and a carbonate group. It is also preferable that unit Y does not have a hydroxyl group or an acid group such as a hexafluoropropanol group.

[0215] 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- to 7-membered cyclic lactone structure or a 5- to 7-membered cyclic sultone structure. Among these, a 5- to 7-membered cyclic lactone structure to which another ring structure is fused in the form of a bicyclo or spiro structure, or a 5- to 7-membered cyclic sultone structure to which another ring structure is fused in the form of a bicyclo or spiro structure, is more preferred. Resin (A) preferably has a repeating unit having a lactone group, sultone group, or carbonate group obtained by removing one or more hydrogen atoms from a ring atom of a lactone structure represented by any one of formulas (LC1-1) to (LC1-22) below, a sultone structure represented by any one of formulas (SL1-1) to (SL1-3) below, or a cyclic carbonate ester structure represented by any one of formulas (CC1-1) to (CC1-2) below, and the lactone group, sultone group, or carbonate group may be directly bonded to the main chain. For example, ring atoms of a lactone group, a sultone group, or a carbonate group may constitute the main chain of the resin (A). The lactone group, the sultone group, and the carbonate group may have a substituent.

[0216] R in the following structural formula Ｌ represents a substituent. Ｌ If there are multiple R Ｌ may be the same or different. Ｌ Examples of R include an alkyl group having 1 to 8 carbon atoms, a cycloalkyl group having 4 to 10 carbon atoms, an alkoxy group having 1 to 8 carbon atoms, an alkoxycarbonyl group having 2 to 8 carbon atoms, a carboxyl group, a halogen atom, a cyano group, and an acid-decomposable group. e1 represents an integer of 0 to 4. When multiple e1s are present, the multiple e1s may be the same or different. When e1 is 2 or more, the multiple RＬ may be the same or different, and multiple R Ｌ They may be bonded to each other to form a ring.

[0217]

[0218] Examples of repeating units having a lactone group, a sultone group, or a carbonate group include repeating units represented by the following formula (AI-2).

[0219]

[0220] In formula (AI-2), Rb ０ represents a hydrogen atom, a halogen atom, or an alkyl group having 1 to 4 carbon atoms. ０ Preferred substituents that the alkyl group of Rb may have include a hydroxyl group and a halogen atom. ０ Examples of the halogen atom in Rb include a fluorine atom, a chlorine atom, a bromine atom, and an iodine atom. ０ is preferably a hydrogen atom or a methyl group. Ab represents a single bond, an alkylene group, a divalent linking group having a monocyclic or polycyclic alicyclic hydrocarbon structure, an ether group, an ester group, a carbonyl group, a carboxyl group, or a divalent linking group formed by combining these. Among these, Ab is preferably a single bond or -Ab １ -CO ２ A linking group represented by - is preferred. １ is a linear or branched alkylene group, or a monocyclic or polycyclic cycloalkylene group, and is preferably a methylene group, an ethylene group, a cyclohexylene group, an adamantylene group, or a norbornylene group. V is a group obtained by removing one hydrogen atom from a ring member atom of a lactone structure represented by any of formulas (LC1-1) to (LC1-22), a group obtained by removing one hydrogen atom from a ring member atom of a sultone structure represented by any of formulas (SL1-1) to (SL1-3), or a group obtained by removing one hydrogen atom from a ring member atom of a cyclic carbonate structure represented by any of formulas (CC1-1) to (CC1-2).

[0221] When optical isomers exist in the repeating unit having a lactone group or a sultone group, any optical isomer may be used. One optical isomer may be used alone, or multiple optical isomers may be used in combination. When one optical isomer is primarily used, its optical purity (ee) is preferably 90 or more, more preferably 95 or more.

[0222] The carbonate group is preferably a cyclic carbonate ester group. For repeating units having a cyclic carbonate ester group, see, for example, paragraphs

[0127] to

[0133] of WO 2022 / 024928. The above description is incorporated herein by reference.

[0223] When the resin (A) contains the unit Y, the content of the unit Y is preferably 1 mol% or more, more preferably 10 mol% or more, based on all repeating units in the resin (A), and the upper limit thereof 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, based on all repeating units in the resin (A).

[0224] (Repeating unit having a photoacid generating group) The resin (A) may have, as a repeating unit other than the above, a repeating unit having a group that generates an acid upon irradiation with actinic rays or radiation (also referred to as a "photoacid generating group"). Examples of the repeating unit having a photoacid generating group include a repeating unit represented by formula (4).

[0225]

[0226] R ４１ represents a hydrogen atom or a methyl group. ４１ represents a single bond or a divalent linking group. ４２ represents a divalent linking group. ４０represents a structural moiety that decomposes upon irradiation with actinic rays or radiation to generate an acid in a side chain. Specific examples of repeating units having a photoacid generating group include the repeating units described in

[0094] to

[0105] of JP 2014-041327 A, the repeating unit described in

[0094] of WO 2018 / 193954 A, and the repeating unit described in

[0138] of WO 2022 / 024928 A. The above descriptions are incorporated herein by reference.

[0227] Examples of the repeating unit represented by formula (4) include the repeating units described in paragraphs

[0094] to

[0105] of JP 2014-041327 A and the repeating unit described in paragraph

[0094] of WO 2018 / 193954 A.

[0228] When the resin (A) contains a repeating unit having a photoacid generating group, the content of the repeating unit having a photoacid generating group is preferably 1 mol% or more, more preferably 3 mol% or more, and particularly preferably 5 mol% or more, based on the total repeating units in the resin (A).Furthermore, the content of the repeating unit having a photoacid generating group is preferably 40 mol% or less, more preferably 30 mol% or less, and particularly preferably 20 mol% or less, based on the total repeating units in the resin (A).It is also preferable that the resin (A) does not contain a repeating unit having a photoacid generating group.

[0229] (Repeating unit represented by formula (V-1) or the following formula (V-2)) The resin (A) may have a repeating unit represented by the following formula (V-1) or the following formula (V-2). The repeating units represented by the following formula (V-1) and the following formula (V-2) are preferably repeating units different from the above-mentioned repeating units.

[0230]

[0231] In the formula, R ６ and R ７each independently represents 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 a fluorinated alkyl group having 1 to 6 carbon atoms), or a carboxyl group. As the alkyl group, a linear, branched or cyclic alkyl group having 1 to 10 carbon atoms is preferred. ３ represents an integer of 0 to 6. ４ represents an integer of 0 to 4. ４ is a methylene group, an oxygen atom, or a sulfur atom. Examples of repeating units represented by formula (V-1) or (V-2) are shown below. Examples of repeating units represented by formula (V-1) or (V-2) include the repeating units described in paragraph

[0100] of WO 2018 / 193954.

[0232] (Repeating Unit for Reducing Mobility of Main Chain) Resin (A) preferably has a high glass transition temperature (Tg) in order to suppress excessive diffusion of generated acid or pattern collapse during development. Tg is preferably higher than 90°C, more preferably higher than 100°C, even more preferably higher than 110°C, and particularly preferably higher than 125°C. In order to achieve an excellent dissolution rate in a developer, Tg is preferably 400°C or lower, 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 repeating unit") is calculated by the following method. First, the Tg of a homopolymer consisting of only each repeating unit contained in the polymer is calculated using the Bicerano method. Next, the mass proportion (%) of each repeating unit relative to all repeating units in the polymer is calculated. Next, the Tg at each mass ratio is calculated using the Fox formula (described in Materials Letters 62 (2008) 3152, etc.), and the sum of these values ​​is used to determine the Tg (°C) of the polymer. The Bicerano method is described in "Prediction of Polymer Properties," Marcel Dekker Inc., New York (1993). Calculation of Tg by the Bicerano method can be performed using polymer property estimation software MDL Polymer (MDL Information Systems, Inc.).

[0233] In order 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 a bulky substituent into the main chain; (b) Introduction of multiple substituents into the main chain; (c) Introduction of a substituent that induces interactions between resins (A) near the main chain; (d) Formation of a main chain with a cyclic structure; (e) Linking of a cyclic structure to the main chain. It is preferable that resin (A) has a repeating unit that exhibits a homopolymer Tg of 130°C or higher. The type of repeating unit that exhibits a homopolymer Tg of 130°C or higher is not particularly limited, and it is sufficient that the repeating unit exhibits a homopolymer Tg of 130°C or higher as calculated by the Bicerano method. It is to be noted that depending on the type of functional group in the repeating units represented by formulas (A) to (E) described below, it may be considered a repeating unit that exhibits a homopolymer Tg of 130°C or higher.

[0234] One example of a specific means for achieving the above (a) is to introduce a repeating unit represented by formula (A) into resin (A).

[0235]

[0236] Formula (A), R Ａ 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, and the multiple ring structures may be condensed or not condensed. Specific examples of the repeating unit represented by formula (A) include those described in paragraphs

[0107] to

[0119] of WO 2018 / 193954.

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

[0238]

[0239] In formula (B), R ｂ１ ~R ｂ４ each independently represents a hydrogen atom or an organic group; R ｂ１ ~R ｂ４At least two of the above represent organic groups. When 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 type of the other organic groups is not particularly limited. Furthermore, when none of the organic groups is a group in which a ring structure is directly linked to the main chain in the repeating unit, at least two of the organic groups are substituents having three or more constituent atoms excluding hydrogen atoms. Specific examples of the repeating unit represented by formula (B) include those described in paragraphs

[0113] to

[0115] of WO 2018 / 193954.

[0240] One example of a specific means for achieving the above (c) is to introduce a repeating unit represented by formula (C) into resin (A).

[0241]

[0242] In formula (C), R ｃ１ ~R ｃ４ each independently represents a hydrogen atom or an organic group; R ｃ１ ~R ｃ４ At least one of the repeating units represented by formula (C) is a group containing a hydrogen-bonding hydrogen atom within three atoms from the main chain carbon. In particular, in order to induce interactions between the main chains of resin (A), it is preferable to have a hydrogen-bonding hydrogen atom within two atoms (closer to the main chain). Specific examples of the repeating unit represented by formula (C) include those described in paragraphs

[0119] to

[0121] of WO 2018 / 193954.

[0243] One example of a specific means for achieving the above (d) is to introduce a repeating unit represented by formula (D) into resin (A).

[0244]

[0245] In formula (D), "Cyclic" represents a group that forms a main chain with a cyclic structure. The number of constituent atoms of the ring is not particularly limited. Specific examples of the repeating unit represented by formula (D) include those described in paragraphs

[0126] to

[0127] of WO 2018 / 193954.

[0246] One example of a specific means for achieving the above (e) is to introduce a repeating unit represented by formula (E) into resin (A).

[0247]

[0248] In formula (E), Re each independently represents a hydrogen atom or an organic group. Examples of the organic group include an alkyl group, a cycloalkyl group, an aryl group, an aralkyl group, and an alkenyl group, each of which may have a substituent. "Cyclic" refers to a cyclic group containing carbon atoms in the main chain. The number of atoms contained in the cyclic group is not particularly limited. Specific examples of the repeating unit represented by formula (E) include those described in paragraphs

[0131] to

[0133] of WO 2018 / 193954.

[0249] (Repeating unit having at least one group selected from a lactone group, a sultone group, a carbonate group, a hydroxyl group, a cyano group, and an alkali-soluble group) The resin (A) may have a repeating unit having at least one group selected from a lactone group, a sultone group, a carbonate group, a hydroxyl group, a cyano group, and an alkali-soluble group. Examples of the repeating unit having a lactone group, a sultone group, or a carbonate group contained in the resin (A) include the repeating units described above in <Repeating unit having a lactone group, a sultone group, or a carbonate group>. The preferred content is also as described above in <Repeating unit having a lactone group, a sultone group, or a carbonate group>.

[0250] The resin (A) may have a repeating unit having a hydroxyl group or a cyano group. 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. The repeating unit having a hydroxyl group or a cyano group preferably does not have an acid-decomposable group. Examples of repeating units having a hydroxyl group or a cyano group include those described in paragraphs

[0081] to

[0084] of JP 2014-098921 A.

[0251] The resin (A) may have a repeating unit having an alkali-soluble group. Examples of the alkali-soluble group include a carboxyl group, a sulfonamide group, a sulfonylimide group, a bissulfonylimide group, and an aliphatic alcohol group (e.g., a hexafluoroisopropanol group) substituted at the α-position with an electron-withdrawing group, with a carboxyl group being preferred. When the resin (A) contains a repeating unit having an alkali-soluble group, the resolution in contact hole applications is improved. Examples of repeating units having an alkali-soluble group include those described in paragraphs

[0085] and

[0086] of JP 2014-098921 A.

[0252] (Repeating unit having an alicyclic hydrocarbon structure and not exhibiting acid decomposability) Resin (A) may have a repeating unit having an alicyclic hydrocarbon structure and not exhibiting acid decomposability. This can reduce elution of low-molecular-weight components from the resist film into the immersion liquid during immersion exposure. Examples of repeating units having an alicyclic hydrocarbon structure and not exhibiting acid decomposability include repeating units derived from 1-adamantyl(meth)acrylate, diamantyl(meth)acrylate, tricyclodecanyl(meth)acrylate, or cyclohexyl(meth)acrylate.

[0253] (Repeating Unit Represented by Formula (III) Having Neither a Hydroxyl Group nor a Cyano Group) The resin (A) may have a repeating unit represented by formula (III) having neither a hydroxyl group nor a cyano group.

[0254]

[0255] In formula (III), R ５ represents a hydrocarbon group having at least one cyclic structure and having neither a hydroxyl group nor a cyano group. Ra represents a hydrogen atom, an alkyl group, or a —CH ２ -O-Ra ２ represents a group. ２ represents a hydrogen atom, an alkyl group, or an acyl group. Examples of the repeating unit represented by formula (III) that does not have either a hydroxyl group or a cyano group include those described in paragraphs

[0087] to

[0094] of JP 2014-098921 A.

[0256] (Repeating Unit Represented by Formula (AP-1)) It is also preferable that the resin (A) has a repeating unit represented by the following formula (AP-1).

[0257]

[0258] In formula (AP-1), R Ａ１１ represents a hydrogen atom, a halogen atom or an alkyl group. Ａ１１ represents a single bond or a divalent linking group. Ａ１２ is SO ２ represents a cyclic group containing a group.

[0259] R in formula (AP-1) Ａ１１ Examples of the halogen atom represented by R include a fluorine atom, a chlorine atom, a bromine atom, and an iodine atom. Ａ１１ The alkyl group represented by is preferably an alkyl group having 1 to 4 carbon atoms, more preferably a methyl group. Ａ１１ The alkyl group represented by R may have a substituent. Examples of the substituent include a hydroxyl group and a halogen atom. Ａ１１ is preferably a hydrogen atom or a methyl group.

[0260] L in formula (AP-1) Ａ１１ The divalent linking group represented by is not particularly limited, but examples thereof include an alkylene group, a divalent linking group having a monocyclic or polycyclic alicyclic hydrocarbon structure, an ether group, an ester group, a carbonyl group, a carboxyl group, or a divalent linking group formed by combining these groups. Ａ１１ is a single bond, or -L Ａ１１１ -CO ２ A linking group represented by - is preferred. Ａ１１１ represents a linear or branched alkylene group, or a monocyclic or polycyclic cycloalkylene group, and preferably represents a methylene group, an ethylene group, a cyclohexylene group, an adamantylene group, or a norbornylene group.

[0261] R in formula (AP-1) Ａ１２ SO represented by ２ The cyclic group containing the group is not particularly limited, but examples thereof include monocyclic or polycyclic groups having 3 to 20 carbon atoms. ２ The cyclic group containing the group is SO ２In addition to the group, it may further have at least one heteroatom selected from the group consisting of a sulfur atom, an oxygen atom, and a nitrogen atom. ２ The number of ring atoms in the cyclic group containing the SO group is preferably 4 to 30, and more preferably 5 to 20. ２ The cyclic group containing the group is preferably a sultone group obtained by removing one or more hydrogen atoms from a ring atom of the sultone structure represented by any one of the above formulae (SL1-1) to (SL1-3).

[0262] When resin (A) contains a repeating unit represented by formula (AP-1), the content of the repeating unit represented by formula (AP-1) is preferably 1 mol% or more, more preferably 10 mol% or more, based on all repeating units in resin (A). The upper limit of this content 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, based on all repeating units in resin (A).

[0263] (Repeating Unit Represented by Formula (AP-2)) It is also preferable that the resin (A) has a repeating unit represented by the following formula (AP-2).

[0264]

[0265] In formula (AP-2), R Ａ２１ represents a hydrogen atom, a halogen atom or an alkyl group. Ａ２１ represents a single bond or a divalent linking group. Ａ２２ represents an alkyl group.

[0266] R in formula (AP-2) Ａ２１ Examples of the halogen atom represented by R include a fluorine atom, a chlorine atom, a bromine atom, and an iodine atom. Ａ２１ The alkyl group represented by is preferably an alkyl group having 1 to 4 carbon atoms, more preferably a methyl group. Ａ２１ is preferably a hydrogen atom or a methyl group.

[0267] L in formula (AP-2) Ａ２１ The divalent linking group represented by is not particularly limited, but examples thereof include —O—, —NR １ -, -S-, -SO-, -SO ２-, an organic group (preferably a divalent organic group), and a group formed by combining two or more of these groups, and -O-, -CO-, -COO-, -OCOO-, -NR １ --, --CONR １ -, -S-, -SO-, -SO ２ -, an alkylene group, a cycloalkylene group, an alkenylene group, an arylene group, or a group formed by combining two or more of these groups is preferred. １ represents a hydrogen atom or an alkyl group. Ａ２１ The alkylene group represented by is not particularly limited, but is preferably an alkylene group having 1 to 8 carbon atoms, such as a methylene group, an ethylene group, a propylene group, a butylene group, a hexylene group, or an octylene group. Ａ２１ The number of carbon atoms in the cycloalkylene group represented by is not particularly limited, but is preferably 3 to 20, and more preferably 4 to 15. The cycloalkylene group may be a monocyclic cycloalkylene group such as a cyclopentylene group or a cyclohexylene group, or a polycyclic cycloalkylene group such as a norbornylene group, a tetracyclodecanylene group, a tetracyclododecanylene group, or an adamantylene group. One of the methylene groups constituting the cycloalkane ring of the cycloalkylene group may be replaced with a heteroatom such as an oxygen atom, a group having a heteroatom such as a carbonyl group or an ester bond, or a vinylidene group. Furthermore, in the cycloalkylene group, one or more of the ethylene groups constituting the cycloalkane ring may be replaced with a vinylene group. Ａ２１ The alkenylene group represented by is not particularly limited, but is preferably, for example, an alkenylene group having 2 to 8 carbon atoms. Ａ２１ The arylene group represented by is not particularly limited, but examples thereof include arylene groups having 6 to 20 carbon atoms, and preferably arylene groups having 6 to 15 carbon atoms. The arylene group is preferably a phenylene group or a naphthylene group, and particularly preferably a phenylene group. １When represents an alkyl group, examples of the alkyl group include alkyl groups having 20 or less carbon atoms, such as a methyl group, an ethyl group, a propyl group, an isopropyl group, an n-butyl group, a sec-butyl group, a hexyl group, a 2-ethylhexyl group, an octyl group, and a dodecyl group, and alkyl groups having 8 or less carbon atoms are preferred.

[0268] R in formula (AP-2) Ａ２２ The alkyl group represented by is not particularly limited, but preferably represents a linear or branched alkyl group having 1 to 5 carbon atoms.

[0269] When resin (A) contains a repeating unit represented by formula (AP-2), the content of the repeating unit represented by formula (AP-2) is preferably 1 mol% or more, more preferably 10 mol% or more, based on all repeating units in resin (A). 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, based on all repeating units in resin (A).

[0270] (Repeating Unit Represented by Formula (AP-3)) ​​It is also preferable that the resin (A) has a repeating unit represented by the following formula (AP-3).

[0271]

[0272] In formula (AP-3), R Ａ３１ represents a hydrogen atom, a halogen atom or an alkyl group. Ａ３１ represents a single bond or a divalent linking group. Ａ３２ represents an alicyclic hydrocarbon group. Ａ３３ represents a substituent having a double bond.

[0273] R in formula (AP-3) Ａ３１ Examples of the halogen atom represented by R include a fluorine atom, a chlorine atom, a bromine atom, and an iodine atom. Ａ３１ The alkyl group represented by is preferably an alkyl group having 1 to 4 carbon atoms, more preferably a methyl group. Ａ３１ is preferably a hydrogen atom or a methyl group.

[0274] L in formula (AP-3) Ａ３１The divalent linking group represented by is not particularly limited, but examples thereof include —O—, —NR １ -, -S-, -SO-, -SO ２ -, an organic group (preferably a divalent organic group), and a group formed by combining two or more of these groups, and -O-, -CO-, -COO-, -OCOO-, -NR １ --, --CONR １ -, -S-, -SO-, -SO ２ -, an alkylene group, a cycloalkylene group, an alkenylene group, an arylene group, or a group formed by combining two or more of these groups is preferred. １ represents a hydrogen atom or an alkyl group. Ａ３１ The alkylene group represented by is not particularly limited, but is preferably an alkylene group having 1 to 8 carbon atoms, such as a methylene group, an ethylene group, a propylene group, a butylene group, a hexylene group, or an octylene group. Ａ３１ The number of carbon atoms in the cycloalkylene group represented by is not particularly limited, but is preferably 3 to 20, and more preferably 4 to 15. The cycloalkylene group may be a monocyclic cycloalkylene group such as a cyclopentylene group or a cyclohexylene group, or a polycyclic cycloalkylene group such as a norbornylene group, a tetracyclodecanylene group, a tetracyclododecanylene group, or an adamantylene group. One of the methylene groups constituting the cycloalkane ring of the cycloalkylene group may be replaced with a heteroatom such as an oxygen atom, a group having a heteroatom such as a carbonyl group or an ester bond, or a vinylidene group. Furthermore, in the cycloalkylene group, one or more of the ethylene groups constituting the cycloalkane ring may be replaced with a vinylene group. Ａ３１ The alkenylene group represented by is not particularly limited, but is preferably, for example, an alkenylene group having 2 to 8 carbon atoms. Ａ３１ The arylene group represented by is not particularly limited, but examples thereof include arylene groups having 6 to 20 carbon atoms, and preferably arylene groups having 6 to 15 carbon atoms. The arylene group is preferably a phenylene group or a naphthylene group, and particularly preferably a phenylene group. １When represents an alkyl group, examples of the alkyl group include alkyl groups having 20 or less carbon atoms, such as a methyl group, an ethyl group, a propyl group, an isopropyl group, an n-butyl group, a sec-butyl group, a hexyl group, a 2-ethylhexyl group, an octyl group, and a dodecyl group, and alkyl groups having 8 or less carbon atoms are preferred.

[0275] R in formula (AP-3) Ａ３２ The alicyclic hydrocarbon group represented by is not particularly limited, but examples thereof include monocyclic or polycyclic alicyclic hydrocarbon groups having 3 to 20 carbon atoms.

[0276] R in formula (AP-3) Ａ３３ The substituent having a double bond represented by is preferably an alkenyl group or an aryl group. The alkenyl group is not particularly limited, but an alkenyl group having 2 to 20 carbon atoms is preferred, and an allyl group is more preferred. The aryl group is not particularly limited, but an aryl group having 6 to 20 carbon atoms is preferred, and a phenyl group or a naphthyl group is more preferred. R Ａ３３ It is particularly preferred that represents an allyl group, a phenyl group or a naphthyl group.

[0277] When resin (A) contains a repeating unit represented by formula (AP-3), the content of the repeating unit represented by formula (AP-3) is preferably 1 mol% or more, more preferably 10 mol% or more, based on all repeating units in resin (A). The upper limit of this content 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, based on all repeating units in resin (A).

[0278] (Other Repeating Units) Furthermore, the resin (A) may have a repeating unit other than the repeating units described above. For example, the resin (A) may have a repeating unit selected from the group consisting of a repeating unit having an oxathiane ring group, a repeating unit having an oxazolone ring group, a repeating unit having a dioxane ring group, and a repeating unit having a hydantoin ring group.

[0279] In addition to the repeating structural units described above, the resin (A) may have various repeating structural units for the purpose of adjusting dry etching resistance, suitability for a standard developer, substrate adhesion, resist profile, resolution, heat resistance, sensitivity, and the like.

[0280] As the resin (A), particularly when the composition of the present invention is used as an actinic ray-sensitive or radiation-sensitive resin composition for ArF, it is preferable that all of the repeating units are composed of repeating units derived from a compound having an ethylenically unsaturated bond. In particular, it is also preferable that all of the repeating units are composed of (meth)acrylate repeating units. When all of the repeating units are composed of (meth)acrylate repeating units, any of those in which all of the repeating units are methacrylate repeating units, all of the repeating units are acrylate repeating units, or all of the repeating units are a combination of methacrylate repeating units and acrylate repeating units can be used, and it is preferable that the acrylate repeating units account for 50 mol% or less of the total repeating units.

[0281] Resin (A) can be synthesized according to a conventional method (e.g., radical polymerization). The weight average molecular weight (Mw) of resin (A), as measured by GPC in terms of polystyrene, is preferably 30,000 or less, more preferably 1,000 to 30,000, even more preferably 3,000 to 30,000, and particularly preferably 5,000 to 15,000. The dispersity (molecular weight distribution, Mw / Mn) of resin (A) is preferably 1 to 5, more preferably 1 to 3, even more preferably 1.2 to 3.0, and particularly preferably 1.2 to 2.0. The smaller the dispersity, the better the resolution and resist shape, and furthermore, the smoother the sidewalls of the resist pattern and the better the roughness.

[0282] The content of resin (A) in the composition of the present invention is preferably 30.0 to 99.9 mass%, more preferably 40.0 to 99.9 mass%, and even more preferably 60.0 to 90.0 mass%, based on the total solid content of the composition of the present invention. Resin (A) may be used alone or in combination of two or more. When two or more types are used, the total content thereof is preferably within the above-mentioned preferred content range.

[0283] [Acid Diffusion Controller] The composition of the present invention may further contain an acid diffusion controller (also referred to as "compound (C)"). Compound (C) is a compound different from the onium salt (B-1) and the onium salt (B-2). The acid diffusion controller traps acid generated from a photoacid generator or the like upon exposure and acts as a quencher to suppress a reaction of the resin, which would otherwise be caused by excess acid generated and increase polarity due to the action of the acid in unexposed areas. The type of compound (C) is not particularly limited, and examples include a basic compound (CA), a low-molecular-weight compound (CB) having a nitrogen atom and a group that is cleaved by the action of an acid, and a compound (CC) whose acid diffusion control ability is reduced or eliminated by irradiation with actinic rays or radiation. Examples of compound (CC) include an onium salt compound (CD) that is a weaker acid relative to the photoacid generator, and a basic compound (CE) whose basicity is reduced or eliminated by irradiation with actinic rays or radiation. Specific examples of the basic compound (CA) include those described in paragraphs

[0132] to

[0136] of WO 2020 / 066824, and specific examples of the basic compound (CE) whose basicity is reduced or eliminated by irradiation with actinic rays or radiation include those described in paragraphs

[0137] to

[0155] of WO 2020 / 066824, and those described in paragraph

[0164] of WO 2020 / 066824. Specific examples of the low molecular weight compound (CB) having a nitrogen atom and having a group that leaves under the action of an acid include those described in paragraphs

[0156] to

[0163] of WO 2020 / 066824. Specific examples of the onium salt compound (CD) that is a weak acid relative to the photoacid generator include those described in paragraphs

[0305] to

[0314] of WO 2020 / 158337.

[0284] In addition to the above, for example, known compounds disclosed in paragraphs

[0627] to

[0664] of U.S. Patent Application Publication No. 2016 / 0070167A1, paragraphs

[0095] to

[0187] of U.S. Patent Application Publication No. 2015 / 0004544A1, paragraphs

[0403] to

[0423] of U.S. Patent Application Publication No. 2016 / 0237190A1, and paragraphs

[0259] to

[0328] of U.S. Patent Application Publication No. 2016 / 0274458A1 can be suitably used as the acid diffusion controller.

[0285] When the composition of the present invention contains compound (C), the content of compound (C) is preferably 0.01 to 30.0 mass%, more preferably 0.05 to 20.0 mass%, and even more preferably 0.1 to 15.0 mass%, based on the total solid content of the composition of the present invention. Compound (C) may be used alone, or two or more types may be used. When two or more types are used, the total content thereof preferably falls within the above-mentioned preferred content range.

[0286] [Resin (D)] The composition of the present invention may further contain a resin (D) (also referred to as a "hydrophobic resin") different from the resin (A). However, the resin (D) satisfies the following requirement (i): (i) The SP value of the resin (D) is smaller than the SP value of the resin (A) and is 17.2 or less.

[0287] (Method for calculating SP value of resin) The method for calculating the SP value (solubility parameter) of a resin is as follows. 1. The SP value of the monomer corresponding to each repeating unit constituting the resin is calculated using "HSPiP 5th Edition 5.1.08". 2. The content ratio of each repeating unit in the resin on a mass basis is multiplied by the SP value of the monomer corresponding to each repeating unit obtained in 1 above, and the sum of these values ​​is taken as the SP value of the resin.

[0288] According to the above calculation method, the SP value of resin (A) (SP Ａ ) and the SP value of resin (D) (SP Ｄ When two or more resins are used in combination, the SP value of each resin is calculated by multiplying the content ratio of each resin by mass in the above calculation method 2 by the SP value of each resin, and the sum of these values ​​is the SP value of the resin.

[0289] Resin (D) is preferably designed to be unevenly distributed on the surface of the resist film, but unlike surfactants, it does not necessarily have to have a hydrophilic group in its molecule, and does not necessarily have to contribute to uniform mixing of polar and non-polar substances. The effects of adding resin (D) include controlling the static and dynamic contact angles of water on the resist film surface, and suppressing outgassing.

[0290] Resin (D) is a resin containing fluorine atoms, silicon atoms, and CH atoms contained in the side chain portion of the resin in order to be unevenly distributed on the surface layer of the film. ３ It is preferable to have at least one of the partial structures, and more preferably two or more. Resin (D) preferably has a hydrocarbon group having 5 or more carbon atoms. These groups may be present in the main chain of the resin or may be substituted on a side chain. Examples of resin (D) include the compounds described in paragraphs

[0275] to

[0279] of WO 2020 / 004306.

[0291] When the composition of the present invention contains resin (D), the content of resin (D) is 0.01 to 10 mass% and preferably 0.1 to 5 mass% based on the total solid content of the composition of the present invention. Resin (D) may be used alone or in combination of two or more. When two or more types are used, the total content thereof is preferably within the above-mentioned preferred content range.

[0292] When the composition of the present invention contains resin (D), it preferably satisfies both of the following requirements (ii) and (iii): (ii) the total content of repeating units that do not contain fluorine atoms among the repeating units contained in resin (D) is 80 mol % or more based on all repeating units in resin (D), and (iii) the content of resin (D) is 0.01 to 10 mass % based on the total solid content in the actinic ray-sensitive or radiation-sensitive resin composition.

[0293] [Surfactant] The composition of the present invention may contain a surfactant. When a surfactant is contained, a pattern with better adhesion and fewer development defects can be formed. The surfactant is preferably a fluorine-based and / or silicon-based surfactant. Examples of the fluorine-based and / or silicon-based surfactant include the surfactants disclosed in paragraphs

[0218] and

[0219] of WO 2018 / 193954.

[0294] The surfactant may be used alone or in combination of two or more.

[0295] When the composition of the present invention contains a surfactant, the content of the surfactant is preferably 0.0001 to 2.0 mass%, more preferably 0.0005 to 1.0 mass%, and even more preferably 0.1 to 1.0 mass%, based on the total solid content of the composition of the present invention. The surfactant may be used alone, or two or more types may be used. When two or more types are used, the total content thereof is preferably within the above-mentioned preferred content range.

[0296] [Solvent] The composition of the present invention preferably contains a solvent. The solvent preferably contains (M1) propylene glycol monoalkyl ether carboxylate and (M2) at least one selected from the group consisting of propylene glycol monoalkyl ether, lactate ester, acetate ester, alkoxypropionate ester, linear ketone, cyclic ketone, lactone, and alkylene carbonate. The solvent may further contain components other than components (M1) and (M2).

[0297] Combining the above-mentioned solvent with the above-mentioned resin is preferable in terms of improving the coatability of the composition of the present invention and reducing the number of development defects in the pattern. The above-mentioned solvent has a good balance of the solubility, boiling point, and viscosity of the above-mentioned resin, and therefore can suppress unevenness in the film thickness of the resist film and the occurrence of precipitates during spin coating. Details of component (M1) and component (M2) are described in paragraphs

[0218] to

[0226] of WO 2020 / 004306, the contents of which are incorporated herein by reference.

[0298] When the solvent further contains components other than the components (M1) and (M2), the content of the components other than the components (M1) and (M2) is preferably 5 to 30 mass % based on the total amount of the solvent.

[0299] The content of the solvent in the composition of the present invention is preferably determined so that the solids concentration is 0.5 to 30% by mass, more preferably 1 to 20% by mass, which further improves the coatability of the composition of the present invention.

[0300] [Other Additives] The composition of the present invention may further contain a dissolution inhibiting compound, a dye, a plasticizer, a photosensitizer, a light absorber, and / or a compound that promotes solubility in a developer (for example, a phenol compound having a molecular weight of 1,000 or less, or an alicyclic or aliphatic compound containing a carboxyl group).

[0301] The "dissolution inhibiting compound" is a compound having a molecular weight of 3,000 or less, which is decomposed by the action of an acid and has a reduced solubility in an organic developer.

[0302] The content of fluorine atoms in the total solid content of the composition of the present invention is preferably 1% by mass or less, more preferably 0.5% by mass or less, and even more preferably 0.1% by mass or less.

[0303] The content of fluorine atoms represents the mass ratio of fluorine atoms in the total solid content to the total atoms in the total solid content in the composition of the present invention. For example, when the total solid content in the composition of the present invention is composed of carbon atoms, hydrogen atoms, fluorine atoms, nitrogen atoms, oxygen atoms, and sulfur atoms, the content of fluorine atoms (mass%) can be calculated using the following formula (1a): 100 x 19 x [F] / (12 x [C] + 1 x [H] + 19 x [F] + 14 x [N] + 16 x [O] + 32 x [S]) ... (1a) [C] represents the molar ratio of carbon atoms in the total solid content, [H] represents the molar ratio of hydrogen atoms in the total solid content, [F] represents the molar ratio of fluorine atoms in the total solid content, [N] represents the molar ratio of nitrogen atoms in the total solid content, [O] represents the molar ratio of oxygen atoms in the total solid content, and [S] represents the molar ratio of sulfur atoms in the total solid content. The molar ratio of carbon atoms in the total solid content [C] can be calculated from the number of carbon atoms, molecular weight, and content of each component in the solid content. For example, the molar ratio of carbon atoms in the onium salt (B-1) can be calculated by the following formula (1b): ｗ / A Ｍ ×A Ｃ ... (1b) A ｗ is the amount of onium salt (B-1) in the total solid content (unit: "g" or "% by mass"), A Ｍ is the molecular weight of the onium salt (B-1), A Ｃ represents the number of carbon atoms in the onium salt (B-1). The molar ratios of carbon atoms for other constituent components are calculated in the same manner, and the molar ratio [C] of carbon atoms in the total solid content can be calculated by summing them up. By replacing the carbon atom in the above formula with another atom, the molar ratio of the other atom can be calculated in the same manner. Furthermore, when the total solid content in the composition of the present invention contains an atom other than those mentioned above, the molar ratio can be calculated in the same manner using the atomic weight of that atom and the molar ratio in the total solid content. In addition to the above method, the molar ratio can also be calculated by analytical techniques such as elemental analysis of a resist film obtained by evaporating the solvent component of the composition of the present invention.

[0304] The composition of the present invention is also suitable as a photosensitive composition for EUV exposure.

[0305] <Actinic ray- or radiation-sensitive film, pattern forming method> The present invention also relates to an actinic ray- or radiation-sensitive film formed from the composition of the present invention. The actinic ray- or radiation-sensitive film of the present invention is preferably a resist film. The procedure of the pattern forming method using the composition of the present invention is not particularly limited, but preferably includes the following steps: Step 1: forming a resist film on a substrate using the composition of the present invention; Step 2: exposing the resist film; Step 3: developing the exposed resist film using a developer. The procedure of each of the above steps will be described in detail below.

[0306] (Step 1: Resist Film Forming Step) Step 1 is a step of forming a resist film on a substrate using the composition of the present invention.

[0307] A method for forming a resist film on a substrate using the composition of the present invention includes, for example, applying the composition of the present invention to a substrate. It is preferable to filter the composition of the present invention before application, if necessary. The pore size of the filter is preferably 0.1 μm or less, more preferably 0.05 μm or less, and even more preferably 0.03 μm or less. The filter is preferably made of polytetrafluoroethylene, polyethylene, or nylon.

[0308] The composition of the present invention can be applied onto a substrate (e.g., silicon, silicon coated with silicon dioxide) such as those used in the manufacture of integrated circuit elements by an appropriate application method such as a spinner or coater. Spin application using a spinner is preferred. The rotation speed during spin application using a spinner is preferably 1,000 to 3,000 rpm (rotations per minute). After application of the composition of the present invention, the substrate may be dried to form a resist film. If necessary, various undercoating films (inorganic film, organic film, anti-reflective film) may be formed below the resist film.

[0309] An example of a drying method is a method of drying by heating. Heating can be performed by means provided in a normal exposure machine and / or developing machine, and may also be performed 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 1,000 seconds, more preferably 60 to 800 seconds, and even more preferably 60 to 600 seconds.

[0310] The thickness of the resist film is not particularly limited, but is preferably 10 to 120 nm from the viewpoint of forming a finer pattern with higher precision. In particular, when EUV exposure is used, the thickness of the resist film is more preferably 10 to 65 nm, and even more preferably 15 to 50 nm. When ArF immersion exposure is used, the thickness of the resist film is more preferably 10 to 120 nm, and even more preferably 15 to 90 nm.

[0311] A top coat may be formed on the resist film using a top coat composition. It is preferable that the top coat composition does not mix with the resist film and can be uniformly applied to the resist film. The top coat is not particularly limited, and a conventionally known top coat can be formed by a conventionally known method. For example, a top coat can be formed based on the description in paragraphs

[0072] to

[0082] of JP 2014-059543 A. For example, a top coat containing a basic compound such as that described in JP 2013-61648 A is preferably formed on the resist film. Specific examples of basic compounds that may be contained in the top coat include the basic compounds that may be contained in the composition of the present invention. It is also preferable that the top coat contain a compound containing at least one group or bond selected from the group consisting of an ether bond, a thioether bond, a hydroxyl group, a thiol group, a carbonyl bond, and an ester bond.

[0312] (Step 2: Exposure Step) Step 2 is a step of exposing the resist film to light. Examples of exposure methods include irradiating the formed resist film with actinic rays or radiation through a predetermined mask. Examples of actinic rays or radiation include infrared light, visible light, ultraviolet light, far ultraviolet light, extreme ultraviolet light, X-rays, and electron beams. The actinic rays or radiation preferably have a wavelength of 250 nm or less, more preferably 220 nm or less, and particularly preferably far ultraviolet light with a wavelength of 1 to 200 nm. Specific examples of such radiation include KrF excimer laser (248 nm), ArF excimer laser (193 nm), and F ２ Excimer laser (157 nm), EUV (13.5 nm), X-ray, and electron beam.

[0313] After exposure, it is preferable to bake (heat) the film before developing. Baking promotes the reaction of 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 1,000 seconds, more preferably 10 to 180 seconds, and even more preferably 30 to 120 seconds. Heating can be performed using means provided in a typical exposure machine and / or development machine, and may also be performed using a hot plate or the like. This process is also called post-exposure baking.

[0314] (Step 3: Development Step) Step 3 is a step of developing the exposed resist film with a developer to form a pattern. The developer may be an alkaline developer or a developer containing an organic solvent (hereinafter also referred to as an organic developer).

[0315] Examples of development methods include a method in which a substrate is immersed in a tank filled with a developer for a certain period of time (dip method), a method in which a developer is piled up on the surface of a substrate by surface tension and left to stand for a certain period of time for development (puddle method), a method in which a developer is sprayed onto the surface of the substrate (spray method), and a method in which a developer is continuously dispensed onto a substrate rotating at a constant speed while a developer dispense nozzle is scanned at a constant speed (dynamic dispense method). Furthermore, after the development step, a step of stopping development while replacing the solvent with another solvent may be carried out. The development time is not particularly limited as long as it is long enough to sufficiently dissolve the resin in the unexposed areas, and is preferably 10 to 300 seconds, more preferably 20 to 120 seconds. The temperature of the developer is preferably 0 to 50°C, more preferably 15 to 35°C.

[0316] The alkaline developer is preferably an aqueous alkaline solution containing an alkali. The type of alkaline aqueous solution is not particularly limited, but examples include aqueous alkaline solutions containing a quaternary ammonium salt, such as tetramethylammonium hydroxide, an inorganic alkali, a primary amine, a secondary amine, a tertiary amine, an alcohol amine, or a cyclic amine. Of these, the alkaline developer is preferably an aqueous solution of a quaternary ammonium salt, such as tetramethylammonium hydroxide (TMAH). Appropriate amounts of alcohols, surfactants, and the like may be added to the alkaline developer. The alkaline concentration of the alkaline developer is usually preferably 0.1 to 20% by mass. The pH of the alkaline developer is usually preferably 10.0 to 15.0.

[0317] The organic developer is preferably a developer containing at least one organic solvent selected from the group consisting of ketone-based solvents, ester-based solvents, alcohol-based solvents, amide-based solvents, ether-based solvents, and hydrocarbon-based solvents.

[0318] The above-mentioned solvents may be mixed in plural, or may be mixed with a solvent other than the above 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 free of water. The content of the organic solvent in the organic developer is preferably 50% by mass or more and 100% by mass or less, more preferably 80% by mass or more and 100% by mass or less, even more preferably 90% by mass or more and 100% by mass or less, and particularly preferably 95% by mass or more and 100% by mass or less, based on the total amount of the developer.

[0319] (Other Steps) The pattern formation method preferably includes, after step 3, a step of cleaning with a rinse liquid.

[0320] The rinse liquid used in the rinse step after the development step using an alkaline developer can be, for example, pure water. A suitable amount of surfactant may be added to the pure water. A suitable amount of surfactant may be added to the rinse liquid.

[0321] The rinse liquid used in the rinse step after the development step using an organic developer is not particularly limited as long as it does not dissolve the pattern, and a solution containing a general organic solvent can be used. The rinse liquid is preferably a rinse liquid containing at least one organic solvent selected from the group consisting of hydrocarbon solvents, ketone solvents, ester solvents, alcohol solvents, amide solvents, and ether solvents.

[0322] The method for the rinsing step is not particularly limited, and examples include a method in which a rinsing solution is continuously discharged onto a substrate rotating at a constant speed (spin coating method), a method in which a substrate is immersed in a tank filled with the rinsing solution for a certain period of time (dipping method), and a method in which the rinsing solution is sprayed onto the substrate surface (spray method). The pattern formation method may also include a heating step (post-bake) after the rinsing step. This step removes the developer and rinsing solution remaining between and within the pattern by baking. This step also has the effect of annealing the resist pattern and improving the surface roughness of the pattern. The heating step after the rinsing step is typically performed at 40 to 250°C (preferably 90 to 200°C) for typically 10 seconds to 3 minutes (preferably 30 to 120 seconds).

[0323] Alternatively, the substrate may be etched using the formed pattern as a mask. That is, the substrate (or the underlayer film and the substrate) may be processed using the pattern formed in step 3 as a mask to form a pattern on the substrate. The method for processing the substrate (or the underlayer film and the substrate) is not particularly limited, but a method of forming a pattern on the substrate by dry etching the substrate (or the underlayer film and the substrate) using the pattern formed in step 3 as a mask is preferred. The dry etching is preferably oxygen plasma etching.

[0324] The composition of the present invention and various materials used in the pattern formation method (e.g., solvents, developers, rinse solutions, anti-reflective coating compositions, top coat compositions, etc.) preferably do not contain impurities such as metals. The content of impurities contained in these materials is preferably 1 mass ppm (parts per million) or less, more preferably 10 mass ppb (parts per billion) or less, even more preferably 100 mass ppt or less, particularly preferably 10 mass ppt or less, and most preferably 1 mass ppt or less. There is no particular lower limit, and 0 mass ppt or more is preferred. Here, 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.

[0325] Examples of methods for removing impurities such as metals from various materials include filtration using a filter. Details of filtration using a filter are described in paragraph

[0321] of WO 2020 / 004306.

[0326] Methods for reducing impurities such as metals contained in various materials include, for example, selecting raw materials with a low metal content as raw materials for the various materials, filtering the raw materials for the various materials, and performing distillation under conditions that minimize contamination as much as possible, for example by lining the inside of the apparatus with Teflon (registered trademark).

[0327] In addition to filter filtration, impurities may be removed using an adsorbent, or a combination of filter filtration and an adsorbent may be used. Known adsorbents can be used as the adsorbent, including inorganic adsorbents such as silica gel and zeolite, and organic adsorbents such as activated carbon. In order to reduce impurities such as metals contained in the various materials, it is necessary to prevent the incorporation 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 contained in the cleaning solution used to clean the manufacturing equipment. The content of metal components contained in the used cleaning solution is preferably 100 parts per trillion (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, and 0 ppt by mass or more is preferred.

[0328] A conductive compound may be added to an organic processing liquid such as a rinse solution to prevent breakdown of the chemical solution piping and various parts (filters, O-rings, tubes, etc.) due to static charging and subsequent electrostatic discharge. The conductive compound is not particularly limited, but examples include methanol. The amount added is not particularly limited, but in order to maintain favorable development or rinsing characteristics, it is preferably 10% by mass or less, more preferably 5% by mass or less. There is no particular lower limit, but 0.01% by mass or more is preferred. For the chemical solution piping, for example, stainless steel (SUS), or various piping coated with antistatically treated polyethylene, polypropylene, or fluororesin (such as polytetrafluoroethylene or perfluoroalkoxy resin), can be used. Similarly, for the filters and O-rings, antistatically treated polyethylene, polypropylene, or fluororesin (such as polytetrafluoroethylene or perfluoroalkoxy resin), can be used.

[0329] <Method for manufacturing an electronic device> The present invention also relates to a method for manufacturing an electronic device, including the above-mentioned pattern formation method, and an electronic device manufactured by this manufacturing method. A preferred embodiment of the electronic device of the present invention is one that is installed in electrical and electronic equipment (such as home appliances, office automation (OA), media-related equipment, optical equipment, and communication equipment).

[0330] The present invention will be described in more detail below with reference to the following examples. The materials, amounts used, ratios, treatment details, and treatment procedures shown in the following examples can be appropriately changed without departing from the spirit of the present invention. Therefore, the scope of the present invention should not be construed as being limited by the following examples.

[0331] (Acid (AC Ｂ１ ) and acid (AC Ｂ２ The pKa of the acid (AC) generated from the onium salt (B-1) upon irradiation with actinic rays or radiation Ｂ１ ) pKa (pKa Ｂ１ ), and an acid (AC) generated from the onium salt (B-2) upon irradiation with actinic rays or radiation. Ｂ２ ) pKa (pKa Ｂ２The structure of each onium salt in which the anion moiety is protonated (for example, the anion moiety is SO ３ － If so, SO ３ H), calculations were performed using software (Advanced Chemistry Development (ACD / Labs) Software V8.14 for Solaris (1994-2007 ACD / Labs)). When multiple onium salts are contained as onium salt (B-1), the calculated value of the onium salt species with the lowest pKa was used to calculate ΔpKa (pKa Ｂ１ -pKa Ｂ２ In addition, when the onium salt (B-2) contains a plurality of onium salts, the calculated value of the onium salt species with the highest pKa was used to calculate ΔpKa (pKa Ｂ１ -pKa Ｂ２ ) was calculated.

[0332] (Fluorine Content of Onium Salt (B-1)) The fluorine content of the onium salt (B-1) represents the mass ratio (mass %) of fluorine atoms to all atoms in the onium salt (B-1), and was calculated by the following formula (1): 100×19×F Ｂ１ / MW Ｂ１ (1) In formula (1), F Ｂ１ is the number of fluorine atoms contained in the onium salt (B-1), MW Ｂ１ represents the molecular weight of the onium salt (B-1).

[0333] (Fluorine Content of Onium Salt (B-2)) The fluorine content of the onium salt (B-2) represents the mass ratio (mass %) of fluorine atoms to all atoms in the onium salt (B-2), and can be calculated by the following formula (2): 100×19×F Ｂ２ / MW Ｂ２ (2) In formula (2), F Ｂ２ is the number of fluorine atoms contained in the onium salt (B-2), MW Ｂ２ represents the molecular weight of the onium salt (B-2).

[0334] <Onium Salt (B-1)> B1-1 to B1-18 were used as the onium salt (B-1). B1-1 to B1-18 can act as acid diffusion controllers whose acid diffusion control ability is reduced or eliminated by irradiation with actinic rays or radiation. In addition, Z1-1 to Z1-4 were used as acid diffusion controllers that are not onium salt (B-1). For convenience, Z1-1 to Z1-4 are also listed in the onium salt (B-1) column in the table below.

[0335]

[0336]

[0337]

[0338] The following Table 1 shows the fluorine content of the onium salt (B-1) and the acid (AC) generated from the onium salt (B-1). Ｂ１ ) pKa (pKa Ｂ１ ) is shown.

[0339]

[0340] <Onium Salt (B-2)> B2-1 to B2-30 were used as the onium salt (B-2). B2-1 to B2-30 can act as photoacid generators. Furthermore, Z2-1 was used as a photoacid generator that is not an onium salt (B-2). For convenience, Z2-1 is also listed in the onium salt (B-2) column in the table below.

[0341]

[0342]

[0343]

[0344]

[0345] Table 2 below shows the fluorine content of the onium salt (B-2) and the acid (AC) generated from the onium salt (B-2). Ｂ２ ) pKa (pKa Ｂ２ ) is shown.

[0346]

[0347] A synthesis example of the onium salt (B-2) is shown below.

[0348] (Synthesis Example 1: Synthesis of B2-4) <Synthesis of intermediate B2-4-1>

[0349]

[0350] A mixed solution of 66.3 g (0.65 mol) of triethylamine and 175 ml of acetonitrile was stirred at -40°C under a nitrogen atmosphere, to which 50.0 g (0.44 mol) of methanesulfonyl chloride was slowly added dropwise. After stirring for 1 hour, 16.2 g (0.22 mol) of 2-butanol was slowly added dropwise, and the mixture was stirred for an additional 2 hours. After removing the precipitated triethylamine hydrochloride by filtration, 400 ml of ethyl acetate was added to the filtrate, and the resulting solution was added to 300 ml of 1 mol / l aqueous hydrochloric acid cooled to below 10°C. After removing the aqueous layer by separation, the organic layer was washed three times with 300 ml of water, and the solvent was distilled off by vacuum concentration. The resulting residue was dissolved in 20 ml of ethyl acetate, and 120 ml of hexane was added while stirring at room temperature (23°C), resulting in the precipitation of crystals. After stirring for 30 minutes, the mixture was filtered to collect the crystals, thereby obtaining 31.2 g of intermediate B2-4-1 (yield 62%). １ H NMR (CDCl ３ ): 4.56, 4.22, 3.25, 2.11, 1.01ppm

[0351] <Synthesis of Intermediate B2-4-2>

[0352]

[0353] A mixed solution of 10 g (0.060 mol) of 1-adamantanemethanol, 11.1 g (0.13 mol) of sodium hydrogencarbonate, and 120 ml of acetonitrile was stirred at 5°C or below under ice cooling, while 13.4 g (0.066 mol) of bromoacetic acid bromide was slowly added dropwise. The mixture was stirred for 1 hour under ice cooling, and then 100 ml of water was slowly added dropwise. 200 ml of methylene chloride and 100 ml of water were added, and the aqueous layer was removed by liquid separation. The organic layer was then washed three times with 200 ml of water. The organic layer was concentrated under reduced pressure and the solvent was distilled off, yielding 16 g of crude intermediate B2-4-2. This crude product was used directly in the next reaction without further purification.

[0354] <Synthesis of Intermediate B2-4-3>

[0355]

[0356] To a mixed solution of 5.0 g (0.022 mol) of intermediate B2-4-1, 50 ml of tetrahydrofuran (THF), and 20 ml of N,N-dimethylformamide (DMF), 2.6 g (0.023 mol) of potassium tert-butoxide was slowly added at 0°C under a nitrogen atmosphere, and the mixture was stirred for 10 minutes. Subsequently, 6.9 g (0.024 mol) of intermediate B2-4-2 was slowly added, and the mixture was further stirred at room temperature (23°C) for 5 hours. The reaction solution was added to 70 ml of 1 mol / L aqueous hydrochloric acid at 10°C or below under ice cooling. 150 ml of ethyl acetate was added and the aqueous layer was removed. The organic layer was washed three times with 70 ml of water, and the solvent was removed by vacuum concentration. The resulting residue was purified by silica gel column chromatography (hexane / ethyl acetate = 4 / 1 (volume ratio)), yielding 3.5 g of intermediate B2-4-3 (yield 37%). １ H NMR (CDCl ３ ): 5.06, 4.21, 3.79, 3.34-3.18, 3.27, 2.06, 2.00, 1.78-1.61, 1.54, 1.00ppm

[0357] <Synthesis of Intermediate B2-4-4>

[0358]

[0359] To a mixed solution of 3.0 g (6.9 mmol) of intermediate B2-4-3 and 50 ml of acetonitrile, 1.1 g (7.6 mmol) of sodium iodide was added and stirred for 3 hours at 50° C. The precipitated crystals were collected by filtration, and 2.4 g of intermediate B2-4-4 was obtained (yield 87%). １ H NMR (DMSO-d6): 4.27, 3.65, 3.13, 2.98-2.80, 1.94, 1.73-1.56, 1.50ppm

[0360] <Synthesis of B2-4>

[0361]

[0362] To a mixed solvent of 2.1 g (5.2 mmol) of intermediate B2-4-4, 35 ml of methylene chloride, and 35 ml of water, 1.8 g (5.4 mmol) of triphenylsulfonium bromide was added and stirred at room temperature (23°C) for 1 hour. After the reaction, the organic layer was extracted and washed once with 35 ml of 0.1 mol / L aqueous hydrochloric acid and four times with 35 ml of water, followed by concentration under reduced pressure. 30 ml of tert-butyl methyl ether was added to the residue, and the mixture was stirred at room temperature. The solid obtained after filtration was dried under vacuum, yielding 3 g of B2-4 (yield 88%). １ H NMR (CDCl ３ ): 7.82-7.66, 4.76, 3.68, 3.31, 3.35-3.12, 1.95, 1.74-1.58, 1.52ppm

[0363] Other onium salts (B-2) were synthesized in the same manner as above. B1-1 was synthesized according to the method described in JP-A-2010-155824. Other onium salts (B-1) were also synthesized in the same manner.

[0364] <Resin (A)> Resins A-1 to A-20 shown in Table 3 were used as resins (A) (resins whose polarity increases under the action of an acid). Table 3 shows the content (mol %; corresponding in order from left to right) of each repeating unit shown below in resin (A), the weight average molecular weight (Mw) of resin (A), and the dispersity (Mw / Mn) of resin (A). The weight average molecular weight (Mw) and dispersity (Mw / Mn) were measured by GPC (carrier: tetrahydrofuran (THF)) (amounts calculated as polystyrene). The content of each repeating unit was １３ The SP value of each resin was measured by C-NMR (Nuclear Magnetic Resonance). Ａ ) was also listed.

[0365] In this example, the SP value of the resin was calculated as follows.

[0366] (Method for calculating SP value of resin) The method for calculating the SP value of a resin is as follows. 1. The SP value of a monomer corresponding to each repeating unit constituting the resin was calculated using "HSPiP 5th Edition 5.1.08". 2. The content ratio of each repeating unit in the resin on a mass basis was multiplied by the SP value of the monomer corresponding to each repeating unit obtained in 1 above, and the sum of these values ​​was taken as the SP value of the resin.

[0367] According to the above calculation method, the SP value of resin (A) (SP Ａ ) and the SP value of resin (D) (SP Ｄ When two or more resins were used in combination, the content ratio of each resin on a mass basis was multiplied by the SP value of each resin in the above calculation method 2, and the sum was used as the SP value of the resin.

[0368]

[0369]

[0370]

[0371] <Basic Compound> C-1 to C-4 were used as basic compounds, which can act as acid diffusion controllers.

[0372]

[0373] <Resin (D)> Resins D-1 to D-6 shown in Table 4 were used as resins (D). Table 4 shows the content (mol %; corresponding in order from left to right) of each repeating unit shown below in resin (D), the weight average molecular weight (Mw) of resin (D), and the dispersity (Mw / Mn) of resin (D). The weight average molecular weight (Mw) and dispersity (Mw / Mn) were measured by GPC (carrier: tetrahydrofuran (THF)) (amounts calculated as polystyrene). The content of each repeating unit was １３ The SP value of each resin was measured by C-NMR (Nuclear Magnetic Resonance). Ｄ ) was also listed.

[0374]

[0375]

[0376] <Surfactant> E-1 was used as the surfactant. E-1: PolyFox PF-6320 (manufactured by OMNOVA Solutions Inc.; fluorine-based)

[0377] <Solvents> The solvents used are as follows: S1: Propylene glycol monomethyl ether acetate (PGMEA) S2: Propylene glycol monomethyl ether (PGME) S3: γ-butyrolactone S4: Ethyl lactate S5: Cyclohexanone S6: 2-heptanone

[0378] (ArF Exposure) <Preparation of Resist Compositions> Components other than the solvents shown in Tables 5 to 8 were dissolved in the solvents shown in Tables 5 to 8 to prepare solutions with a solids concentration of 4.0% by mass. These solutions were then filtered through a polyethylene filter with a pore size of 0.02 μm to prepare resist compositions (RA-1 to RA-87 and RZ-1 to RZ-10). The solids content refers to all components other than the solvent. The resulting resist compositions were used in the examples and comparative examples. In Tables 5 to 8, the "mass %" column indicates the content (mass %) of each component relative to the total solids content in the resist composition. Tables 5 to 8 also list the amount (mass ratio) of the solvent used. When two or more types of each component were used, the type and content (mass %) of each component are separated by a " / " (type and content correspond in order from left to right). Tables 5 to 8 also show the acid (AC) generated from the onium salt (B-1) in each resist composition. Ｂ１ ) pKa (pKa Ｂ１ ) and the acid (AC) generated from the onium salt (B-2) Ｂ２ ) pKa (pKa Ｂ２ ) difference △pKa (pKa Ｂ１ -pKa Ｂ２ ) was described.

[0379]

[0380]

[0381]

[0382]

[0383] <Pattern Formation Method (1): ArF Exposure, Alkali Development (Positive), Examples 1-1 to 1-59, Comparative Examples X1-1 to X1-5> The resist compositions shown in Tables 9 to 10 were applied to 6-inch Si wafers previously treated with hexamethyldisilazane (HMDS) using a Tokyo Electron Mark 8 spin coater. The wafers were then dried on a hot plate at 100°C for 60 seconds to obtain resist films with a thickness of 90 nm. Here, 1 inch is 0.0254 m. The wafers on which the resist films were formed were subjected to pattern exposure through an exposure mask using an ArF excimer laser scanner (ASML, PAS5500 / 1500, wavelength 193 nm, NA 0.50). The wafers were then baked at 115°C for 60 seconds, developed with a 2.38% by weight aqueous tetramethylammonium hydroxide solution (TMAHaq) for 30 seconds, rinsed with pure water, and spin-dried. As a result, a resist pattern having a 1:1 line and space pattern with a line width of 50 nm was obtained.

[0384] <Performance Evaluation> [LWR (Line Width Roughness) Performance] When a 50 nm 1:1 line and space pattern resolved with the optimum exposure dose for resolving a line pattern with an average line width of 50 nm was observed from above the pattern using a critical dimension scanning electron microscope (SEM (Hitachi, Ltd. S-9380II)), the line width was observed at 50 locations and the standard deviation (σ) was calculated. The measurement variation in line width was evaluated using 3σ, and the value of 3σ was defined as the LWR (nm). The smaller the LWR value, the better the LWR performance. The LWR is preferably 4.8 nm or less, more preferably 4.2 nm or less, and particularly preferably 3.9 nm or less.

[0385] [Pattern Shape] The cross-sectional shape of the line portion of a 1:1 line and space pattern with a line width of 50 nm was visually observed using a scanning electron microscope (S-4800 manufactured by Hitachi, Ltd.). The cross-sectional shape of the pattern was judged to be either "rectangular," "tapered," "slightly tapered," "reverse tapered," or "slightly reverse tapered." "Tapered" and "slightly tapered" are shapes in which the width of the line portion gradually increases from the top of the pattern to the bottom of the pattern. "Slightly tapered" has a smaller rate of increase in the width of the line portion than "tapered." "Reverse tapered" and "slightly reverse tapered" are shapes in which the width of the line portion gradually decreases from the top of the pattern to the bottom of the pattern. "Slightly reverse tapered" has a smaller rate of decrease in the width of the line portion than "reverse tapered." The cross-sectional shape of the pattern is preferably rectangular.

[0386] The results are shown in Tables 9 and 10.

[0387]

[0388]

[0389] <Pattern Forming Method (2): ArF Exposure, Organic Solvent Development (Negative), Examples 2-1 to 2-59, Comparative Examples X2-1 to X2-5> The resist compositions shown in Tables 11 and 12 were applied to a 6-inch Si wafer previously treated with hexamethyldisilazane (HMDS) using a Tokyo Electron Mark 8 spin coater. The wafer was then dried on a hot plate at 100°C for 60 seconds to obtain a resist film with a thickness of 90 nm. Here, 1 inch is 0.0254 m. The wafer on which the resist film was formed was subjected to pattern exposure through an exposure mask using an ArF excimer laser scanner (ASML, PAS5500 / 1500, wavelength 193 nm, NA 0.50). The wafer was then baked at 115°C for 60 seconds, developed with n-butyl acetate for 30 seconds, and spin-dried. This resulted in a 1:1 line-and-space resist pattern with a line width of 50 nm.

[0390] The LWR performance and pattern shape were evaluated in the same manner as in the performance evaluation of the above-mentioned pattern formation method (1). The results are shown in Table 10.

[0391]

[0392]

[0393] (EUV Exposure) <Preparation of Resist Compositions> Resist compositions (ERA-1 to ERA-87 and ERZ-1 to ERZ-10) were prepared by the same procedures as in the preparation of the aforementioned resist compositions (RA-1 to RA-87 and RZ-1 to RZ-10), except that the solids concentration was changed from 4.0% by mass to 2.0% by mass, and the resulting mixed solution was filtered first through a polyethylene filter with a 50 nm pore size, then a nylon filter with a 10 nm pore size, and finally a polyethylene filter with a 5 nm pore size, in that order. That is, the types and contents (mass%) of components other than the solvent contained in ERA-1 to ERA-87 and ERZ-1 to ERZ-10, and the types of solvents and the mass ratios of each solvent were the same as those for RA-1 to RA-87 and RZ-1 to RZ-10, respectively, listed in Tables 5 to 8 above.

[0394] <Pattern Forming Method (3): EUV Exposure, Alkali Development (Positive), Examples 3-1 to 3-41, Comparative Examples X3-1 to X3-5> An underlayer film-forming composition AL412 (manufactured by Brewer Science) was applied to a silicon wafer and baked at 205°C for 60 seconds to form an underlayer film with a thickness of 20 nm. A resist composition shown in Tables 13 to 14 was applied to the underlayer film and baked at 100°C for 60 seconds to form a resist film with a thickness of 30 nm. Using an EUV exposure system (manufactured by Exitech, Micro Exposure Tool, NA 0.3, Quadruple, outer sigma 0.68, inner sigma 0.36), the silicon wafer having the resulting resist film was subjected to pattern irradiation. A mask with a line size of 25 nm and a line:space ratio of 1:1 was used as the reticle. The exposed resist film was baked at 90° C. for 60 seconds, developed with an aqueous solution of tetramethylammonium hydroxide (2.38% by mass) for 30 seconds, rinsed with pure water for 30 seconds, and then spin-dried to obtain a positive pattern.

[0395] <Performance Evaluation> [LWR Performance] A 25 nm (1:1) line and space pattern resolved with the optimum exposure dose for resolving a line pattern with an average line width of 25 nm was observed from above using a critical dimension scanning electron microscope (SEM (Hitachi, Ltd. S-9380II)), and the line width was observed at 50 locations to determine the standard deviation (σ). The measurement variation in line width was evaluated using 3σ, and the value of 3σ was defined as the LWR (nm). The smaller the LWR value, the better the LWR performance. The LWR is preferably 4.5 nm or less, more preferably 4.0 nm or less, and particularly preferably 3.7 nm or less.

[0396] [Pattern Shape] The cross-sectional shape of the line portion of a 1:1 line and space pattern with a line width of 25 nm was visually observed using a scanning electron microscope (S-4800 manufactured by Hitachi, Ltd.). The cross-sectional shape of the pattern was judged to be either "rectangular," "tapered," "slightly tapered," "reverse tapered," or "slightly reverse tapered." The cross-sectional shape is preferably rectangular.

[0397] The results are shown in Tables 13 and 14.

[0398]

[0399]

[0400] <Pattern Forming Method (4): EUV Exposure, Organic Solvent Development (Negative), Examples 4-1 to 4-41, Comparative Examples X4-1 to X4-5> ​​An underlayer film-forming composition AL412 (manufactured by Brewer Science) was applied to a silicon wafer and baked at 205°C for 60 seconds to form an underlayer film with a thickness of 20 nm. A resist composition shown in Tables 15 and 16 was applied to the underlayer film and baked at 100°C for 60 seconds to form a resist film with a thickness of 30 nm. Using an EUV exposure system (manufactured by Exitech, Micro Exposure Tool, NA 0.3, Quadrupol, outer sigma 0.68, inner sigma 0.36), the silicon wafer having the resulting resist film was subjected to pattern irradiation. A mask with a line size of 25 nm and a line:space ratio of 1:1 was used as the reticle. The exposed resist film was baked at 90° C. for 60 seconds, developed with n-butyl acetate for 30 seconds, and then spin-dried to obtain a negative pattern.

[0401] The LWR performance and pattern shape were evaluated in the same manner as in the performance evaluation of the above-mentioned pattern formation method (3). The results are shown in Tables 15 and 16.

[0402]

[0403]

[0404] The results in Tables 9 to 16 show that the resist compositions used in the examples were capable of forming patterns with excellent LWR performance and pattern shape.

[0405] The present invention can provide an actinic ray-sensitive or radiation-sensitive resin composition, a resist film, a pattern formation method, and a method for manufacturing an electronic device including the pattern formation method, which are capable of forming a pattern with excellent LWR performance and pattern shape.

[0406] 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 present invention. This application is based on a Japanese patent application (Patent Application No. 2023-170588) filed on September 29, 2023, the contents of which are incorporated herein by reference.

Claims

1. Resin (A) whose polarity increases when exposed to acid, and resin (A) whose polarity increases when exposed to acid (AC) when exposed to actinic rays or radiation. Ｂ１ and an onium salt (B-1) which generates an acid (AC Ｂ２ and an onium salt (B-2) that generates the acid (AC Ｂ１ The pKa of the acid (AC Ｂ２ ), which is 1.0 or more higher than the pKa of the onium salt (B-1), the onium salt (B-1) does not contain a fluorine atom, or, if it contains a fluorine atom, the content of fluorine atoms is 3 mass% or less based on all atoms contained in the onium salt (B-1), the onium salt (B-2) does not contain a fluorine atom, or, if it contains a fluorine atom, the content of fluorine atoms is 3 mass% or less based on all atoms contained in the onium salt (B-2), the onium salt (B-1) is at least one selected from the group consisting of onium salts represented by the following formula (b1-1) and onium salts represented by the following formula (b1-2), and the onium salt (B-2) is an onium salt represented by the following formula (b2-1). In formula (b1-1) and formula (b1-2), R １１ represents an organic group. １２ represents a single bond or a divalent linking group. １１ － Ha-O － , -COO － , -SO ３ － Or -SO ２ N － Y １１ (R １１１ ) ｋ Represents R １１１ represents an alkyl group, a cycloalkyl group, or an aryl group. １１ is -CO-, -SO-, -SO ２ k represents 0 or 1. When k represents 0, R １１１ does not exist, and Y １１ is R １１ When k is 1, R １１１ is R １１ It may be bonded to X １２ － Ha-O － , -COO － , -SO ３ － Or -SO ２ N － Y １２ (R １１２ ) ｈ Represents １１２ represents an alkyl group, a cycloalkyl group, or an aryl group. １２ is -CO-, -SO-, -SO ２ - or a single bond. h represents 0 or 1. When h represents 0, R １１２ does not exist, and Y １２ Is L １２ Or Z １２ ＋ When h is 1, R １１２ Is L １２ Or Z １２ ＋ Z may be bonded to １１ ＋ represents an organic cation. １２ ＋ represents an organic cation group. １１ -X １１ － does not represent an anion represented by any of the following formulas (i)-1 to (i)-3. In formula (b2-1), R ２ａ represents an electron-withdrawing group. ２ｂ and R ２ｃ R each independently represents a hydrogen atom or an organic group. ２ａ , R ２ｂ and R ２ｃ may be bonded to form a ring. ２ｂ and R ２ｃ and Z do not both represent hydrogen atoms. ２ ＋ represents an organic cation.

2. R in the above formula (b2-1) ２ａ The actinic ray-sensitive or radiation-sensitive resin composition according to claim 1 , wherein represents a cyano group, a nitro group, a dicyanomethyl group, or a group represented by the following formula (1A): In formula (1A), Y １ and Y ３ Each independently represents -O- or -NR ３ - represents. ３ represents a hydrogen atom or an alkyl group. ２ is -C(=O)- or -SO ２ - represents. ４ represents an alkyl group, a cycloalkyl group, or an aryl group. ３ and R ４ At least two selected from the group consisting of may be bonded to form a ring. p and r each independently represent 0 or 1. q represents 1 or 2. * represents the bonding position.

3. The actinic ray-sensitive or radiation-sensitive resin composition according to claim 1, wherein the onium salt (B-1) is at least one selected from the group consisting of onium salts represented by any of the following formulas (b1-2a) to (b1-2e) and the onium salt represented by the formula (b1-2): In formula (b1-2a), R ２１ａ ~R ２１ｅ Each independently represents a hydrogen atom or an organic group. ２１ｃ and R ２１ｄ At least one selected from the group consisting of a cyano group, a nitro group, a group represented by the following formula (2A) and a group represented by the following formula (2B), R ２１ａ and R ２１ｂ does not represent a group selected from the group consisting of a cyano group, a nitro group, a group represented by the following formula (2A), and a group represented by the following formula (2B). ２１ represents a single bond or a divalent linking group. ２１ represents an integer of 1 to 4. ２１ When R represents an integer of 2 or more, a plurality of R ２１ｃ may be the same or different, and multiple R ２１ｄ may be the same or different. ２１ａ , R ２１ｂ , R ２１ｃ , R ２１ｄ and L ２１ At least two selected from the group consisting of may be bonded to form a ring. １１ ＋ represents an organic cation. In formula (2A), Y ２１ａ and Y ２２ａ Each independently represents -O- or -NR ３２ａ - represents. ３２ａ represents a hydrogen atom or an alkyl group. ４２ａ represents an alkyl group, a cycloalkyl group, or an aryl group. ２１ａ and r ２１ａ Each independently represents 0 or 1. ２１ａ and r ２１ａ Both do not represent 0. ２１ａ represents 1 or 2. * represents a bonding position. In formula (2B), Y ２１ｂ and Y ２２ｂ Each independently represents -O- or -NR ３２ｂ - represents. ３２ｂ represents a hydrogen atom or an alkyl group. ４２ｂ represents an alkyl group, a cycloalkyl group, or an aryl group. ２１ｂ and r ２１ｂ Each independently represents 0 or 1. * represents a bonding position. In formula (b1-2b), R ２２ａ represents an organic group other than a halogen atom, a hydroxyl group, or a carboxyl group. １２ represents an aromatic group. １２ represents an integer of 0 or more. １２ When R represents an integer of 2 or more, a plurality of R ２２ａ may be the same or different. １１ ＋ represents an organic cation. １３ represents an aromatic group. ２３ａ represents a halogen atom or an organic group. １３ and q １３ Each independently represents an integer of 0 or more. １３ When R represents an integer of 2 or more, a plurality of R ２３ａ may be the same or different, provided that p １３ and q １３ Both do not represent 0. １３ If represents 1, then p １３ represents an integer of 1 or more. １１ ＋ represents an organic cation. ２４ａ represents an organic group. ２４ａ When has an aromatic ring, the —COO － The carbon atom of Z is not directly bonded to the aromatic ring. １１ ＋ represents an organic cation. ２５ａ is -CO-, -SO-, -SO ２ R represents - or a single bond. ２５ａ and R ２５ｂ R each independently represents an alkyl group, a cycloalkyl group, or an aryl group. ２５ａ and R ２５ｂ may be bonded to form a ring. １１ ＋ represents an organic cation.

4. The actinic ray-sensitive or radiation-sensitive resin composition according to claim 1, further comprising a resin (D) different from the resin (A), provided that the resin (D) satisfies the following requirement (i): (i) the SP value of the resin (D) is smaller than the SP value of the resin (A) and is 17.2 or less.

5. The actinic ray-sensitive or radiation-sensitive resin composition according to claim 1, wherein the onium salt (B-1) does not contain a fluorine atom.

6. The actinic ray-sensitive or radiation-sensitive resin composition according to claim 1, wherein the onium salt (B-2) does not contain a fluorine atom.

7. The actinic ray-sensitive or radiation-sensitive resin composition according to claim 1, wherein the resin (A) has a repeating unit represented by the following formula (AP-1): In formula (AP-1), R Ａ１１ represents a hydrogen atom, a halogen atom or an alkyl group. Ａ１１ R represents a single bond or a divalent linking group. Ａ１２ SO ２ represents a cyclic group containing a group.

8. The actinic ray-sensitive or radiation-sensitive resin composition according to claim 1, wherein the resin (A) has a repeating unit represented by the following formula (AP-2): In formula (AP-2), R Ａ２１ represents a hydrogen atom, a halogen atom or an alkyl group. Ａ２１ R represents a single bond or a divalent linking group. Ａ２２ represents an alkyl group.

9. The actinic ray-sensitive or radiation-sensitive resin composition according to claim 1, wherein the resin (A) has a repeating unit represented by the following formula (AP-3): In formula (AP-3), R Ａ３１ represents a hydrogen atom, a halogen atom or an alkyl group. Ａ３１ R represents a single bond or a divalent linking group. Ａ３２ R represents an alicyclic hydrocarbon group. Ａ３３ represents a substituent having a double bond.

10. The actinic ray-sensitive or radiation-sensitive resin composition according to claim 4, further satisfying both of the following requirements (ii) and (iii): (ii) the total content of repeating units not containing a fluorine atom among the repeating units contained in the resin (D) is 80 mol % or more based on all repeating units in the resin (D), and (iii) the content of the resin (D) is 0.01 to 10 mass % based on the total solid content in the actinic ray-sensitive or radiation-sensitive resin composition.

11. A resist film formed using the actinic ray-sensitive or radiation-sensitive resin composition according to any one of claims 1 to 10.

12. A pattern forming method comprising the steps of forming a resist film on a substrate using the actinic ray-sensitive or radiation-sensitive resin composition according to any one of claims 1 to 10, exposing the resist film to light, and developing the exposed resist film using a developer.

13. A method for manufacturing an electronic device, comprising the pattern formation method according to claim 12.

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