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

Abstract

The present invention provides a pattern-forming method comprising: (1) a step of polymerizing at least a compound having a specific structure and a monomer having an acid-decomposable group to obtain a polymer (Q); (2) a step of decomposing the polymer (Q) by the action of an acid or a base to obtain a polymer (P); (3) a step of obtaining an actinic ray-sensitive or radiation-sensitive resin composition containing the polymer (P), a photoacid generator and a solvent; (4) a step of forming a film using the actinic ray-sensitive or radiation-sensitive resin composition; (5) a step of exposing the film; and (6) a step of developing the exposed film with an organic processing liquid containing butyl acetate and a hydrocarbon having a carbon number (9) to (12) inclusive. The present invention also provides an electronic device production method comprising the above-described pattern-forming method.　The present invention also provides an actinic ray-sensitive or radiation-sensitive resin composition comprising a resin (A) containing a repeating unit (a) having an acid-decomposable group, a compound (B) that generates an acid upon irradiation with actinic rays or radiation, a solvent, and a crosslinking agent, wherein the repeating unit (a) content in the resin (A) is (40) mol% or more relative to the total repeating unit of the resin (A). The present invention also provides a resist film formed of the actinic ray-sensitive or radiation-sensitive resin composition, a pattern-forming method using the actinic ray-sensitive or radiation-sensitive resin composition, and a method for producing an electronic device.

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 method for producing a resist pattern by forming a composition layer using a resist composition containing a specific compound, an acid-decomposable resin, and a photoacid generator, exposing the composition layer to electron beams, and developing the composition layer with butyl acetate.

[0005] Patent Document 2 describes a photosensitive resin composition containing a polyhydroxystyrene resin, a photoacid generator, and a methylol-type crosslinking agent, in which some of the phenolic hydroxyl groups in the polyhydroxystyrene resin are protected with acetal-type protecting groups, and the methylol-type crosslinking agent is a compound having two or more groups selected from a methylol group, an alkoxymethyl group, and an acyloxymethyl group in the molecule.

[0006] Japanese Patent Publication No. 2022-41917 International Publication No. 2024 / 053579

[0007] Recently, with the trend toward finer patterns, the performance required of pattern formation methods has become increasingly higher.

[0008] Furthermore, as in Patent Document 2, when a pattern is formed using a resist composition containing a resin including a repeating unit having an acid-decomposable group, a compound (photoacid generator) that generates an acid upon irradiation with actinic rays or radiation, and a crosslinking agent, the number of defects can increase due to unintended crosslinking reactions occurring in weakly exposed regions, particularly in negative patterning. A weakly exposed region is a region with a low exposure dose, and is a portion where pattern formation is not intended in the design. For example, a weakly exposed region can occur near the boundary between an exposed portion and an unexposed portion.

[0009] An object of a first aspect of the present invention is to provide a pattern formation method with excellent resolution, and a method for manufacturing an electronic device that includes the pattern formation method.

[0010] An object of a second aspect of the present invention is to provide an actinic ray-sensitive or radiation-sensitive resin composition capable of suppressing the occurrence of defects, a resist film formed from the actinic ray-sensitive or radiation-sensitive resin composition, a pattern formation method using the actinic ray-sensitive or radiation-sensitive resin composition, and a method for manufacturing an electronic device.

[0011] The present inventors have found that the above problems can be solved by the following configuration.

[0012] [1] (1) a step of polymerizing at least a compound represented by formula (i) and a monomer having an acid-decomposable group to obtain a polymer (Q);

[0013]

[0014] In formula (i), X １ represents a hydrogen atom or a substituent. １ represents a single bond or a divalent linking group. Ar represents an aromatic ring group. R Ｘ represents a group that is eliminated by the action of an acid or a base. n1 represents an integer of 1 or more. When n1 represents an integer of 2 or more, a plurality of R Ｘ may be the same or different, and multiple R Ｘ may be bonded to form a ring. Ｘ R in Ｘ is another -O-R Ｘ R in Ｘ (2) a step of decomposing the polymer (Q) by the action of an acid or a base to obtain a polymer (P) having a repeating unit represented by formula (ii);

[0015]

[0016] In formula (ii), X １ , L １ , Ar and n1 are each X in formula (i). １ , L １ , Ar and n1 have the same meanings as those of n1 and n2. A pattern forming method comprising: (3) a step of obtaining an actinic ray-sensitive or radiation-sensitive resin composition containing the polymer (P), a photoacid generator and a solvent; (4) a step of forming a film using the actinic ray-sensitive or radiation-sensitive resin composition; (5) a step of exposing the film; and (6) a step of developing the exposed film with an organic processing liquid containing butyl acetate and a hydrocarbon having from 9 to 12 carbon atoms. [2] L in the above formulas (i) and (ii) １[3] The pattern forming method according to [1] or [2], wherein in the step (2), the polymer (Q) is decomposed by the action of a base to obtain the polymer (P). [4] The pattern forming method according to [1] or [2], wherein R in the formula (i) represents a single bond. Ｘ [5] The pattern forming method according to any one of [1] to [3], wherein in the step (2), the polymer (Q) is decomposed by the action of an acid to obtain the polymer (P). [6] The pattern forming method according to any one of [1] to [4], wherein R in the formula (i) Ｘ The pattern forming method according to any one of [1] to [5], wherein Rx represents a group represented by any one of formulas (Y1) to (Y4): 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 １ In formula (Y1) and formula (Y2), Rx １ ~Rx ３ Rx each independently represents an alkyl group, a cycloalkyl group, an alkenyl group, or an aryl group. １ ~Rx ３ In formula (Y3), two of R may be bonded to form a ring. ３６ ~R ３８ R each independently represents a hydrogen atom or a monovalent organic group. ３７ and R ３８ may be bonded to form a ring. １ represents an aromatic ring group. Rn represents an alkyl group, a cycloalkyl group, or an aryl group. Rn and Ar １and may be bonded to form a non-aromatic ring. [7] The pattern forming method according to any one of [1] to [6], wherein the polymer (Q) contains a repeating unit having at least one selected from the group consisting of a lactone group, a sultone group, a carbonate group, a sulfonyl group, an alcoholic hydroxyl group, and a carboxy group. [8] The pattern forming method according to any one of [1] to [7], wherein the content of the photoacid generator is 10% by mass or more based on the total solid content of the actinic ray-sensitive or radiation-sensitive resin composition. [9] The pattern forming method according to any one of [1] to [8], wherein the polymer (P) contains repeating units having an acid-decomposable group in an amount of more than 50 mol% based on the total repeating units.

[10] The pattern forming method according to any one of [1] to [9], wherein the photoacid generator contains a fluorine atom or an iodine atom.

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

[10] , wherein the photoacid generator contains a cation having a fluorine atom.

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

[11] , wherein the photoacid generator contains an anion having an iodine atom.

[13] A method for manufacturing an electronic device, comprising the pattern formation method according to any one of [1] to

[12] .

[0017]

[14] An actinic ray-sensitive or radiation-sensitive resin composition comprising a resin (A) containing a repeating unit (a) having an acid-decomposable group, a compound (B) that generates an acid upon irradiation with actinic rays or radiation, a solvent, and a crosslinking agent, wherein the content of the repeating unit (a) in the resin (A) is 40 mol % or more based on all repeating units of the resin (A).

[15] The actinic ray-sensitive or radiation-sensitive resin composition according to

[14] , wherein the content of the repeating unit (a) in the resin (A) is 50 mol % or more based on all repeating units of the resin (A).

[16] The actinic ray-sensitive or radiation-sensitive resin composition according to

[14] or

[15] , wherein the content of the repeating unit (a) in the resin (A) is 55 mol % or more based on all repeating units of the resin (A).

[17] The actinic ray-sensitive or radiation-sensitive resin composition according to any one of

[14] to

[16] , wherein the repeating unit (a) has a structure in which a carboxy group is protected by a group that is cleaved by the action of an acid.

[18] The actinic ray-sensitive or radiation-sensitive resin composition according to any one of

[14] to

[17] , wherein the resin (A) contains a repeating unit represented by the following formula (b-1):

[0018]

[0019] In formula (b-1), R １１ , R １２ and R １３ each independently represents a hydrogen atom, an alkyl group, a halogen atom, a cyano group, or an alkoxycarbonyl group. １ is a single bond, —COO— or —CONR ｍ１ - represents. ｍ１ represents a hydrogen atom or an alkyl group. ｍ１ and R １２ and may be bonded to each other to form a ring. １ represents a single bond or an alkylene group. １ and R １２ may be bonded to each other to form a ring. １ represents an aromatic group. １ and R １２may be bonded to each other to form a ring. n represents an integer of 1 to 4.

[19] The actinic ray-sensitive or radiation-sensitive resin composition according to any one of

[14] to

[18] , wherein the compound (B) contains a cation having a halogen atom.

[20] The actinic ray-sensitive or radiation-sensitive resin composition according to any one of

[14] to

[19] , wherein the compound (B) contains an anion having an iodine atom.

[21] The actinic ray-sensitive or radiation-sensitive resin composition according to any one of

[14] to

[20] , wherein the content of the resin (A) is 75 mass% or less based on the total solid content in the actinic ray-sensitive or radiation-sensitive resin composition.

[22] The actinic ray-sensitive or radiation-sensitive resin composition according to any one of

[14] to

[21] , wherein the compound (B) is at least one selected from the group consisting of the following compound (I) and the following compound (II): Compound (I): A compound having one or more structural moieties Z1 and one or more structural moieties Z2, which satisfies the following condition (I). When compound (I) has two or more structural moieties Z1, the two or more structural moieties Z1 may be the same or different, and when compound (I) has two or more structural moieties Z2, the two or more structural moieties Z2 may be the same or different. Condition (I): Structural moieties Z1 and Z2 are structural moieties that generate an acid upon irradiation with actinic rays or radiation, and the acid generated from structural moiety Z1 is stronger than the acid generated from structural moiety Z2. Compound (II): A compound having two or more structural moieties Z1 and one or more structural moieties Z3, which generates an acid containing two or more acidic moieties derived from structural moiety Z1 and structural moiety Z3 upon irradiation with actinic rays or radiation. The two or more structural moieties Z1 in compound (II) may be the same or different.

[23] The actinic ray-sensitive or radiation-sensitive resin composition according to any one of

[14] to

[22] , wherein the resin (A) has a weight average molecular weight of not more than 20,000.

[24] The actinic ray-sensitive or radiation-sensitive resin composition according to any one of

[14] to

[23] , wherein the crosslinking agent has at least one group selected from the group consisting of a methylol group and a methoxymethyl group.

[25] The actinic ray-sensitive or radiation-sensitive resin composition according to any one of

[14] to

[24] , wherein the crosslinking agent has at least two groups selected from the group consisting of a methylol group and a methoxymethyl group.

[26] The actinic ray-sensitive or radiation-sensitive resin composition according to any one of

[14] to

[25] , wherein the content of the crosslinking agent is 0.5% by mass or less, relative to the actinic ray-sensitive or radiation-sensitive resin composition.

[27] The actinic ray-sensitive or radiation-sensitive resin composition according to any one of

[14] to

[26] , wherein the content of the crosslinking agent is 0.3% by mass or less, relative to the actinic ray-sensitive or radiation-sensitive resin composition.

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

[14] to

[27] .

[29] A pattern forming method comprising the steps of forming a resist film using the actinic ray-sensitive or radiation-sensitive resin composition according to any one of

[14] to

[27] , exposing the resist film to light, and developing the exposed resist film with a developer.

[30] The pattern forming method according to

[29] , wherein the developer contains an organic solvent, and the formed pattern is a negative pattern.

[31] A method for producing an electronic device, comprising the pattern forming method according to

[29] or

[30] .

[0020] According to a first aspect of the present invention, it is possible to provide a pattern formation method with excellent resolution, and a method for manufacturing an electronic device including the pattern formation method.

[0021] According to a second aspect of the present invention, it is possible to provide an actinic ray-sensitive or radiation-sensitive resin composition capable of suppressing the occurrence of defects, a resist film formed from the actinic ray-sensitive or radiation-sensitive resin composition, a pattern formation method using the actinic ray-sensitive or radiation-sensitive resin composition, and a method for manufacturing an electronic device.

[0022] The first aspect of the present invention will be described in detail below. The following description of the components may be based on representative embodiments of the present invention, but the present invention is not limited to such embodiments.

[0023] 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.

[0024] 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.

[0025] 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 (polymer) 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).

[0026] 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:

[0027] (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, an acryloyl group, a methacrylate group, a methyl ... Examples of the substituent T include acyl groups such as thiazolyl and methoxalyl groups; sulfanyl groups; alkylsulfanyl groups such as methylsulfanyl and tert-butylsulfanyl groups; arylsulfanyl groups such as phenylsulfanyl and p-tolylsulfanyl groups; alkylsulfonyl groups; arylsulfonyl groups; alkyl groups; alkenyl groups; cycloalkyl groups; aryl groups; heteroaryl groups; hydroxy groups; carboxyl groups; formyl groups; sulfo groups; cyano groups; alkylaminocarbonyl groups; arylaminocarbonyl groups; sulfonamide groups; silyl groups; amino groups; carbamoyl groups; etc. 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.).

[0028] 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".

[0029] 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).

[0030] 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.

[0031] 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.

[0032] In this specification, the term "solid content" refers to components contained in the actinic ray-sensitive or radiation-sensitive resin composition and that form an actinic ray-sensitive or radiation-sensitive film, and does not include solvents. Furthermore, any component contained in the actinic ray-sensitive or radiation-sensitive resin composition and that forms an actinic ray-sensitive or radiation-sensitive film is considered to be a solid content even if it is in a liquid state.

[0033] <Pattern Forming Method> The pattern forming method of the present invention includes: (1) a step of polymerizing at least a compound represented by formula (i) and a monomer having an acid-decomposable group to obtain a polymer (Q);

[0034]

[0035] In formula (i), X １ represents a hydrogen atom or a substituent. １ represents a single bond or a divalent linking group. Ar represents an aromatic ring group. R Ｘ represents a group that is eliminated by the action of an acid or a base. n1 represents an integer of 1 or more. When n1 represents an integer of 2 or more, a plurality of R Ｘ may be the same or different, and multiple R Ｘ may be bonded to form a ring. Ｘ R in Ｘ is another -O-R Ｘ R in Ｘ (2) a step of decomposing the polymer (Q) by the action of an acid or a base to obtain a polymer (P) having a repeating unit represented by formula (ii);

[0036]

[0037] In formula (ii), X １ , L １ , Ar and n1 are each X in formula (i). １ , L １, Ar and n1 have the same meaning as Ar and n2. The pattern forming method includes: (3) a step of obtaining an actinic ray-sensitive or radiation-sensitive resin composition containing the polymer (P), a photoacid generator and a solvent; (4) a step of forming a film using the actinic ray-sensitive or radiation-sensitive resin composition; (5) a step of exposing the film; and (6) a step of developing the exposed film with an organic treatment liquid containing butyl acetate and a hydrocarbon having from 9 to 12 carbon atoms.

[0038] Although the details of the mechanism by which the pattern forming method of the present invention exhibits excellent resolution are unclear, the inventors speculate as follows. However, the present invention is not limited by the following speculated mechanism. It is believed that when a pattern is formed by an organic solvent development process using a resist composition, the developer may penetrate into and swell the resist film formed using the resist composition, which may result in an inability to achieve the expected resolution. In the present invention, the use of an organic treatment liquid containing butyl acetate and a hydrocarbon having 9 to 12 carbon atoms as the developer is believed to suppress penetration and swelling of the developer into the resist film, thereby improving resolution. Furthermore, resins (polymers) having phenolic hydroxyl groups are often used as components of resist compositions. However, if a polymer obtained by polymerizing a monomer having a phenolic hydroxyl group is used as the resin having a phenolic hydroxyl group, the oligomer component having a phenolic hydroxyl group generated during polymerization may become a penetration site for the developer, preventing the expected resolution from being achieved. In the present invention, a polymer obtained by polymerizing a monomer in which the phenolic hydroxyl group is protected with a leaving group and then eliminating the leaving group is used. This is thought to reduce the generation of oligomer components having phenolic hydroxyl groups that serve as penetration sites for the developer, thereby improving the resolution.

[0039] Each of the above steps will be described in detail below.

[0040] [Step (1)] Step (1) is a step of polymerizing at least a compound represented by formula (i) and a monomer having an acid-decomposable group to obtain a polymer (Q). The compound represented by formula (i) and the monomer having an acid-decomposable group may be the same compound or different compounds. In step (1), in addition to the compound represented by formula (i) and the monomer having an acid-decomposable group, other monomers may also be polymerized.

[0041] (Compound Represented by Formula (i)) The compound represented by formula (i) will be described.

[0042]

[0043] In formula (i), X １ represents a hydrogen atom or a substituent. １ represents a single bond or a divalent linking group. Ar represents an aromatic ring group. R Ｘ represents a group that is eliminated by the action of an acid or a base. n1 represents an integer of 1 or more. When n1 represents an integer of 2 or more, a plurality of R Ｘ may be the same or different, and multiple R Ｘ may be bonded to form a ring. Ｘ R in Ｘ is another -O-R Ｘ R in Ｘ It may also serve as both.

[0044] X in formula (i) １ The substituent represented by is not particularly limited, but is preferably an alkyl group, a cycloalkyl group, a halogen atom, a cyano group, or an alkoxycarbonyl group. １ The alkyl group represented by may be either linear or branched. The number of carbon atoms in the alkyl group is not particularly limited, but is preferably 1 to 10, more preferably 1 to 5, and particularly preferably 1 to 3. Examples of the alkyl group include a methyl group, an ethyl group, an n-propyl group, an isopropyl group, an n-butyl group, an isobutyl group, and a t-butyl group. The alkyl group may have a substituent. X １The number of carbon atoms in the cycloalkyl group represented by is not particularly limited, but is preferably 3 to 20, and more preferably 5 to 15. 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 cycloalkyl group may have a substituent. X １ Examples of the halogen atom represented by X include a fluorine atom, a chlorine atom, a bromine atom, and an iodine atom, and a fluorine atom or an iodine atom is preferred. １ The alkyl group contained in the alkoxycarbonyl group represented by the formula (I) may be either linear or branched. The number of carbon atoms in the alkyl group contained in the alkoxycarbonyl group is not particularly limited, but is preferably 1 to 5, and more preferably 1 to 3. The alkoxycarbonyl group may have a substituent.

[0045] X １ preferably represents a hydrogen atom or an alkyl group, and more preferably represents a hydrogen atom.

[0046] L in formula (i) １ represents a single bond or a divalent linking group. １ The divalent linking group represented by is not particularly limited, but examples thereof include -COO-, -CONR ａ -, an alkylene group, or a group formed by combining two or more of these groups. ａ represents a hydrogen atom or an alkyl group. The alkylene group 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. The alkylene group may have a substituent. R ａ Examples of the alkyl group represented by 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.

[0047] L １ preferably represents a single bond or —COO—, and more preferably represents a single bond.

[0048] In formula (i), Ar represents an aromatic ring group. The aromatic ring group represented by Ar may be an aromatic hydrocarbon group or an aromatic heterocyclic group. The aromatic hydrocarbon group is preferably a group containing an aromatic hydrocarbon having 6 to 18 carbon atoms, such as benzene, naphthalene, anthracene, or naphthacene. 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 aromatic heterocyclic group is preferably a group containing an aromatic heterocycle having 4 to 20 ring atoms, such as thiophene, furan, pyridine, pyrrole, benzothiophene, benzofuran, benzopyrrole, triazine, imidazole, benzimidazole, triazole, thiadiazole, or thiazole.

[0049] The aromatic ring group represented by Ar is —O—R Ｘ and may further have other substituents.

[0050] Ar preferably represents an aromatic hydrocarbon group, more preferably a benzene ring group or a naphthalene ring group, and even more preferably a benzene ring group.

[0051] R in formula (i) Ｘ represents a group which is eliminated by the action of an acid or a base.

[0052] R in formula (i) Ｘ The group that is eliminated by the action of an acid represented by is not particularly limited, but examples thereof include groups represented by any of formulae (Y1) to (Y4). Ｘ In a preferred embodiment of the present invention, R represents a group represented by any one of formulas (Y1) to (Y4). Ｘ More preferably, represents a group represented by any one of formulas (Y1) to (Y3). 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 ) (OR３８ ) Formula (Y4): -C(Rn)(H)(Ar １ )

[0053] In formula (Y1) and formula (Y2), Rx １ ~Rx ３ Rx each independently represents an alkyl group, a cycloalkyl group, an alkenyl group, or an aryl group. １ ~Rx ３ In formula (Y3), two of R may be bonded to form a ring. ３６ ~R ３８ R each independently represents a hydrogen atom or a monovalent organic group. ３７ and R ３８ may be bonded to form a ring. １ represents an aromatic ring group. Rn represents an alkyl group, a cycloalkyl group, or an aryl group. Rn and Ar １ may be bonded to form a non-aromatic ring.

[0054] 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 Preferably, at least two of Rx are methyl groups. １ ~Rx ３ Rx preferably each independently represents a linear or branched alkyl group, and more preferably represents a linear alkyl group. １ ~Rx ３ The alkyl group represented by is preferably an alkyl group having 1 to 10 carbon atoms, such as a methyl group, an ethyl group, an n-propyl group, an isopropyl group, an n-butyl group, an isobutyl group, or a t-butyl group, and more preferably an alkyl group having 1 to 5 carbon atoms. １ ~Rx ３The cycloalkyl group represented by Rx 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. １ ~Rx ３ The cycloalkyl group represented by Rx is preferably a cycloalkyl group having 3 to 20 carbon atoms, more preferably a cycloalkyl group having 4 to 15 carbon atoms. １ ~Rx ３ The aryl group represented by Rx is preferably an aryl group having 6 to 20 carbon atoms, more preferably an aryl group having 6 to 10 carbon atoms. １ ~Rx ３ Examples of the aryl group represented by Rx include a phenyl group, a naphthyl group, and an anthryl group. １ ~Rx ３ The alkenyl group represented by is preferably an alkenyl group having 2 to 10 carbon atoms, more preferably an alkenyl group having 2 to 5 carbon atoms. １ ~Rx ３ The alkenyl group represented by the formula (I) is, for example, a vinyl group.

[0055] Rx １ ~Rx ３ Two of Rx may be bonded to form a ring (which may be a monocyclic or polycyclic ring). １ ~Rx ３ The ring formed by combining two of Rx is preferably a cycloalkyl group. １ ~Rx ３ The cycloalkyl group formed by combining two of these 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, but is preferably a monocyclic cycloalkyl group having 5 to 6 carbon atoms. １ ~Rx ３In the cycloalkyl group formed by bonding two of the above, one or more of the methylene groups constituting the cycloalkane 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 are preferably bonded to form the above-mentioned cycloalkyl group.

[0056] When the actinic ray-sensitive or radiation-sensitive resin composition prepared in step (3) of the present invention is, for example, a resist composition for EUV exposure, Rx 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.

[0057] In formula (Y3), R ３６ ~R ３８ R each independently represents a hydrogen atom or a monovalent organic group. ３７ and R ３８ may be bonded to form a ring. ３６ ~R ３８ Examples of the monovalent organic group represented by R 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 at least one heteroatom such as an oxygen atom and 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 at least one heteroatom such as an oxygen atom and a group containing a heteroatom such as a carbonyl group.

[0058] When the actinic ray-sensitive or radiation-sensitive resin composition prepared in step (3) of the present invention is, for example, a resist composition for EUV exposure, R 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 of further has a fluorine atom or an iodine atom as a substituent.

[0059] Formula (Y3) is preferably a group represented by the following formula (Y3-1).

[0060]

[0061] Here, L Ｙ１ and L Ｙ２ each independently represents a hydrogen atom, an alkyl group, a cycloalkyl group, an aryl group, or a group formed by combining these (for example, a group formed by combining an alkyl group and an aryl group). Ｙ１ represents a single bond or a divalent linking group. Ｙ１ represents an alkyl group which may contain a heteroatom, a cycloalkyl group which may contain a heteroatom, an aryl group which may contain a heteroatom, an amino group, an ammonium group, a mercapto group, a cyano group, an aldehyde group, or a group which combines these (for example, a group which combines an alkyl group and a cycloalkyl group). In the alkyl group and the cycloalkyl group, for example, one or more methylene groups may be replaced with a heteroatom such as an oxygen atom, or a group which contains a heteroatom such as a carbonyl group. Ｙ１ and L Ｙ２ Preferably, one of Q 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. Ｙ１ , M Ｙ１ , and L Ｙ１ At least two of the groups may be bonded to form a ring (preferably a 5- or 6-membered ring). Ｙ２is 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 high, thereby ensuring film strength and suppressing fogging. In formula (Y3-1), * represents a bonding position.

[0062] In formula (Y4), Ar １ represents an aromatic ring group. Rn represents an alkyl group, a cycloalkyl group, or an aryl group. Rn and Ar １ Ar may be bonded to form a non-aromatic ring. １ preferably represents an aryl group.

[0063] R in formula (i) Ｘ The group represented by the formula (i) that is eliminated by the action of a base is not particularly limited, but examples thereof include an acyl group. Ｘ In a preferred embodiment of the present invention, R represents an acyl group. ＸThe acyl group represented by is preferably an alkylcarbonyl group, a cycloalkylcarbonyl group, or an arylcarbonyl group. The alkyl group in the alkylcarbonyl group may be linear or branched, and examples thereof include alkyl groups having 1 to 10 carbon atoms. The alkyl group in the alkylcarbonyl group is preferably an alkyl group having 1 to 6 carbon atoms, and more preferably an alkyl group having 1 to 3 carbon atoms. The cycloalkyl group in the cycloalkylcarbonyl 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 cycloalkyl group in the cycloalkylcarbonyl group preferably has 3 to 20 carbon atoms, and more preferably has 4 to 15 carbon atoms. The aryl group in the arylcarbonyl group may be a monocyclic or a polycyclic aryl group, and examples thereof include aryl groups having 6 to 20 carbon atoms. The aryl group in the arylcarbonyl group is preferably an aryl group having 6 to 10 carbon atoms, more preferably a phenyl group or a naphthyl group, and even more preferably a phenyl group.

[0064] In formula (i), n1 represents an integer of 1 or more, preferably an integer of 1 to 5, more preferably an integer of 1 to 3, and even more preferably 1 or 2.

[0065] When n1 represents an integer of 2 or more, a plurality of R Ｘ may be the same or different, and multiple R Ｘ may be bonded to form a ring. Ｘ R in Ｘ is another -O-R Ｘ R in Ｘ "One -O-R Ｘ R in Ｘ is another -O-R Ｘ R in Ｘ "Combined with" means one R Ｘ represents that the oxygen atom is bonded to two or more oxygen atoms bonded to Ar. Ｘ R in Ｘ is another -O-RＸ R in Ｘ An example of an embodiment having both functions is a compound represented by formula (i-2).

[0066]

[0067] In formula (i-2), X １ , L １ and Ar are each X in formula (i). １ , L １ and Ar have the same meaning. Ｘ represents a group (divalent group) that is eliminated by the action of an acid or a base. Ｘ As for R Ｘ A group obtained by removing one hydrogen atom from is preferred.

[0068] Among the compounds represented by formula (i), R Ｘ Specific examples of groups which are cleaved by the action of an acid are shown below, but are not limited to these.

[0069]

[0070] Among the compounds represented by formula (i), R Ｘ Specific examples of the group which is eliminated by the action of a base are shown below, but are not limited to these.

[0071]

[0072] The amount of the compound represented by formula (i) used is not particularly limited, but is preferably 1 mol% or more, more preferably 5 mol% or more, and even more preferably 10 mol% or more, based on all the monomers used in the synthesis of polymer (Q). The amount of the compound represented by formula (i) used is 100 mol% or less, or may be 90 mol% or less, or may be 80 mol% or less, based on all the monomers used in the synthesis of polymer (Q). The compound represented by formula (i) used may be one type, or two or more types. When two or more types of compounds represented by formula (i) are used, it is preferable that the total amount used is within the above range.

[0073] (Monomer Having Acid-Decomposable Group) A monomer having an acid-decomposable group will be described. By polymerizing a monomer having an acid-decomposable group, an acid-decomposable group can be introduced into the polymer (Q). The monomer having an acid-decomposable group may be the same compound as the compound represented by the above formula (i), or may be a different compound. For example, among the compounds represented by the above formula (i), R Ｘ represents a group that is eliminated by the action of an acid, the monomer also has an acid-decomposable group. Ｘ represents a group that is eliminated by the action of an acid, and may have an acid-decomposable group separately. Ｘ Even when represents a group that is eliminated by the action of a base, it may additionally have an acid-decomposable group.

[0074] The acid-decomposable group is a group that decomposes under the action of an acid and increases its polarity. The acid-decomposable group preferably has a structure in which a polar group is protected by a group (leaving group) that leaves under the action of an acid. The acid-decomposable group is preferably a group that decomposes under the action of an acid to generate a polar group. Examples of the polar group include acidic groups 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, an (alkylsulfonyl) (alkylcarbonyl) methylene group, an (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 a tris(alkylsulfonyl) methylene group, as well as an alcoholic hydroxyl group. Of 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.

[0075] Examples of the group that is eliminated by the action of an acid include groups represented by any of the above formulae (Y1) to (Y4).

[0076] 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.

[0077] As an embodiment in which the compound represented by formula (i) is also a monomer having an acid-decomposable group, an embodiment in which Ar in formula (i) has a group represented by formula (Y2) above is preferred.

[0078] The monomer having an acid-decomposable group may be a compound represented by formula (MA1).

[0079]

[0080] In formula (MA1), L ｍ１ represents a divalent linking group, R ｍ１ represents a hydrogen atom, a fluorine atom, an iodine atom, an alkyl group, or an aryl group; R ｍ２ represents a group that is eliminated by the action of an acid.

[0081] L ｍ１ Examples of the divalent linking group represented by the formula: ２ Examples of the alkylene group include alkylene groups (e.g., alkylene groups, cycloalkylene groups, alkenylene groups, arylene groups, etc.), and linking groups formed by linking a plurality of these groups. The hydrocarbon group may have a substituent. 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 5. The cycloalkylene group may be a monocyclic cycloalkylene group or a polycyclic cycloalkylene group. The number of carbon atoms in the cycloalkylene group is not particularly limited, but is preferably 3 to 20, and more preferably 4 to 15. The alkenylene group may be linear or branched. The number of carbon atoms in the alkenylene group is not particularly limited, but is preferably 2 to 10, and more preferably 2 to 5. The number of carbon atoms in the arylene group is not particularly limited, but is preferably 6 to 20, and more preferably 6 to 10. A phenylene group is particularly preferred as the arylene group.

[0082] R ｍ１The 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. ｍ１ The alkyl group represented by the formula (I) may have a substituent. ｍ１ The number of carbon atoms in the aryl group represented by R is not particularly limited, but is preferably 6 to 10. ｍ１ The aryl group represented by the following formula may have a substituent.

[0083] R ｍ２ Examples of the group that is eliminated by the action of an acid and is represented by the formula (Y1) include groups represented by any of the formulae (Y1) to (Y4).

[0084] L ｍ１ , R ｍ１ and R ｍ２ In another preferred embodiment, at least one of the groups has an iodine atom.

[0085] The monomer having an acid-decomposable group may be a compound represented by formula (AI).

[0086]

[0087] In formula (AI), Xa １ represents a hydrogen atom or an alkyl group. T represents a single bond or a divalent linking group. Rx １ ~Rx ３ Rx each independently represents an alkyl group, a cycloalkyl group, an alkenyl group, or an aryl group. １ ~Rx ３ Two of these may be bonded to form a ring.

[0088] Xa １ The alkyl group represented by may be linear or branched. The number of carbon atoms in the alkyl group is not particularly limited, but is preferably 1 to 10, more preferably 1 to 3. The alkyl group may have a substituent. Examples of the alkyl group include a methyl group or a -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. １１Examples 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 Preferably, represents a hydrogen atom, a methyl group, a trifluoromethyl group, or a hydroxymethyl group.

[0089] Examples of the divalent linking group represented by T include an alkylene group, an aromatic ring group, a -COO-Rt- group, and a -O-Rt- group. Rt represents an alkylene group or a cycloalkylene group. T preferably represents 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.

[0090] Rx １ ~Rx ３ The alkyl group represented by is preferably an alkyl group having 1 to 10 carbon atoms, such as a methyl group, an ethyl group, an n-propyl group, an isopropyl group, an n-butyl group, an isobutyl group, or a t-butyl group, and more preferably an alkyl group having 1 to 5 carbon atoms. １ ~Rx ３ The cycloalkyl group represented by Rx 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. １ ~Rx ３ The cycloalkyl group represented by Rx is preferably a cycloalkyl group having 3 to 20 carbon atoms, more preferably a cycloalkyl group having 4 to 15 carbon atoms. １ ~Rx ３ The aryl group represented by Rx is preferably an aryl group having 6 to 20 carbon atoms, more preferably an aryl group having 6 to 10 carbon atoms. １ ~Rx ３Examples of the aryl group represented by Rx include a phenyl group, a naphthyl group, and an anthryl group. １ ~Rx ３ The alkenyl group represented by is preferably an alkenyl group having 2 to 10 carbon atoms, more preferably an alkenyl group having 2 to 5 carbon atoms. １ ~Rx ３ The alkenyl group represented by the formula (I) is, for example, a vinyl group.

[0091] Rx １ ~Rx ３ Two of Rx may be bonded to form a ring (which may be a monocyclic or polycyclic ring). １ ~Rx ３ The ring formed by combining two of Rx is preferably a cycloalkyl group. １ ~Rx ３ The cycloalkyl group formed by combining two of these 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, but is preferably a monocyclic cycloalkyl group having 5 to 6 carbon atoms. １ ~Rx ３ In a cycloalkyl group formed by bonding two of the above, one or more of the methylene groups constituting the cycloalkane 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.

[0092] Rx １ is a methyl group or an ethyl group, and Rx ２ and Rx ３ In a preferred embodiment of the compound represented by formula (AI),

[0093] 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.

[0094] Xa １ In a preferred embodiment of the compound represented by formula (AI), represents a hydrogen atom or a methyl group, and T represents a single bond.

[0095] Specific examples of the monomer having an acid-decomposable group are shown below, but are not limited to these.

[0096]

[0097] The amount of the monomer having an acid-decomposable group used is not particularly limited, but is preferably 30 mol% or more, more preferably 40 mol% or more, and even more preferably more than 50 mol% based on all the monomers used in the synthesis of polymer (Q). The amount of the monomer having an acid-decomposable group used is 100 mol% or less, or may be 90 mol% or less, or may be 80 mol% or less, based on all the monomers used in the synthesis of polymer (Q). The monomer having an acid-decomposable group used may be one type, or two or more types. When two or more types of monomers having an acid-decomposable group are used, the total amount used is preferably within the above range.

[0098] In step (1), in addition to the compound represented by formula (i) and the monomer having an acid-decomposable group, other monomers may be polymerized to obtain polymer (Q).

[0099] (Other Monomers) The other monomers will be described. The structure of the other monomers is not particularly limited. In the present invention, other monomers may or may not be used when synthesizing polymer (Q). When other monomers are used, the amount of the other monomers used is not particularly limited, but may be 1 mol% or more, 5 mol% or more, or 10 mol% or more, based on all the monomers used in the synthesis of polymer (Q). Furthermore, the amount of the other monomers used may be 50 mol% or less, 40 mol% or less, or 30 mol% or less, based on all the monomers used in the synthesis of polymer (Q). The other monomers used may be one type, or two or more types. When two or more types of other monomers are used, it is preferable that the total amount used is within the above range.

[0100] Examples of other monomers include monomers having at least one group selected from the group consisting of a lactone group, a sultone group, a carbonate group, a sulfonyl group, an alcoholic hydroxyl group, and a carboxy group.

[0101] The lactone group may have a lactone structure. The lactone structure is preferably a 5- to 7-membered lactone structure. The lactone structure is preferably one in which another ring structure is fused to a 5- to 7-membered lactone structure in the form of a bicyclo or spiro structure. Examples of lactone groups include lactone groups formed by removing one or more hydrogen atoms from a ring atom of a lactone structure represented by any of the following formulae (LC1-1) to (LC1-22). The sultone group may have a sultone structure. The sultone structure is preferably a 5- to 7-membered sultone structure. The sultone structure is preferably one in which another ring structure is fused to a 5- to 7-membered sultone structure in the form of a bicyclo or spiro structure. Examples of sultone groups include sultone groups formed by removing one or more hydrogen atoms from a ring atom of a sultone structure represented by any of the following formulae (SL1-1) to (SL1-3). The carbonate group is preferably a cyclic carbonate ester group. Examples of the carbonate group include carbonate groups obtained by removing one or more hydrogen atoms from ring atoms of a cyclic carbonate ester structure represented by any one of the following formulae (CC1-1) and (CC1-2): The lactone group, sultone group, and carbonate group may have a substituent.

[0102] 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 halogen atom, and a cyano 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 R Ｌ may be the same or different, and multiple R Ｌ They may be bonded to each other to form a ring.

[0103]

[0104] As the monomer having at least one group selected from the group consisting of a lactone group, a sultone group, a carbonate group, a sulfonyl group, an alcoholic hydroxyl group and a carboxy group, a compound represented by formula (MA2) is preferred.

[0105]

[0106] In formula (MA2), L ｍ２ represents a single bond or a divalent linking group, R ｍ３ represents a hydrogen atom, a fluorine atom, an iodine atom, an alkyl group, or an aryl group; R ｍ４ represents at least one selected from the group consisting of a group containing a lactone group, a group containing a sultone group, a group containing a carbonate group, a group containing a sulfonyl group, a group containing an alcoholic hydroxyl group, and a group containing a carboxy group.

[0107] L ｍ２ Examples of the divalent linking group represented by the formula: ２ Examples of the alkylene group include alkylene groups (e.g., alkylene groups, cycloalkylene groups, alkenylene groups, arylene groups, etc.), and linking groups formed by linking a plurality of these groups. The hydrocarbon group may have a substituent. 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 5. The cycloalkylene group may be a monocyclic cycloalkylene group or a polycyclic cycloalkylene group. The number of carbon atoms in the cycloalkylene group is not particularly limited, but is preferably 3 to 20, and more preferably 4 to 15. The alkenylene group may be linear or branched. The number of carbon atoms in the alkenylene group is not particularly limited, but is preferably 2 to 10, and more preferably 2 to 5. The number of carbon atoms in the arylene group is not particularly limited, but is preferably 6 to 20, and more preferably 6 to 10. A phenylene group is particularly preferred as the arylene group.

[0108] R ｍ３ The alkyl group represented by R may be linear or branched. ｍ３ The number of carbon atoms in the alkyl group represented by R is not particularly limited, but is preferably 1 to 10, and more preferably 1 to 3. ｍ３The alkyl group represented by the formula (I) may have a substituent. ｍ３ The number of carbon atoms in the aryl group represented by R is not particularly limited, but is preferably 6 to 10. ｍ３ The aryl group represented by the following formula may have a substituent.

[0109] R ｍ４ The group containing a lactone group represented by the formula (I) may be a lactone group or a group consisting of a lactone group and a group other than a lactone group. ｍ４ Examples of groups containing a lactone group represented by the formula (LC1-1) to (LC1-22) include lactone groups obtained by removing one or more hydrogen atoms from ring atoms of the lactone structure represented by any of the formulas (LC1-1) to (LC1-22) above.

[0110] R ｍ４ The group containing a sultone group represented by the formula (I) may be a sultone group itself, or may be a group consisting of a sultone group and a group other than a sultone group. ｍ４ Examples of groups containing a sultone group represented by the formula (SL1-1) to (SL1-3) include sultone groups obtained by removing one or more hydrogen atoms from ring atoms of the sultone structure represented by any one of the formulas (SL1-1) to (SL1-3) above.

[0111] R ｍ４ The group containing a carbonate group represented by the formula (I) may be a carbonate group, or may be a group consisting of a carbonate group and a group other than a carbonate group. ｍ４ Examples of the group containing a carbonate group represented by the formula (CC1-1) or (CC1-2) include carbonate groups obtained by removing one or more hydrogen atoms from ring atoms of a cyclic carbonate structure represented by the formula (CC1-1) or (CC1-2) above.

[0112] R ｍ４The sulfonyl group-containing group represented by the formula (I) is preferably an aliphatic group containing a sulfonyl group, more preferably a group in which one or more methylene groups in an alkyl group or cycloalkyl group are replaced with a sulfonyl group, and even more preferably a group in which one or more methylene groups in a cycloalkyl group are replaced with a sulfonyl group. The number of carbon atoms in the aliphatic group containing a sulfonyl group is not particularly limited, but is preferably 1 to 20, more preferably 1 to 10. The sulfonyl group-containing group may contain one or more heteroatoms other than the sulfonyl group. Furthermore, the sulfonyl group-containing group may have a substituent. R ｍ４ Examples of the group containing a sulfonyl group represented by the formula (SN1-1) to (SN1-5) include groups obtained by removing one or more hydrogen atoms from the structure represented by the formula (SN1-1) to (SN1-5). 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 halogen atom, and a cyano group. e1 represents an integer of 0 to 4. When e1 is 2 or more, multiple R Ｌ may be the same or different, and multiple R Ｌ They may be bonded to each other to form a ring.

[0113]

[0114] The alcoholic hydroxyl group is a hydroxyl group bonded to a hydrocarbon group other than an aromatic ring. ｍ４ The group containing an alcoholic hydroxyl group represented by the formula (I) may be an alcoholic hydroxyl group, or may be a group consisting of an alcoholic hydroxyl group and a group other than an alcoholic hydroxyl group. ｍ４The group containing an alcoholic hydroxyl group represented by the formula (I) is preferably a saturated hydrocarbon group having 1 to 20 carbon atoms and a hydroxyl group, more preferably a saturated hydrocarbon group having 3 to 15 carbon atoms. The saturated hydrocarbon group may be linear, branched, or cyclic, but is preferably a cyclic (alicyclic) group. The alicyclic group is preferably a cycloalkyl group, and 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. When the saturated hydrocarbon group is linear or branched, it may contain a group containing a heteroatom such as an oxygen atom or a heteroatom such as a carbonyl group in the chain. When the saturated hydrocarbon group is an alicyclic group, at least one of the methylene groups constituting the ring may be replaced with a group containing a heteroatom such as an oxygen atom or a heteroatom such as a carbonyl group. R ｍ４ The number of hydroxyl groups contained in the group containing an alcoholic hydroxyl group represented by the formula (I) is not particularly limited, but is preferably 1 to 5.

[0115] R ｍ４ The group containing a carboxy group represented by the formula (I) may be a carboxy group or a group consisting of a carboxy group and a group other than a carboxy group. ｍ４ When the group containing a carboxy group represented by the formula (I) is a group consisting of a carboxy group and a group other than a carboxy group, it is preferably a hydrocarbon group having 1 to 20 carbon atoms and a carboxy group (for example, an alkyl group, a cycloalkyl group, an aryl group, etc.).

[0116] Specific examples of the monomer having at least one group selected from the group consisting of a lactone group, a sultone group, a carbonate group, a sulfonyl group, an alcoholic hydroxyl group, and a carboxy group are shown below, but are not limited to these.

[0117]

[0118] In the present invention, when synthesizing polymer (Q), a monomer having at least one selected from the group consisting of a lactone group, a sultone group, a carbonate group, a sulfonyl group, an alcoholic hydroxyl group, and a carboxy group may or may not be used. When a monomer having at least one selected from the group consisting of a lactone group, a sultone group, a carbonate group, a sulfonyl group, an alcoholic hydroxyl group, and a carboxy group is used, the amount of the monomer having at least one selected from the group consisting of a lactone group, a sultone group, a carbonate group, a sulfonyl group, an alcoholic hydroxyl group, and a carboxy group used is not particularly limited, and may be 1 mol % or more, 5 mol % or more, or 10 mol % or more, based on all the monomers used in the synthesis of polymer (Q). The amount of the monomer having at least one selected from the group consisting of a lactone group, a sultone group, a carbonate group, a sulfonyl group, an alcoholic hydroxyl group, and a carboxy group used may be 50 mol% or less, 40 mol% or less, or 30 mol% or less, based on all the monomers used in the synthesis of polymer (Q). The monomer having at least one selected from the group consisting of a lactone group, a sultone group, a carbonate group, a sulfonyl group, an alcoholic hydroxyl group, and a carboxy group used may be one type or two or more types. When two or more types of monomers having at least one selected from the group consisting of a lactone group, a sultone group, a carbonate group, a sulfonyl group, an alcoholic hydroxyl group, and a carboxy group are used, it is preferable that the total amount used is within the above range.

[0119] As the other monomer, a monomer having a photoacid generating group may be used. The photoacid generating group is a group that generates an acid upon irradiation with actinic rays or radiation. A polymer containing a repeating unit derived from a monomer having a photoacid generating group can function as a photoacid generator or an acid diffusion controller, depending on the strength of the acid generated from the photoacid generating group. An example of a monomer having a photoacid generating group is a compound represented by formula (MA3).

[0120]

[0121] In formula (MA3), R ４１ represents a hydrogen atom or an alkyl group (preferably a methyl group). ４１ represents a single bond or a divalent linking group. ４２ represents a divalent linking group. ４０ represents a structural moiety that decomposes upon irradiation with actinic rays or radiation to generate an acid in the side chain.

[0122] L ４１ represents a single bond or a divalent linking group, and preferably represents a single bond or an ester bond (—COO—).

[0123] L ４２ represents an alkylene group, a cycloalkylene group, an arylene group, —O—, —CO—, —S—, —SO—, —SO ２ Preferably, the linking group is at least one selected from the group consisting of - and -NR-. R represents a hydrogen atom or an organic group (preferably an organic group having 1 to 10 carbon atoms, such as an alkyl group, a cycloalkyl group, or an aryl group). The alkylene group may be either linear or branched. The number of carbon atoms in the alkylene group is not particularly limited, but preferably 1 to 10. The cycloalkylene group may be a monocyclic cycloalkylene group or a polycyclic cycloalkylene group. The number of carbon atoms in the cycloalkylene group is not particularly limited, but preferably 3 to 20, more preferably 5 to 15. The number of carbon atoms in the arylene group is not particularly limited, but preferably 6 to 20, more preferably 6 to 10. The alkylene group, cycloalkylene group, and arylene group may have a substituent, and examples of the substituent include the substituent T described above.

[0124] R ４０ is preferably a group represented by the following formula (S4-1).

[0125]

[0126] In formula (S4-1), Q － represents an acid residue, M ＋ represents a cation. * represents L ４１ The bond position of the acid residue is a group formed by dissociating a proton from an acid. － is a carboxylate anion group (COO －), sulfonate anion group (SO ３ － ), or a sulfonamide group (N － -SO ２ R Ｎ１ It is expressed as: R Ｎ１ represents an organic group, and examples thereof include organic groups having 1 to 10 carbon atoms, and an alkyl group, a fluoroalkyl group, or an aryl group is preferred. ＋ The explanation, specific examples and preferred ranges of M in the explanation of the photoacid generator to be described later ＋ is the same as

[0127] Specific examples of the monomer having a photoacid generating group are shown below, but are not limited to these.

[0128]

[0129] In the present invention, a monomer having a photoacid generating group may or may not be used when synthesizing polymer (Q). When a monomer having a photoacid generating group is used, the amount of the monomer having a photoacid generating group used is not particularly limited, but may be 1 mol% or more, 3 mol% or more, or 5 mol% or more relative to all monomers used in the synthesis of polymer (Q). Furthermore, the amount of the monomer having a photoacid generating group used may be 40 mol% or less, 35 mol% or less, or 30 mol% or less relative to all monomers used in the synthesis of polymer (Q). The monomer having a photoacid generating group used may be one type, or two or more types. When two or more types of monomers having a photoacid generating group are used, the total amount used is preferably within the above range.

[0130] As the other monomer, a monomer having neither an acid-decomposable group nor an acid group but having a fluorine atom, a bromine atom, or an iodine atom (also referred to as "monomer X") may be used. Monomer X may be a compound represented by formula (MA4).

[0131]

[0132] In formula (MA4), L ５ represents a single bond or an ester group. ９represents a hydrogen atom or an alkyl group which may have a fluorine atom, a bromine atom or an iodine atom. １０ represents a hydrogen atom, an alkyl group which may have a fluorine atom, a bromine atom or an iodine atom, a cycloalkyl group which may have a fluorine atom, a bromine atom or an iodine atom, an aryl group which may have a fluorine atom, a bromine atom or an iodine atom, or a group which is a combination of these.

[0133] In the present invention, when synthesizing polymer (Q), monomer X may or may not be used. When monomer X is used, the amount of monomer X used is not particularly limited, and may be 1 mol % or more, 5 mol % or more, or 10 mol % or more, based on all monomers used in the synthesis of polymer (Q). Furthermore, the amount of monomer X used may be 40 mol % or less, 35 mol % or less, or 30 mol % or less, based on all monomers used in the synthesis of polymer (Q). Monomer X may be used in one type or in two or more types. When two or more types of monomer X are used, the total amount used is preferably within the above range.

[0134] As the other monomer, a monomer represented by formula (MA5) or formula (MA6) may be used.

[0135]

[0136] In formula (MA5) and formula (MA6), R ６ and R ７ each independently represents 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.

[0137] As the other monomer, a monomer for reducing the mobility of the main chain of the polymer (Q) may be used. The monomer for reducing the mobility of the main chain becomes a repeating unit for reducing the mobility of the main chain by polymerization. With regard to the repeating unit for reducing the mobility of the main chain, the contents of

[0144] to

[0160] of WO 2022 / 024928 are incorporated by reference.

[0138] As the other monomer, a monomer having at least one type of group selected from a cyano group and an alkali-soluble group may be used. The monomer having a cyano group is preferably a monomer having a saturated hydrocarbon group having a cyano group (substituted with a cyano group). It may also be a monomer having an alicyclic group substituted with a cyano group. The monomer having a cyano group preferably does not have an acid-decomposable group. Examples of the monomer having a cyano group include monomers corresponding to the repeating units described in paragraphs

[0081] to

[0084] of JP 2014-098921 A.

[0139] As used herein, the term "monomer corresponding to a repeating unit" refers to a structure obtained by polymerizing the monomer (i.e., by polymerizing the polymerizable group of the monomer), which is the structure of the repeating unit. When a repeating unit in a polymer is described as a corresponding monomer, the repeating unit does not necessarily have to have been obtained using the corresponding monomer (for example, the repeating unit may be obtained by polymerizing another monomer and then modifying the structure through a chemical reaction). Examples of the polymerizable group of the monomer include groups containing a carbon-carbon double bond, such as a vinyl group, an allyl group, an acryloyl group, and a methacryloyl group. Examples of polymerization reactions include addition polymerization reactions. Examples of repeating units and monomers corresponding to the repeating unit include a repeating unit represented by the following formula (RM-1) and a corresponding monomer, represented by the following formula (RM-2). In the above relationship (i.e., when a monomer corresponds to the repeating unit), the repeating unit is also referred to as a "repeating unit derived from a monomer." For example, the repeating unit represented by the following formula (RM-1) is a repeating unit derived from a monomer represented by the following formula (RM-2).

[0140]

[0141] In formulas (RM-1) and (RM-2), R １００ represents a hydrogen atom or a substituent. １０１ represents a substituent. １ and ※ ２ represents the bond position.

[0142] 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. Examples of the monomer having an alkali-soluble group include monomers corresponding to the repeating units described in paragraphs

[0085] and

[0086] of JP 2014-098921 A.

[0143] As the other monomer, a monomer having an alicyclic hydrocarbon structure and not exhibiting acid decomposition may be used, for example, 1-adamantyl (meth)acrylate, diamantyl (meth)acrylate, tricyclodecanyl (meth)acrylate, or cyclohexyl (meth)acrylate.

[0144] As the other monomer, a monomer represented by formula (MA7) having neither a hydroxyl group nor a cyano group may be used.

[0145]

[0146] In formula (MA7), 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 monomer represented by formula (MA7) that does not have either a hydroxyl group or a cyano group include monomers corresponding to the repeating units described in paragraphs

[0087] to

[0094] of JP2014-098921A.

[0147] As the other monomer, a monomer other than those mentioned above may be used, for example, a monomer selected from the group consisting of a monomer having an oxathiane ring group, a monomer having an oxazolone ring group, a monomer having a dioxane ring group, and a monomer having a hydantoin ring group.

[0148] In step (1), the compound represented by formula (i), a monomer having an acid-decomposable group, and optionally other monomers are polymerized to obtain polymer (Q). Specific polymerization methods that can be used include known methods (e.g., radical polymerization).

[0149] (Polymer (Q)) The polymer (Q) has repeating units derived from the polymerized monomers. The polymer (Q) has at least repeating units derived from the compound represented by formula (i) and the monomer having an acid-decomposable group, and when other monomers are polymerized, the polymer (Q) further has repeating units derived from the other monomers. The content of each repeating unit relative to all repeating units in the polymer (Q) is the same as the content of the monomer corresponding to each repeating unit described above.

[0150] The content of the repeating unit derived from the compound represented by formula (i) in polymer (Q) is not particularly limited, but is preferably 1 mol% or more, more preferably 5 mol% or more, and even more preferably 10 mol% or more, based on the total repeating units in polymer (Q). Furthermore, the content of the repeating unit derived from the compound represented by formula (i) in polymer (Q) is 100 mol% or less, or may be 90 mol% or less, or may be 80 mol% or less, based on the total repeating units in polymer (Q). The repeating unit derived from the compound represented by formula (i) contained in polymer (Q) may be one type, or two or more types. When there are two or more types of repeating units derived from the compound represented by formula (i), it is preferable that the total content thereof is within the above range.

[0151] The content of repeating units derived from monomers having an acid-decomposable group in polymer (Q) is not particularly limited, but is preferably 30 mol% or more, more preferably 40 mol% or more, and even more preferably more than 50 mol%, based on the total repeating units in polymer (Q). Furthermore, the content of repeating units derived from monomers having an acid-decomposable group in polymer (Q) is 100 mol% or less, or may be 90 mol% or less, or may be 80 mol% or less, based on the total repeating units in polymer (Q). The repeating units derived from monomers having an acid-decomposable group contained in polymer (Q) may be one type, or two or more types. When there are two or more types of repeating units derived from monomers having an acid-decomposable group, it is preferable that the total content thereof is within the above range.

[0152] The repeating units derived from a monomer having an acid-decomposable group are preferably repeating units having an acid-decomposable group. In one preferred embodiment of the present invention, the polymer (Q) contains repeating units having an acid-decomposable group in an amount of more than 50 mol % based on the total repeating units.

[0153] In a preferred embodiment of the present invention, polymer (Q) contains a repeating unit having at least one selected from the group consisting of a lactone group, a sultone group, a carbonate group, a sulfonyl group, an alcoholic hydroxyl group, and a carboxy group. The repeating unit having at least one selected from the group consisting of a lactone group, a sultone group, a carbonate group, a sulfonyl group, an alcoholic hydroxyl group, and a carboxy group is preferably a repeating unit derived from the aforementioned monomer having at least one selected from the group consisting of a lactone group, a sultone group, a carbonate group, a sulfonyl group, an alcoholic hydroxyl group, and a carboxy group. The content of the repeating unit having at least one selected from the group consisting of a lactone group, a sultone group, a carbonate group, a sulfonyl group, an alcoholic hydroxyl group, and a carboxy group is not particularly limited, but may be 1 mol % or more, 5 mol % or more, or 10 mol % or more, based on the total repeating units in polymer (Q). Furthermore, the content of repeating units having at least one selected from the group consisting of lactone groups, sultone groups, carbonate groups, sulfonyl groups, alcoholic hydroxyl groups, and carboxy groups may be 50 mol% or less, 40 mol% or less, or 30 mol% or less, based on the total repeating units in polymer (Q). The repeating units having at least one selected from the group consisting of lactone groups, sultone groups, carbonate groups, sulfonyl groups, alcoholic hydroxyl groups, and carboxy groups contained in polymer (Q) may be one type or two or more types. When there are two or more types of repeating units having at least one selected from the group consisting of lactone groups, sultone groups, carbonate groups, sulfonyl groups, alcoholic hydroxyl groups, and carboxy groups, it is preferable that the total content thereof is within the above range.

[0154] The weight average molecular weight (Mw) of the polymer (Q), as a polystyrene equivalent value measured by a GPC method, 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 (also referred to as "molecular weight distribution," "Mw / Mn," or "Pd") of the polymer (Q) is preferably 1.0 to 5.0, more preferably 1.0 to 3.0, even more preferably 1.1 to 2.0, and particularly preferably 1.1 to 1.5.

[0155] [Step (2)] Step (2) is a step of decomposing the polymer (Q) by the action of an acid or a base to obtain a polymer (P) having a repeating unit represented by formula (ii).

[0156]

[0157] In formula (ii), X １ , L １ , Ar and n1 are each X in formula (i). １ , L １ , Ar and n1 have the same meaning.

[0158] In step (2), the repeating units derived from the compound represented by formula (i) in polymer (Q) are decomposed by the action of an acid or a base to become repeating units represented by formula (ii). In step (2), all of the repeating units derived from the compound represented by formula (i) in polymer (Q) may become repeating units represented by formula (ii), or some of them may become repeating units represented by formula (ii). However, based on the repeating units derived from the compound represented by formula (i) in polymer (Q), it is preferable that 50 mol % to 100 mol % of them become repeating units represented by formula (ii), and more preferably 80 mol % to 100 mol % become repeating units represented by formula (ii).

[0159] X in formula (ii) １ , L １ The explanation, specific examples and preferred ranges of Ar and n1 are given in X in formula (i), respectively. １ , L １ , Ar and n1.

[0160] The content of the repeating unit represented by formula (ii) is not particularly limited, but is preferably 1 mol% or more, more preferably 5 mol% or more, and even more preferably 10 mol% or more, based on the total repeating units in the polymer (P). The content of the repeating unit represented by formula (ii) is 100 mol% or less, or may be 90 mol% or less, or may be 80 mol% or less, based on the total repeating units in the polymer (P). The repeating unit represented by formula (ii) contained in the polymer (P) may be one type, or two or more types. When there are two or more types of repeating units represented by formula (ii), it is preferable that the total content thereof is within the above range.

[0161] The repeating units contained in the polymer (P) other than the repeating units represented by formula (ii) and their content are preferably the same as the repeating units contained in the polymer (Q) other than the repeating units derived from the compound represented by formula (i) and their content. The polymer (P) preferably contains a repeating unit having an acid-decomposable group. The acid-decomposable group is a group that decomposes under the action of acid to increase its polarity, typically a group that decomposes under the action of acid to generate a polar group. The polymer (P) preferably increases in polarity under the action of acid, thereby decreasing its solubility in organic solvents. The polymer (P) preferably contains 30 mol% or more of repeating units having an acid-decomposable group, more preferably 40 mol% or more, and even more preferably more than 50 mol%, based on all repeating units. The content of repeating units having an acid-decomposable group in the polymer (P) is 100 mol% or less, or may be 90 mol% or less, or may be 80 mol% or less, based on all repeating units.

[0162] L in formulas (i) and (ii) １ In a preferred embodiment of the present invention, represents a single bond.

[0163] The weight average molecular weight (Mw) of the polymer (P), as a polystyrene equivalent value measured by a GPC method, 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 (also referred to as "molecular weight distribution," "Mw / Mn," or "Pd") of the polymer (P) is preferably 1.0 to 5.0, more preferably 1.0 to 3.0, even more preferably 1.1 to 2.0, and particularly preferably 1.1 to 1.5.

[0164] In a preferred embodiment of the present invention, in step (2), polymer (Q) is decomposed by the action of a base to obtain polymer (P). The base that can be used in step (2) is not particularly limited, but examples include triethylamine, trimethylamine, ethyldiisopropylamine, N-methylmorpholine, pyridine, 4-dimethylaminopyridine, diisopropylethylamine, ammonia, sodium carbonate, potassium carbonate, cesium carbonate, sodium tert-butoxide, potassium tert-butoxide, sodium hydroxide, potassium hydroxide, potassium methoxide, diazabicycloundecene, and sodium methoxide. The acid dissociation constant (pKa) of the conjugate acid of the base that can be used in step (2) is not particularly limited, but is preferably 6.0 or greater, and more preferably 9.0 or greater, in order to obtain a resist composition that can form a resist film with superior resolution. Furthermore, the pKa of the conjugate acid of the base that can be used in step (2) is preferably 16.0 or less, and more preferably 14.0 or less. Examples of bases having a conjugate acid pKa of 6.0 or higher include, but are not limited to, triethylamine (10.62), 4-dimethylaminopyridine (9.52), morpholine (8.97), diazabicycloundecene (13.28), etc. Commercially available reagents can also be used as the base in step (2).

[0165] In a preferred embodiment of the present invention, in step (2), polymer (Q) is decomposed by the action of an acid to obtain polymer (P). The acid that can be used in step (2) is not particularly limited, but examples include sulfonic acids (sulfuric acid, methanesulfonic acid, p-toluenesulfonic acid, trifluoromethanesulfonic acid, etc.), hydrogen halides (hydrogen fluoride, hydrogen chloride, hydrogen bromide, hydrogen iodide), carboxylic acids (acetic acid, oxalic acid, benzoic acid, etc.), perfluorocarboxylic acids (trifluoroacetic acid, perfluorobutanecarboxylic acid, etc.), and nitric acid. These acids may be used alone or in combination. The acid dissociation constant (pKa) of the acid that can be used in step (2) is not particularly limited, but is preferably −1.0 or greater, and more preferably 0.5 or greater, in order to obtain a resist composition that can form a resist film with superior resolution. Furthermore, the pKa of the acid that can be used in step (2) is preferably 3.0 or less, and more preferably 2.0 or less. Examples of acids with a pKa of -1.0 or higher include, but are not limited to, 10-camphorsulfonic acid (1.17), p-toluenesulfonic acid (-0.43), trifluoroacetic acid (0.53), etc. Commercially available reagents can also be used as the acid in step (2).

[0166] [Step (3)] Step (3) is a step of obtaining an actinic ray-sensitive or radiation-sensitive resin composition containing the polymer (P), a photoacid generator, and a solvent.

[0167] [Actinic ray-sensitive or radiation-sensitive resin composition] The actinic ray-sensitive or radiation-sensitive resin composition obtained in step (3) is typically a resist composition. The actinic ray-sensitive or radiation-sensitive resin composition obtained in step (3) is also conveniently referred to as a "resist composition." Furthermore, the film formed using the actinic ray-sensitive or radiation-sensitive resin composition in step (4) is typically a resist film. The film formed using the actinic ray-sensitive or radiation-sensitive resin composition is also conveniently referred to as a "resist film."

[0168] The resist composition may be a positive resist composition or a negative resist composition, but is preferably a negative resist composition. Furthermore, the resist composition is preferably a resist composition for organic solvent development. The resist composition may be a chemically amplified resist composition or a non-chemically amplified resist composition, but is preferably a chemically amplified resist composition.

[0169] In step (3), the polymer (P), a photoacid generator, and a solvent are mixed to obtain an actinic ray-sensitive or radiation-sensitive resin composition (resist composition). The polymer (P) is as described above.

[0170] The content of the polymer (P) in the resist composition is preferably 30 to 99 mass%, more preferably 40 to 95 mass%, and even more preferably 50 to 90 mass%, based on the total solid content of the resist composition. The polymer (P) 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.

[0171] [Photoacid Generator] The resist composition contains a photoacid generator. The photoacid generator is a compound that generates an acid upon irradiation with actinic rays or radiation. The photoacid generator may be a compound different from the polymer (P), or may be the same compound. The photoacid generator is preferably a compound that generates an acid having a pKa of less than 0 upon irradiation with actinic rays or radiation. The pKa of the acid generated from the photoacid generator upon irradiation with actinic rays or radiation is preferably −0.1 or less, more preferably −0.2 or less. Furthermore, the pKa of the acid generated from the photoacid generator upon irradiation with actinic rays or radiation is preferably −1.5 or more, more preferably −1.0 or more.

[0172] The photoacid generator may be in the form of a low molecular weight compound or may be incorporated into a polymer. Furthermore, a photoacid generator in the form of a low molecular weight compound and a photoacid generator in the form of a polymer may be used in combination. When the photoacid generator is in the form of a low molecular weight compound, the molecular weight of the photoacid generator is not particularly limited, but is preferably 100 to 3,000, more preferably 150 to 2,500, and even more preferably 200 to 2,000. When the photoacid generator is incorporated into a polymer, it may be incorporated into the polymer (P) or into a polymer different from the polymer (P). When the polymer (P) does not have the repeating unit having the photoacid-generating group described above, the resist composition preferably contains a photoacid generator that is a compound different from the polymer (P). When the polymer (P) contains a repeating unit having a photoacid-generating group, the resist composition may or may not contain a separate photoacid generator. The photoacid generator is preferably in the form of a low molecular weight compound. The photoacid generator is preferably an onium salt.

[0173] Examples of the photoacid generator include "M ＋ X － ", and it is preferably a compound that generates an organic acid upon exposure. Examples of the organic acid include sulfonic acids (aliphatic sulfonic acids, aromatic sulfonic acids, camphorsulfonic acids, etc.), carboxylic acids (aliphatic carboxylic acids, aromatic carboxylic acids, aralkyl carboxylic acids, etc.), carbonylsulfonylimido acids, bis(alkylsulfonyl)imido acids, and tris(alkylsulfonyl)methido acids.

[0174] "M ＋ X － In the compound represented by the formula ", M ＋ represents a cation, preferably an organic cation. The cation is not particularly limited. The cation may have a valence of 1 or 2 or more. The cation is preferably a cation represented by formula (ZaI) (hereinafter also referred to as "cation (ZaI)") or a cation represented by formula (ZaII) (hereinafter also referred to as "cation (ZaII)").

[0175]

[0176] 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 listed.

[0177] 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.

[0178] 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 ~R２０３ 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.

[0179] 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.

[0180] 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 (e.g., fluorine and iodine), hydroxyl groups, carboxyl groups, ester groups, sulfinyl groups, sulfonyl groups, alkylthio groups, and phenylthio groups. The above substituents may further have substituents if possible, and it is also preferred that the alkyl group has a halogen atom as a substituent to form a halogenated alkyl group such as a trifluoromethyl group. It is also preferred that the above substituents form an acid-decomposable group in any combination. The acid-decomposable group is intended to be a group that decomposes under the action of acid to generate a polar group, and preferably has a structure in which the polar group is protected by a group that leaves under the action of acid. The above polar groups and leaving groups are as described above.

[0181] 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.

[0182] R ２０１ ~R ２０３Examples 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 ２０３ may be further substituted with a halogen atom, an alkoxy group (e.g., having 1 to 5 carbon atoms), a hydroxyl group, a cyano group, or a nitro group. ２０１ ~R ２０３ It is also preferred that the substituents independently form an acid-decomposable group by any combination of the substituents.

[0183] Next, the cation (ZaI-3b) will be described. The cation (ZaI-3b) is a cation represented by the following formula (ZaI-3b).

[0184]

[0185] 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, 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, 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.

[0186] 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 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.

[0187] 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.

[0188] 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 ｙThe ring formed by bonding together may have a substituent.

[0189] Next, the cation (ZaI-4b) will be described. The cation (ZaI-4b) is a cation represented by the following formula (ZaI-4b).

[0190]

[0191] 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 (for example, a fluorine atom or an iodine atom), a hydroxyl group, an alkyl group, a halogenated alkyl group, 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 (for example, a fluorine atom or an iodine atom), an alkyl group, a halogenated alkyl group, 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.

[0192] In formula (ZaI-4b), R １３ , R１４ , 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.

[0193] 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., a methyl group, an ethyl group, a propyl group, a butyl group, or a pentyl group), or a cycloalkyl group having 3 to 10 carbon atoms (e.g., a cyclopentyl group, a cyclohexyl group, or a norbornyl group).

[0194] R ２０４ and R ２０５ The aryl group, alkyl group, and cycloalkyl group in R may each independently have a substituent. ２０４ and R ２０５Examples of the 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 15 carbon atoms), alkoxy groups (e.g., having 1 to 15 carbon atoms), halogen atoms, hydroxyl groups, and phenylthio groups. ２０４ and R ２０５ It is also preferred that the substituents independently form an acid-decomposable group by any combination of the substituents.

[0195] Specific examples of organic cations are shown below, but are not limited to these.

[0196]

[0197]

[0198] "M ＋ X － In the compound represented by the formula "X － represents an anion, preferably an organic anion. The anion is not particularly limited, and examples thereof include monovalent or divalent or higher anions. The anion is preferably an anion having a significantly low ability to cause a nucleophilic reaction, and more preferably a non-nucleophilic anion.

[0199] Examples of non-nucleophilic anions include sulfonate anions (aliphatic sulfonate anions, aromatic sulfonate anions, camphorsulfonate anions, etc.), carboxylate anions (aliphatic carboxylate anions, aromatic carboxylate anions, aralkyl carboxylate anions, etc.), sulfonylimide anions, bis(alkylsulfonyl)imide anions, and tris(alkylsulfonyl)methide anions.

[0200] The aliphatic moiety in the aliphatic sulfonate anion and the aliphatic carboxylate anion may be a linear or branched alkyl group or a cycloalkyl group, and is preferably a linear or branched alkyl group having 1 to 30 carbon atoms or a cycloalkyl group having 3 to 30 carbon atoms. The alkyl group may be, for example, a fluoroalkyl group (which may have a substituent other than a fluorine atom, or may be a perfluoroalkyl group).

[0201] The aryl group in the aromatic sulfonate anion and aromatic carboxylate anion is preferably an aryl group having 6 to 14 carbon atoms, and examples thereof include a phenyl group, a tolyl group, and a naphthyl group.

[0202] The alkyl group, cycloalkyl group, and aryl group mentioned above may have a substituent. The substituent is not particularly limited, but examples thereof include a nitro group, a halogen atom such as a fluorine atom or a chlorine atom, a carboxyl group, a hydroxyl group, an amino group, a cyano group, an alkoxy group (preferably having 1 to 15 carbon atoms), an alkyl group (preferably having 1 to 10 carbon atoms), a cycloalkyl group (preferably having 3 to 15 carbon atoms), an aryl group (preferably having 6 to 14 carbon atoms), an alkoxycarbonyl group (preferably having 2 to 7 carbon atoms), an acyl group (preferably having 2 to 12 carbon atoms), an alkoxycarbonyloxy group (preferably having 2 to 7 carbon atoms), an alkylthio group (preferably having 1 to 15 carbon atoms), an alkylsulfonyl group (preferably having 1 to 15 carbon atoms), an alkyliminosulfonyl group (preferably having 1 to 15 carbon atoms), and an aryloxysulfonyl group (preferably having 6 to 20 carbon atoms).

[0203] The aralkyl group in the aralkyl carboxylate anion is preferably an aralkyl group having 7 to 14 carbon atoms. Examples of the aralkyl group having 7 to 14 carbon atoms include a benzyl group, a phenethyl group, a naphthylmethyl group, a naphthylethyl group, and a naphthylbutyl group.

[0204] An example of the sulfonylimide anion is a saccharin anion.

[0205] The alkyl group in the bis(alkylsulfonyl)imide anion and the tris(alkylsulfonyl)methide anion is preferably an alkyl group having 1 to 5 carbon atoms. Substituents for these alkyl groups include halogen atoms, alkyl groups substituted with halogen atoms, alkoxy groups, alkylthio groups, alkyloxysulfonyl groups, aryloxysulfonyl groups, and cycloalkylaryloxysulfonyl groups, with fluorine atoms or alkyl groups substituted with fluorine atoms being preferred. Furthermore, the alkyl groups in the bis(alkylsulfonyl)imide anion may be bonded to each other to form a ring structure, which increases the acid strength.

[0206] Other non-nucleophilic anions include, for example, phosphorus fluorides (e.g., PF ６ － ), boron fluorides (e.g., BF ４ － ), and antimony fluorides (e.g., SbF ６ － ) are listed.

[0207] Preferred non-nucleophilic anions include aliphatic sulfonate anions in which at least the α-position of the sulfonic acid is substituted with a fluorine atom, aromatic sulfonate anions substituted with a fluorine atom or a group having a fluorine atom, bis(alkylsulfonyl)imide anions in which an alkyl group is substituted with a fluorine atom, and tris(alkylsulfonyl)methide anions in which an alkyl group is substituted with a fluorine atom. Among these, perfluoroaliphatic sulfonate anions (preferably having 4 to 8 carbon atoms) and benzenesulfonate anions having a fluorine atom are more preferred, and nonafluorobutanesulfonate anions, perfluorooctanesulfonate anions, pentafluorobenzenesulfonate anions, and 3,5-bis(trifluoromethyl)benzenesulfonate anions are even more preferred.

[0208] The non-nucleophilic anion is also preferably an anion represented by the following formula (AN1).

[0209]

[0210] In formula (AN1), R１ and R ２ each independently represents a hydrogen atom or a substituent. The substituent is not particularly limited, but a group that is not an electron-withdrawing group is preferred. Examples of groups that are not electron-withdrawing groups include hydrocarbon groups, hydroxyl groups, oxyhydrocarbon groups, oxycarbonyl hydrocarbon groups, amino groups, hydrocarbon-substituted amino groups, and hydrocarbon-substituted amide groups. Examples of groups that are not electron-withdrawing groups include, each independently, -R', -OH, -OR', -OCOR', -NH ２ , -NR' ２ , —NHR′, or —NHCOR′ is preferred, where R′ is a monovalent hydrocarbon group.

[0211] Examples of the monovalent hydrocarbon group represented by R' include monovalent linear or branched hydrocarbon groups such as alkyl groups such as methyl, ethyl, propyl, and butyl; alkenyl groups such as ethenyl, propenyl, and butenyl; alkynyl groups such as ethynyl, propynyl, and butynyl; cycloalkyl groups such as cyclopropyl, cyclobutyl, cyclopentyl, cyclohexyl, norbornyl, and adamantyl; monovalent alicyclic hydrocarbon groups such as cycloalkenyl groups such as cyclopropenyl, cyclobutenyl, cyclopentenyl, and norbornenyl; aryl groups such as phenyl, tolyl, xylyl, mesityl, naphthyl, methylnaphthyl, anthryl, and methylanthryl; and aralkyl groups such as benzyl, phenethyl, phenylpropyl, naphthylmethyl, and anthrylmethyl. Among these, R １ and R ２ are each independently preferably a hydrocarbon group (preferably a cycloalkyl group) or a hydrogen atom.

[0212] L represents a divalent linking group. When a plurality of L's are present, they may be the same or different. Examples of the divalent linking group include -O-CO-O-, -COO-, -CONH-, -CO-, -O-, -S-, -SO-, and -SO ２Examples of the divalent linking group include -, an alkylene group (preferably having 1 to 6 carbon atoms), a cycloalkylene group (preferably having 3 to 15 carbon atoms), an alkenylene group (preferably having 2 to 6 carbon atoms), and a divalent linking group formed by combining a plurality of these groups. Among these, examples of the divalent linking group include -O-CO-O-, -COO-, -CONH-, -CO-, -O-, and -SO ２ -, -O-CO-O-alkylene group-, -COO-alkylene group-, or -CONH-alkylene group- is preferred, and -O-CO-O-, -O-CO-O-alkylene group-, -COO-, -CONH-, or -SO ２ - or -COO-alkylene group- is more preferred.

[0213] As L, for example, a group represented by the following formula (AN1-1) is preferable: ａ - (CR ２ａ ２ ) Ｘ -Q-(CR ２ｂ ２ ) Ｙ -* ｂ (AN1-1)

[0214] In formula (AN1-1), * ａ is R in formula (AN1). ３ Represents the bonding position with * ｂ represents -C(R １ ) (R ２ X and Y each independently represent an integer of 0 to 10, preferably an integer of 0 to 3. R ２ａ and R ２ｂ R each independently represents a hydrogen atom or a substituent. ２ａ and R ２ｂ When there are multiple R ２ａ and R ２ｂ may be the same or different, provided that when Y is 1 or more, -C(R １ ) (R ２ )- and CR directly bonded ２ｂ ２ R in ２ｂ is other than a fluorine atom. Q is * Ａ -O-CO-O-*Ｂ , * Ａ -CO-* Ｂ , * Ａ -CO-O-* Ｂ , * Ａ -O-CO-* Ｂ , * Ａ -O-* Ｂ , * Ａ -S-* Ｂ , or * Ａ -SO ２ -* Ｂ where X+Y in formula (AN1-1) is 1 or more, and R ２ａ and R ２ｂ are all hydrogen atoms, Q is * Ａ -O-CO-O-* Ｂ , * Ａ -CO-* Ｂ , * Ａ -O-CO-* Ｂ , * Ａ -O-* Ｂ , * Ａ -S-* Ｂ , or * Ａ -SO ２ -* Ｂ Represents. Ａ is R in formula (AN1). ３ represents the bonding position on the side, and * Ｂ represents -SO in formula (AN1). ３ － represents the bonding position on the side.

[0215] In formula (AN1), R ３ represents an organic group. The organic group is not particularly limited as long as it has one or more carbon atoms, and may be a linear group (for example, a linear alkyl group), a branched group (for example, a branched alkyl group such as a t-butyl group), or a cyclic group. The organic group may or may not have a substituent. The organic group may or may not have a heteroatom (such as an oxygen atom, a sulfur atom, and / or a nitrogen atom).

[0216] Among them, R ３is preferably an organic group having a cyclic structure. The cyclic structure may be monocyclic or polycyclic and may have a substituent. The ring in the organic group having a cyclic structure is preferably directly bonded to L in formula (AN1). The organic group having a cyclic structure may or may not have a heteroatom (oxygen atom, sulfur atom, and / or nitrogen atom, etc.). The heteroatom may be substituted for one or more of the carbon atoms forming the cyclic structure. The organic group having a cyclic structure is preferably, for example, a hydrocarbon group having a cyclic structure, a lactone ring group, or a sultone ring group. Among these, the organic group having a cyclic structure is preferably a hydrocarbon group having a cyclic structure. The hydrocarbon group having a cyclic structure is preferably a monocyclic or polycyclic cycloalkyl group. These groups may have a substituent. The cycloalkyl group may be monocyclic (e.g., a cyclohexyl group) or polycyclic (e.g., an adamantyl group), and preferably has 5 to 12 carbon atoms. As the lactone group and sultone group, for example, a group in which one hydrogen atom has been removed from a ring atom constituting the lactone structure or sultone structure in any of the structures represented by the above-mentioned formulae (LC1-1) to (LC1-22) and the structures represented by the above-mentioned formulae (SL1-1) to (SL1-3) is preferred.

[0217] R ３ Preferably, R contains a halogen atom. ３ The halogen atom contained in is preferably a fluorine atom or an iodine atom, and more preferably an iodine atom. When the resist composition is used as an EUV resist, the number of halogen atoms is preferably as large as possible from the viewpoint of the efficiency of absorbing EUV light. When an iodine atom is contained, a structure in which the iodine atom is directly bonded to a carbon atom on an aromatic ring is preferred.

[0218] As the anion represented by formula (AN1), the anions described in

[0040] to

[0044] of JP-A-2018-155908 are also preferred.

[0219] The non-nucleophilic anion may be a benzenesulfonate anion, and is preferably a benzenesulfonate anion substituted with a branched alkyl group or a cycloalkyl group.

[0220] The non-nucleophilic anion is also preferably an anion represented by the following formula (AN2).

[0221]

[0222] In formula (AN2), o represents an integer of 1 to 3. p represents an integer of 0 to 10. q represents an integer of 0 to 10.

[0223] Xf represents a hydrogen atom, a fluorine atom, an alkyl group substituted with at least one fluorine atom, or an organic group having no fluorine atoms. The number of carbon atoms in this alkyl group is preferably 1 to 10, more preferably 1 to 4. The alkyl group substituted with at least one fluorine atom is preferably a perfluoroalkyl group. Xf is preferably a fluorine atom or a perfluoroalkyl group having 1 to 4 carbon atoms, and is preferably a fluorine atom or CF ３ It is more preferable that both Xf's are fluorine atoms.

[0224] R ４ and R ５ R each independently represents a hydrogen atom, a fluorine atom, an alkyl group, or an alkyl group substituted with at least one fluorine atom. ４ and R ５ If there are multiple R ４ and R ５ may be the same or different. ４ and R ５ The alkyl group represented by the formula (I) preferably has 1 to 4 carbon atoms. The alkyl group may have a substituent. ４ and R ５ is preferably a hydrogen atom.

[0225] L represents a divalent linking group, and is defined as L in formula (AN1).

[0226] W represents an organic group containing a cyclic structure. Among these, a cyclic organic group is preferred. Examples of the cyclic organic group include an alicyclic group, an aryl group, and a heterocyclic group. The alicyclic group may be monocyclic or polycyclic. Examples of the monocyclic alicyclic group include a monocyclic cycloalkyl group such as a cyclopentyl group, a cyclohexyl group, and a cyclooctyl group. Examples of the polycyclic alicyclic group include a polycyclic cycloalkyl group such as a norbornyl group, a tricyclodecanyl group, a tetracyclodecanyl group, a tetracyclododecanyl group, and an adamantyl group. Among these, alicyclic groups having a bulky structure with 7 or more carbon atoms, such as a norbornyl group, a tricyclodecanyl group, a tetracyclodecanyl group, a tetracyclododecanyl group, and an adamantyl group, are preferred.

[0227] The aryl group may be monocyclic or polycyclic. Examples of the aryl group include a phenyl group, a naphthyl group, a phenanthryl group, and an anthryl group. The heterocyclic group may be monocyclic or polycyclic. In particular, a polycyclic heterocyclic group can further suppress the diffusion of acid. The heterocyclic group may or may not have aromaticity. Examples of heterocyclic rings having aromaticity include a furan ring, a thiophene ring, a benzofuran ring, a benzothiophene ring, a dibenzofuran ring, a dibenzothiophene ring, and a pyridine ring. Examples of heterocyclic rings having no aromaticity include a tetrahydropyran ring, a lactone ring, a sultone ring, and a decahydroisoquinoline ring. The heterocyclic ring in the heterocyclic group is preferably a furan ring, a thiophene ring, a pyridine ring, or a decahydroisoquinoline ring.

[0228] The cyclic organic group may have a substituent. Examples of the substituent include an alkyl group (which may be either linear or branched, and preferably has 1 to 12 carbon atoms), a cycloalkyl group (which may be either monocyclic, polycyclic, or spirocyclic, and preferably has 3 to 20 carbon atoms), an aryl group (which preferably has 6 to 14 carbon atoms), a hydroxyl group, an alkoxy group, an ester group, an amide group, a urethane group, a ureido group, a thioether group, a sulfonamide group, and a sulfonate ester group. The carbon constituting the cyclic organic group (the carbon that contributes to ring formation) may be a carbonyl carbon.

[0229] W preferably contains a halogen atom. The halogen atom contained in W is preferably a fluorine atom or an iodine atom, and more preferably an iodine atom. When the resist composition is used as an EUV resist, the greater the number of halogen atoms, the better from the viewpoint of the absorption efficiency of EUV light. When an iodine atom is contained, a structure in which the iodine atom is directly bonded to a carbon atom on an aromatic ring is preferred.

[0230] As the anion represented by formula (AN2), the anions described in

[0076] of WO 2023 / 157455,

[0071] to

[0089] of JP-A 2021-81708,

[0033] to

[0045] of JP-A 2018-5224, and

[0031] to

[0039] of JP-A 2018-25789 are also preferred.

[0231] The anion represented by formula (AN2) is SO ３ － -CF ２ -CH ２ -OCO-(L) ｑ’ -W, SO ３ － -CF ２ -CHF-CH ２ -OCO-(L) ｑ’ -W, SO ３ － -CF ２ -COO-(L) ｑ’ -W, SO ３ － -CF ２ -CF ２ -CH ２ -CH２ - (L) ｑ -W or SO ３ － -CF ２ -CH(CF ３ ) -OCO-(L) ｑ’ -W is preferred. Here, L, q and W are the same as those in formula (AN2). q' represents an integer of 0 to 10.

[0232] The non-nucleophilic anion is also preferably an aromatic sulfonate anion represented by the following formula (AN3).

[0233]

[0234] In formula (AN3), Ar represents an aryl group (such as a phenyl group) and may further have a substituent other than the sulfonate anion and the -(D-B) group. Examples of the substituent that may further be had include a fluorine atom and a hydroxyl group. n represents an integer of 0 or greater. n is preferably 1 to 4, more preferably 2 to 3, and even more preferably 3.

[0235] D represents a single bond or a divalent linking group. Examples of the divalent linking group include an ether group, a thioether group, a carbonyl group, a sulfoxide group, a sulfone group, a sulfonate ester group, an ester group, and a group formed by combining two or more of these groups.

[0236] B represents a hydrocarbon group. B is preferably an aliphatic hydrocarbon group, more preferably an isopropyl group, a cyclohexyl group, or an aryl group which may further have a substituent (such as a tricyclohexylphenyl group).

[0237] B preferably contains a halogen atom. The halogen atom contained in B is preferably a fluorine atom or an iodine atom, and more preferably an iodine atom. When the resist composition is used as an EUV resist, the greater the number of halogen atoms, the better, from the viewpoint of the absorption efficiency of EUV light. When an iodine atom is contained, a structure in which the iodine atom is directly bonded to a carbon atom on an aromatic ring is preferred.

[0238] As the anion represented by formula (AN3), the anions described in

[0029] to

[0034] of JP-A No. 2018-159744 and

[0045] of JP-A No. 2018-155908 are also preferred.

[0239] As the non-nucleophilic anion, a disulfonamide anion is also preferred. The disulfonamide anion is, for example, N － (SO ２ -R ｑ ) ２ where R ｑ represents an alkyl group which may have a substituent, preferably a fluoroalkyl group, more preferably a perfluoroalkyl group. ｑ may be bonded to each other to form a ring. ｑ The group formed by bonding together is preferably an alkylene group which may have a substituent, more preferably a fluoroalkylene group, and even more preferably a perfluoroalkylene group. The alkylene group preferably has 2 to 4 carbon atoms.

[0240] Further, examples of the non-nucleophilic anion include anions represented by the following formulas (d1-1) to (d1-4).

[0241]

[0242] In formula (d1-1), R ５１ represents a hydrocarbon group (for example, an aryl group such as a phenyl group) which may have a substituent (for example, a hydroxyl group).

[0243] In formula (d1-2), Z ２ｃ represents a hydrocarbon group having 1 to 30 carbon atoms which may have a substituent (provided that the carbon atom adjacent to S is not substituted with a fluorine atom). ２ｃThe hydrocarbon group in the formula (d1-2) may be linear or branched, or may have a cyclic structure. In addition, a carbon atom in the hydrocarbon group (preferably, a carbon atom that is a ring atom when the hydrocarbon group has a cyclic structure) may be a carbonyl carbon (-CO-). Examples of the hydrocarbon group include a group having a norbornyl group that may have a substituent. The carbon atom forming the norbornyl group may be a carbonyl carbon. ２ｃ -SO ３ － " is preferably different from the anions represented by the above formulae (AN1) to (AN3). For example, Z ２ｃ is preferably other than an aryl group. For example, Z ２ｃ In the -SO ３ － The atoms at the α-position and β-position to Z are preferably atoms other than carbon atoms having a fluorine atom as a substituent. ２ｃ is -SO ３ － The atom at the α-position and / or the atom at the β-position to the aryl group is preferably a ring atom in a cyclic group.

[0244] In formula (d1-3), R ５２ represents an organic group (preferably a hydrocarbon group having a fluorine atom), Y ３ represents a linear, branched, or cyclic alkylene group, an arylene group, or a carbonyl group, and Rf represents a hydrocarbon group.

[0245] In formula (d1-4), R ５３ and R ５４ R each independently represents an organic group (preferably a hydrocarbon group having a fluorine atom). ５３ and R ５４ may be bonded to each other to form a ring.

[0246] The organic anions may be used alone or in combination of two or more.

[0247] It is also preferable that the photoacid generator is at least one selected from the group consisting of compounds (I) to (II).

[0248] (Compound (I)) Compound (I) is a compound having one or more structural moieties X and one or more structural moieties Y, which generates an acid containing the first acidic moiety derived from the structural moiety X and the second acidic moiety derived from the structural moiety Y when irradiated with actinic rays or radiation. Structural moiety X: Anionic moiety A １ － and the cationic moiety M １ ＋ and by irradiation with actinic rays or radiation, HA １ Structural moiety Y: anionic moiety A, which forms a first acidic moiety represented by the formula: ２ － and the cationic moiety M ２ ＋ and by irradiation with actinic rays or radiation, HA ２ The compound (I) satisfies the following condition I:

[0249] Condition I: In the compound (I), the cationic moiety M in the structural moiety X １ ＋ and the cationic moiety M in the structural moiety Y ２ ＋ H ＋ The compound PI in which the cation moiety M in the structural moiety X is replaced by １ ＋ H ＋ HA is replaced by １ and the cationic moiety M in the structural moiety Y. ２ ＋ H ＋ HA is replaced by ２ and an acid dissociation constant a2 derived from the acidic site represented by the formula (I), and the acid dissociation constant a2 is greater than the acid dissociation constant a1.

[0250] Condition I will be explained in more detail below. For example, when compound (I) is an acid-generating compound having one of the first acidic sites derived from the structural moiety X and one of the second acidic sites derived from the structural moiety Y, compound PI is "HA １ and H.A.２ The acid dissociation constant a1 and the acid dissociation constant a2 of the compound PI correspond to "a compound having the formula ". １ － and H.A. ２ The pKa at which the compound becomes "a compound having the above formula (A)" is the acid dissociation constant a1, １ － and H.A. ２ "A compound having １ － and A ２ － The pKa at which the compound becomes "a compound having the above formula (I)" is the acid dissociation constant a2.

[0251] For example, when compound (I) is an acid-generating compound having two of the first acidic sites derived from the structural site X and one of the second acidic sites derived from the structural site Y, compound PI is a compound having "two HAs １ and one HA ２ When the acid dissociation constant of compound PI is calculated, compound PI corresponds to "a compound having one A １ － and one HA １ and one HA ２ and the acid dissociation constant when "a compound having one A １ － and one HA １ and one HA ２ "Compound having two A １ － and one HA ２ The acid dissociation constant when the compound is a compound having two A's corresponds to the acid dissociation constant a1. １ － and one HA ２ "Compound having two A １ － and A ２ － In other words, in the case of compound PI, the acid dissociation constant when the compound becomes a compound having the cation moiety M in the structural moiety X corresponds to the acid dissociation constant a2. １ ＋ H ＋ HA is replaced by１ When the compound PI has a plurality of acid dissociation constants derived from the acidic moiety represented by the formula (I), the value of the acid dissociation constant a2 is larger than the largest value of the plurality of acid dissociation constants a1. １ － and one HA １ and one HA ２ The acid dissociation constant when the compound is aa is defined as "a compound having one A １ － and one HA １ and one HA ２ "Compound having two A １ － and one HA ２ When the acid dissociation constant when the compound becomes "a compound having the formula (I)" is ab, the relationship between aa and ab satisfies aa<ab.

[0252] The acid dissociation constants a1 and a2 are determined by the above-mentioned method for measuring an acid dissociation constant. The compound PI corresponds to the acid generated when compound (I) is irradiated with actinic rays or radiation. When compound (I) has two or more structural moieties X, the structural moieties X may be the same or different. In addition, when two or more of the above A １ － and two or more of the above M １ ＋ In compound (I), the above A １ － and the above A ２ － , and the above M １ ＋ and the above M ２ ＋ may be the same or different, but １ － and the above A ２ － are preferably different from each other.

[0253] In the compound PI, the difference (absolute value) between the acid dissociation constant a1 (the maximum value when there are multiple acid dissociation constants a1) and the acid dissociation constant a2 is preferably 0.1 or more, more preferably 0.5 or more, and even more preferably 1.0 or more. The upper limit of the difference (absolute value) between the acid dissociation constant a1 (the maximum value when there are multiple acid dissociation constants a1) and the acid dissociation constant a2 is not particularly limited, but is, for example, 16 or less.

[0254] In the compound PI, the acid dissociation constant a2 is preferably not more than 20, more preferably not more than 15. The lower limit of the acid dissociation constant a2 is preferably not less than −4.0.

[0255] In the compound PI, the acid dissociation constant a1 is preferably 2.0 or less, and more preferably 0 or less. The lower limit of the acid dissociation constant a1 is preferably −20.0 or more.

[0256] Anion site A １ － and anionic moiety A ２ － is a structural moiety containing a negatively charged atom or atomic group, and examples thereof include structural moieties selected from the group consisting of formulae (AA-1) to (AA-3) and formulae (BB-1) to (BB-6) shown below. １ － As the anionic moiety A, those capable of forming an acidic moiety with a small acid dissociation constant are preferred, and among these, any of formulas (AA-1) to (AA-3) is more preferred, and any of formulas (AA-1) and (AA-3) is even more preferred. ２ － As the anion moiety A １ － Preferably, it is one that can form an acidic site with a larger acid dissociation constant than the above, more preferably any of formulas (BB-1) to (BB-6), and even more preferably any of formulas (BB-1) and (BB-4). In the following formulas (AA-1) to (AA-3) and formulas (BB-1) to (BB-6), * represents a bonding position. In formula (AA-2), R Ａ represents a monovalent organic group. ＡThe monovalent organic group represented by the formula (I) is not particularly limited, but examples thereof include a cyano group, a trifluoromethyl group, and a methanesulfonyl group.

[0257]

[0258]

[0259] Cationic moiety M １ ＋ and cationic moiety M ２ ＋ is a structural moiety containing a positively charged atom or atomic group, and examples thereof include organic cations having a monovalent charge. ＋ Examples of the organic cation include those represented by the following formula:

[0260] (Compound (II)) Compound (II) is a compound having two or more of the above structural moieties X and one or more of the following structural moieties Z, which generates an acid containing two or more of the first acidic moieties derived from the structural moiety X and the structural moiety Z upon irradiation with actinic rays or radiation. Structural moiety Z: a ​​nonionic moiety capable of neutralizing an acid

[0261] In compound (II), the definition of the structural moiety X and A １ － and M １ ＋ The definition of the structural moiety X in compound (I) and A １ － and M １ ＋ The definition and preferred embodiments are also the same.

[0262] In the compound (II), the cation moiety M in the structural moiety X １ ＋ H ＋ In the compound PII, the cationic moiety M in the structural moiety X is replaced by １ ＋ H ＋ HA is replaced by １The preferred range of the acid dissociation constant a1 derived from the acidic moiety represented by the formula (I) is the same as the acid dissociation constant a1 in the compound PI. In addition, when the compound (II) is, for example, a compound that generates an acid having two of the first acidic moieties derived from the structural moiety X and the structural moiety Z, the compound PII is a compound that generates an acid having two HAs. １ When the acid dissociation constant of this compound PII was calculated, it was found that the compound PII has "one A １ － and one HA １ and the acid dissociation constant when "a compound having one A １ － and one HA １ "Compound having two A １ － The acid dissociation constant when the compound becomes "a compound having the formula (I)" corresponds to the acid dissociation constant a1.

[0263] The acid dissociation constant a1 can be determined by the above-mentioned method for measuring an acid dissociation constant. The compound PII corresponds to the acid generated when compound (II) is irradiated with actinic rays or radiation. The two or more structural moieties X may be the same or different. １ － and two or more of the above M １ ＋ may be the same or different.

[0264] The nonionic moiety capable of neutralizing an acid in the structural moiety Z is not particularly limited, and is preferably, for example, a moiety containing a group capable of electrostatically interacting with a proton or a functional group having electrons. Examples of the group capable of electrostatically interacting with a proton or the functional group having electrons include functional groups having a macrocyclic structure such as cyclic polyethers, and functional groups having a nitrogen atom with an unshared electron pair that does not contribute to π-conjugation. The nitrogen atom with an unshared electron pair that does not contribute to π-conjugation is, for example, a nitrogen atom having a partial structure shown in the following formula:

[0265]

[0266] Examples of the partial structure of a functional group having a group or electron capable of electrostatically interacting with a proton include a crown ether structure, an azacrown ether structure, a primary amine structure, a secondary amine structure, a tertiary amine structure, a pyridine structure, an imidazole structure, and a pyrazine structure. Of these, a primary amine structure, a secondary amine structure, a tertiary amine structure, and a tertiary amine structure are preferred.

[0267] Examples of moieties other than cations that Compound (I) and Compound (II) may have are shown below.

[0268]

[0269]

[0270] In a preferred embodiment of the present invention, the photoacid generator contains a fluorine atom or an iodine atom.

[0271] In a preferred embodiment of the present invention, the photoacid generator contains a cation having a fluorine atom.

[0272] In a preferred embodiment of the present invention, the photoacid generator contains an anion having an iodine atom.

[0273] The content of the photoacid generator in the resist composition is not particularly limited, but is preferably 1% by mass or more, more preferably 5% by mass or more, and even more preferably 10% by mass or more, based on the total solid content of the resist composition. Furthermore, the content of the photoacid generator is preferably 70% by mass or less, more preferably 60% by mass or less, and even more preferably 50% by mass or less, based on the total solid content of the resist composition. Only one photoacid generator may be used, or two or more types may be used. When two or more photoacid generators are used, the total content thereof is preferably within the above-mentioned preferred content range.

[0274] [Acid Diffusion Controller] The resist composition may further contain an acid diffusion controller. The acid diffusion controller can act as a quencher that traps acid generated, for example, from a photoacid generator during exposure and suppresses reaction of the polymer (P) in unexposed areas due to excess generated acid. The acid diffusion controller may be a compound different from the polymer (P) or the same compound. The acid diffusion controller may be a compound different from the photoacid generator or the same compound. The acid diffusion controller may be in the form of a low molecular weight compound or may be incorporated into a part of the polymer. Furthermore, an acid diffusion controller in the form of a low molecular weight compound and an acid diffusion controller in the form of an acid diffusion controller incorporated into a part of the polymer may be used in combination. When the acid diffusion controller is incorporated into a part of the polymer, it may be incorporated into a part of the polymer (P) or into a polymer different from the polymer (P). When the polymer (P) does not have the repeating unit having a photoacid generating group that functions as the acid diffusion controller, the resist composition preferably contains an acid diffusion controller that is a compound different from the polymer (P). When the polymer (P) contains a repeating unit having a photoacid-generating group that functions as an acid diffusion controller, the resist composition may or may not contain a separate acid diffusion controller.

[0275] The type of acid diffusion controller is not particularly limited, and examples thereof include a basic compound (DA), a low-molecular-weight compound (DB) having a nitrogen atom and a group that is cleaved by the action of an acid, and a compound (DC) whose acid diffusion control ability is reduced or eliminated by irradiation with actinic rays or radiation. Examples of the compound (DC) include an onium salt compound (DD) of an acid that is relatively weaker than the acid generated from the photoacid generator, and a basic compound (DE) whose basicity is reduced or eliminated by irradiation with actinic rays or radiation.

[0276] (Basic Compound (DA)) As the basic compound (DA), compounds having structures represented by the following formulae (A) to (E) are preferred.

[0277]

[0278] In formulas (A) and (E), R ２００, R ２０１ and R ２０２ may be the same or different, and each independently represents a hydrogen atom, an alkyl group (preferably having 1 to 20 carbon atoms), a cycloalkyl group (preferably having 3 to 20 carbon atoms), or an aryl group (preferably having 6 to 20 carbon atoms). ２００ , R ２０１ and R ２０２ At least two of R may be bonded to form a ring. ２０３ , R ２０４ , R ２０５ and R ２０６ may be the same or different, and each independently represents an alkyl group having 1 to 20 carbon atoms. In formulas (B), (C), (D), and (E), * represents a bonding position.

[0279] R in formulas (A) and (E) ２００ , R ２０１ , R ２０２ , R ２０３ , R ２０４ , R ２０５ and R ２０６ The alkyl group or cycloalkyl group represented by may have a substituent or may be unsubstituted. With regard to the alkyl group, the alkyl group having a substituent is preferably an aminoalkyl group having 1 to 20 carbon atoms, a hydroxyalkyl group having 1 to 20 carbon atoms, or a cyanoalkyl group having 1 to 20 carbon atoms. R in formulas (A) and (E) ２００ , R ２０１ , R ２０２ , R ２０３ , R ２０４ , R ２０５ and R ２０６ The alkyl group or cycloalkyl group represented by is more preferably unsubstituted.

[0280] Examples of the basic compound (DA) include guanidine, aminopyrrolidine, pyrazole, pyrazoline, piperazine, aminomorpholine, aminoalkylmorpholine, and piperidine. The basic compound (DA) may be a compound having at least one structure selected from the group consisting of an imidazole structure, a diazabicyclo structure, an onium hydroxide structure, an onium carboxylate structure, a trialkylamine structure, an aniline structure, and a pyridine structure. The basic compound (DA) may be an alkylamine derivative having at least one structure selected from the group consisting of a hydroxyl group and an ether bond, or an aniline derivative having at least one structure selected from the group consisting of a hydroxyl group and an ether bond.

[0281] The difference between the pKa of the conjugate acid of the basic compound (DA) and the pKa of the acid generated from the photoacid generator (the value obtained by subtracting the pKa of the acid generated from the photoacid generator from the pKa of the conjugate acid of the basic compound (DA)) is preferably 1.00 or more, more preferably 1.00 to 14.00, and even more preferably 2.00 to 13.00. The pKa of the conjugate acid of the basic compound (DA) varies depending on the type of photoacid generator used, but is, for example, preferably 1.00 to 14.00, more preferably 3.00 to 13.00, and even more preferably 3.50 to 12.50.

[0282] (Onium Salt Compound (DD) of an Acid that is Relatively Weaker than the Acid Generated from a Photoacid Generator) The compound (DD) may be a compound that generates an acid upon irradiation with actinic rays or radiation. The compound (DD) is preferably a compound that generates an acid that has a pKa that is 1.00 or more higher than that of the acid generated from the photoacid generator. The difference between the pKa of the acid generated from the compound (DD) and the pKa of the acid generated from the photoacid generator (the value obtained by subtracting the pKa of the acid generated from the photoacid generator from the pKa of the acid generated from the compound (DD)) is preferably 1.00 or more, more preferably 1.00 to 10.00, even more preferably 1.00 to 5.00, and particularly preferably 1.00 to 3.00. The pKa of the acid generated from compound (DD) varies depending on the type of photoacid generator used, but is preferably, for example, 0.50 to 10.00, more preferably 0.80 to 5.00, and even more preferably 1.00 to 5.00.

[0283] Compound (DD) is preferably an onium salt compound consisting of an anion and a cation. Examples of compound (DD) include "M ＋ X － " (preferably an onium salt). ＋ represents a cation, and preferably represents an organic cation. － represents an anion, and preferably represents an organic anion. ＋ As the photoacid generator, M ＋ The same as above can be mentioned. － Examples of the anion include the anions represented by formulas (d1-1) to (d1-4) described in the description of the photoacid generator, and the anion represented by formula (d1-1) or the anion represented by formula (d1-2) is preferred.

[0284] Specific examples of the basic compound (DA) include those described in paragraphs

[0132] to

[0136] of WO 2020 / 066824, and specific examples of the basic compound (DE) 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, and specific examples of the low molecular weight compound (DB) 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 (DD) that is a weaker acid than the acid generated from a photoacid generator or the like include those described in paragraphs

[0305] to

[0314] of WO 2020 / 158337.

[0285] 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.

[0286] The molecular weight of the acid diffusion controller is not particularly limited, but is preferably from 100 to 3,000, more preferably from 150 to 2,500, and even more preferably from 200 to 2,000.

[0287] The acid diffusion controller is also preferably a compound that generates an acid having a pKa of 0 or more upon irradiation with actinic rays or radiation.

[0288] When the resist composition contains an acid diffusion controller, the content of the acid diffusion controller is preferably 0.1% by mass or more, more preferably 0.5% by mass or more, and even more preferably 1% by mass or more, based on the total solid content of the resist composition. Furthermore, the content of the acid diffusion controller is preferably 30% by mass or less, more preferably 20% by mass or less, and even more preferably 10% by mass or less, based on the total solid content of the resist composition. Only one acid diffusion controller may be used, or two or more may be used. When two or more types are used, the total content thereof is preferably within the above-mentioned preferred content range.

[0289] [Hydrophobic Resin] The resist composition may further contain a polymer different from the polymer (P). Examples of the polymer different from the polymer (P) include a hydrophobic resin. The hydrophobic resin is preferably designed so that it is unevenly distributed on the surface of the resist film. However, unlike surfactants, the hydrophobic resin does not necessarily have to have a hydrophilic group in the molecule, and does not necessarily have to contribute to uniform mixing of the polar substance and the non-polar substance.

[0290] The hydrophobic resin contains 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 one or more of the partial structures, and more preferably two or more. The hydrophobic resin 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 hydrophobic resins include the compounds described in paragraphs

[0275] to

[0279] of WO 2020 / 004306.

[0291] When the resist composition contains a hydrophobic resin, the content of the hydrophobic resin is preferably 0.01 to 20.0 mass%, and more preferably 0.1 to 15.0 mass%, based on the total solids content of the resist composition. Only one type of hydrophobic resin may be used, 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.

[0292] [Surfactant] The resist composition may contain a surfactant. When the resist composition contains a surfactant, it is possible to form a pattern with better adhesion and fewer development defects. 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.

[0293] When the resist composition 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%, relative to the total solids content of the resist composition. One type of surfactant may be used, 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 preferred content range.

[0294] [Solvent] The resist composition 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, chain ketone, cyclic ketone, lactone, and alkylene carbonate. The solvent may further contain components other than components (M1) and (M2).

[0295] Combining the above-mentioned solvent with the above-mentioned polymer is preferable in terms of improving the coatability of the resist composition 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, so it is possible to 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.

[0296] 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.

[0297] The content of the solvent in the resist composition is preferably determined so that the solids concentration is from 0.5 to 30 mass %, and more preferably from 1 to 20 mass %, which further improves the coatability of the resist composition.

[0298] [Other Additives] The resist composition may further contain at least one additive selected from the group consisting of a dissolution-inhibiting compound, a dye, a plasticizer, a photosensitizer, a light absorber, a compound that promotes solubility in a developer (e.g., a phenolic compound having a molecular weight of 1,000 or less, or an alicyclic or aliphatic compound containing a carboxyl group), and a crosslinking agent. The "dissolution-inhibiting compound" is a compound having a molecular weight of 3,000 or less that decomposes under the action of acid to reduce its solubility in an organic developer. The "crosslinking agent" is a compound having a molecular weight of 3,000 or less that forms a bond with the polymer (P), a photoacid generator, or other components upon exposure to actinic rays or radiation, heat, acid, base, or the like. The inclusion of a crosslinking agent enables the formation of a pattern with excellent pattern strength, substrate adhesion, and resolution. Furthermore, the crosslinking agent can suppress the volatilization and elution of low-molecular-weight components in the pattern, thereby suppressing deformation of the finished pattern.

[0299] The content of the other additives is not particularly limited, but may be 20.0% by mass or less, 10.0% by mass or less, or 5.0% by mass or less, based on the total solid content of the resist composition. Only one type of other additive may be used, 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 preferred content range.

[0300] The resist composition may also contain water as an impurity. When water is contained as an impurity, the smaller the content of water, the more preferable, but the resist composition may contain 1 to 30,000 ppm by mass of water relative to the entire resist composition. The resist composition may also contain residual monomers (for example, monomers used in the synthesis of the polymer (P)) as impurities. When water is contained as an impurity, the smaller the content of residual monomers, the more preferable, but the resist composition may contain 1 to 30,000 ppm by mass of water relative to the entire solid content of the resist composition.

[0301] [Step (4)] Step (4) is a step of forming a film using the actinic ray-sensitive or radiation-sensitive resin composition (resist composition) obtained in step (3). Step (4) is preferably a step of forming a resist film on a substrate using the resist composition.

[0302] As a method for forming a resist film on a substrate using a resist composition, for example, a method of coating the resist composition on a substrate can be mentioned. If necessary, it is preferable to filter the resist composition before coating. The pore size of the filter is preferably 0.1 μm or less, more preferably 0.03 μm or less, even more preferably 0.01 μm or less, and particularly preferably 0.005 μm or less. The lower limit of the pore size of the filter is not particularly limited, but may be 0.001 μm or more. The material of the filter is not particularly limited. In the case of a polymer, it is preferable to use polyolefins such as polyethylene (PE) and polypropylene (PP) (including high density and ultra-high molecular weight); polyamides such as nylon 6 and nylon 66; polyimide (PI); polyamideimide; polyesters such as polyethylene terephthalate; polyethersulfone; cellulose; polyfluorocarbons such as polytetrafluoroethylene (PTFE) and perfluoroalkoxyalkane; derivatives of the above polymers; etc., and more preferably at least one selected from the group consisting of polyolefins, polyamides, polyimides, polyamideimides, polyesters, polysulfones, cellulose, polyfluorocarbons, and derivatives thereof. In addition to resins, diatomaceous earth, glass, etc. may also be used. The filter used to filter the resist composition may be one filter, or two or more filters may be used in combination. When two or more filters are used, they may be the same filter or different filters.

[0303] The resist composition can be applied onto a substrate (e.g., silicon, silicon coated with silicon dioxide, etc.) 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 when spin application using a spinner is preferably 1000 to 3000 rpm (rotations per minute). After application of the resist composition, the substrate may be dried to form a resist film. If necessary, various undercoating films (inorganic film, organic film, anti-reflective film, etc.) may be formed below the resist film.

[0304] An example of a drying method is a method of drying by heating. Heating can be performed by means provided in at least one of a normal exposure machine and a developing machine, and may be performed using a hot plate or the like. The heating temperature is not particularly limited, but is preferably 80 to 150°C, more preferably 80 to 140°C, and even more preferably 80 to 130°C. The heating time is not particularly limited, but is preferably 30 to 1,000 seconds, more preferably 60 to 800 seconds, and even more preferably 60 to 600 seconds.

[0305] 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. Furthermore, 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.

[0306] 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 basic compounds that may be contained in the resist composition. 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.

[0307] [Step (5)] Step (5) is a step of exposing the film (resist film) formed in step (4). 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, and preferably far ultraviolet light with a wavelength of 250 nm or less, more preferably 220 nm or less, and particularly preferably 1 to 200 nm, specifically KrF excimer laser (248 nm), ArF excimer laser (193 nm), F ２ These include excimer laser (157 nm), EUV (13 nm), X-ray, and electron beam.

[0308] 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 for baking is not particularly limited, but is preferably 80 to 150°C, more preferably 80 to 140°C, and even more preferably 80 to 130°C. The heating time for baking is not particularly limited, but is preferably 10 to 1,000 seconds, more preferably 10 to 180 seconds, and even more preferably 30 to 120 seconds. Heating can be carried out using a means provided in at least one of a conventional exposure machine and a development machine, and may be carried out using a hot plate or the like. This process is also called post-exposure baking.

[0309] [Step (6)] Step (6) is a step of developing the film exposed in step (5) with an organic processing liquid. The organic processing liquid used in step (6) contains butyl acetate and a hydrocarbon having from 9 to 12 carbon atoms. The hydrocarbon having from 9 to 12 carbon atoms contained in the organic processing liquid used in step (6) is preferably at least one selected from the group consisting of alkanes, alkenes, alkynes, and cycloalkanes, more preferably an alkane, even more preferably at least one selected from the group consisting of nonane, decane, undecane, and dodecane, particularly preferably at least one selected from the group consisting of undecane and dodecane, and most preferably undecane. The hydrocarbon having from 9 to 12 carbon atoms may contain a structural isomer when such a structural isomer exists, such as undecane or dodecane. The hydrocarbon having from 9 to 12 carbon atoms contained in the organic processing liquid may be one or more.

[0310] The content of hydrocarbons having from 9 to 12 carbon atoms in the organic treatment liquid (the total amount when multiple hydrocarbons having from 9 to 12 carbon atoms are contained) is preferably from 1 to 40 mass %, more preferably from 1 to 35 mass %, even more preferably from 5 to 30 mass %, and particularly preferably from 10 to 25 mass %, based on 100 mass % of the entire organic treatment liquid.

[0311] The organic treatment liquid contains butyl acetate (n-butyl acetate). The content of butyl acetate in the organic treatment liquid is preferably 60% by mass or more and 99% by mass or less, more preferably 65% ​​by mass or more and 99% by mass or less, even more preferably 70% by mass or more and 95% by mass or less, and particularly preferably 75% by mass or more and 90% by mass or less, based on 100% by mass of the entire organic treatment liquid.

[0312] The mass ratio of butyl acetate to hydrocarbons having from 9 to 12 carbon atoms in the organic treatment liquid (butyl acetate content / hydrocarbon content having from 9 to 12 carbon atoms) is preferably 60 / 40 to 95 / 5, more preferably 70 / 30 to 95 / 5, even more preferably 80 / 20 to 90 / 10, and particularly preferably 90 / 10.

[0313] The organic treatment liquid may contain other components in addition to butyl acetate and hydrocarbons having from 9 to 12 carbon atoms. Examples of other components include water, organic solvents other than butyl acetate and hydrocarbons having from 9 to 12 carbon atoms, surfactants, antioxidants, basic compounds, etc. The content of other components in the organic treatment liquid is preferably from 0 to 5% by mass, more preferably from 0 to 1% by mass, even more preferably from 0 to 0.5% by mass, and particularly preferably 0% by mass (i.e., no other components are contained), based on 100% by mass of the entire organic treatment liquid.

[0314] The developing method in step (6) is not particularly limited, but examples include a method in which the resist film is immersed in a tank filled with a developer (the organic processing liquid) for a certain period of time (dip method), a method in which the developer is raised on the surface of the resist film by surface tension and then left stationary for a certain period of time to develop (puddle method), a method in which the developer is sprayed onto the surface of the resist film (spray method), and a method in which the 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 area to be removed, and is preferably 10 to 300 seconds, more preferably 20 to 120 seconds. The temperature of the developer is not particularly limited, but is preferably 0 to 50°C, more preferably 15 to 35°C.

[0315] By performing step (6), a resist pattern (also simply referred to as a "pattern") is formed. After performing step (6), rinsing may be performed. The rinsing may be performed using the organic treatment liquid described above, or a rinse liquid other than the organic treatment liquid described above. The rinse liquid other than the organic treatment liquid described above is not particularly limited as long as it does not dissolve the pattern, and a solution containing a general organic solvent may be used. The rinse liquid other than the organic treatment liquid described above preferably contains at least one organic solvent selected from the group consisting of hydrocarbon solvents, ketone solvents, ester solvents, alcohol solvents, amide solvents, and ether solvents.

[0316] The rinsing method is not particularly limited, and examples thereof include a method in which the rinse liquid is continuously discharged onto a substrate rotating at a constant speed (spin coating method), a method in which the substrate is immersed in a tank filled with the rinse liquid for a certain period of time (dip method), and a method in which the rinse liquid is sprayed onto the surface of the substrate (spray method).

[0317] The pattern formation method of the present invention may also include a heating step (post-bake) after step (6). This step removes the developer and rinse solution remaining between and within the pattern. This step also has the effect of annealing the resist pattern and improving the surface roughness of the pattern. The heating step after step (6) may be carried out, for example, at 40 to 250°C (preferably 90 to 200°C) for 10 seconds to 3 minutes (preferably 30 to 120 seconds).

[0318] 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 (6) 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 (6) as a mask is preferred. The dry etching is not particularly limited, but oxygen plasma etching is preferred.

[0319] The organic processing liquid, resist composition, and other various materials (e.g., solvent, rinse solution, anti-reflective coating composition, top coat composition, etc.) used in the pattern formation method of the present invention 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 (parts per trillion) or less, particularly preferably 10 mass ppt or less, and most preferably 1 mass ppt or less. The lower limit of the impurity content is not particularly limited, and may be 0 mass ppt or more. 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.

[0320] 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.

[0321] 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).

[0322] 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 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 a content of 0 ppt by mass or more is preferred.

[0323] A conductive compound may be added to the organic processing solution and 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 terms of maintaining favorable development characteristics or rinsing characteristics, it is preferably 10% by mass or less, more preferably 5% by mass or less. The lower limit of the amount of the conductive compound added is not particularly limited, and may be 0.01% by mass or more. 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.

[0324] <Method for manufacturing an electronic device> This specification 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. Preferred embodiments of the electronic device of this specification include those installed in electrical and electronic devices (such as home appliances, office automation (OA), media-related devices, optical devices, and communication devices).

[0325] The second aspect of the present invention will be described in detail below. The following description of the components may be based on representative embodiments of the present invention, but the present invention is not limited to such embodiments.

[0326] 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. In this specification, "exposure" refers to not only exposure using the bright line spectrum of a mercury lamp, far ultraviolet rays typified by excimer lasers, extreme ultraviolet rays, and X-rays, but also drawing using particle beams such as electron beams and ion beams, unless otherwise specified.

[0327] 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. In this specification, (meth)acrylate refers to at least one of acrylate and methacrylate. Furthermore, (meth)acrylic acid refers to at least one of acrylic acid and methacrylic acid.

[0328] 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).

[0329] 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:

[0330] (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, an acryloyl group, a methacryloyl group, a methyl ... Examples of the substituent T include acyl groups such as yl groups and methoxalyl groups; sulfanyl groups; alkylsulfanyl groups such as methylsulfanyl groups and tert-butylsulfanyl groups; arylsulfanyl groups such as phenylsulfanyl groups and p-tolylsulfanyl groups; alkylsulfonyl groups; arylsulfonyl groups; alkyl groups; alkenyl groups; cycloalkyl groups; aryl groups; heteroaryl groups; hydroxy groups; carboxy groups; formyl groups; sulfo groups; cyano groups; alkylaminocarbonyl groups; arylaminocarbonyl groups; sulfonamide groups; silyl groups; amino groups; nitro groups; carbamoyl groups; and the like. 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 (for example, a monoalkylamino group, a dialkylamino group, an arylamino group, a trifluoromethyl group, etc.).

[0331] 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".

[0332] In this specification, the acid dissociation constant (pKa) refers to the pKa in an aqueous solution, and specifically, is a value calculated based on a database of Hammett's substituent constants and known literature values ​​using the following software package 1. All pKa values ​​described in this specification are values ​​calculated using this software package. Software package 1: Advanced Chemistry Development (ACD / Labs) Software V8.14 for Solaris (1994-2007 ACD / Labs).

[0333] 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.

[0334] In this specification, pKa refers to a value calculated based on a database of Hammett's substituent constants and 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.

[0335] In this specification, the term "solid content" refers to components contained in the actinic ray-sensitive or radiation-sensitive resin composition and that form a film (e.g., a resist film) formed using the actinic ray-sensitive or radiation-sensitive resin composition, and does not include solvents. Furthermore, any component contained in the actinic ray-sensitive or radiation-sensitive resin composition and that forms a film (e.g., 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.

[0336] [Actinic Ray- or Radiation-Sensitive Resin Composition] The actinic ray- or radiation-sensitive resin composition of the present invention (also referred to as "the composition of the present invention") is an actinic ray- or radiation-sensitive resin composition containing a resin (A) containing a repeating unit (a) having an acid-decomposable group, a compound (B) that generates an acid upon irradiation with actinic rays or radiation, a solvent, and a crosslinking agent, wherein the content of the repeating unit (a) in the resin (A) is 40 mol % or more based on the total repeating units of the resin (A).

[0337] Although the mechanism by which the composition of the present invention achieves the above-mentioned effects is not fully understood, the inventors have hypothesized it as follows. However, the present invention is not limited in any way by the hypothesized mechanism below. The composition of the present invention contains a resin (A) containing 40 mol% or more of repeating units (a) having an acid-decomposable group relative to all repeating units. By containing 40 mol% or more of repeating units (a) having an acid-decomposable group relative to all repeating units, the resin (A) improves solubility in unexposed and weakly exposed regions, so that even if an unintended crosslinking reaction occurs in a weakly exposed region, it is less likely to manifest as residue. This is thought to suppress the occurrence of defects. A high content of repeating units (a) having an acid-decomposable group means that there are fewer other repeating units in the resin, which reduces the number of reactive sites for the crosslinking reaction. However, it is thought that the above-mentioned effect is achieved as a result of the aforementioned solubility improvement effect outweighing the disadvantage of reducing the number of crosslinking reactive sites.

[0338] The composition of the present invention is typically a resist composition, and is preferably a negative resist composition. A negative resist composition is a resist composition that can form a pattern by removing unexposed areas by development and leaving exposed areas. 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 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.

[0339] First, the various components of the composition of the present invention will be described in detail below.

[0340] [Resin (A)] The composition of the present invention contains a resin (A) (also simply referred to as "resin (A)") that includes a repeating unit (a) having an acid-decomposable group. The resin (A) is a resin that decomposes under the action of an acid (acid-decomposable resin), and is preferably a resin whose polarity changes under the action of an acid, and more preferably a resin whose polarity increases under the action of an acid.

[0341] <Repeating Unit (a)> The resin (A) contains a repeating unit (a) (also simply referred to as "repeating unit (a)") having an acid-decomposable group. The acid-decomposable group is a group that decomposes under the action of an acid to increase its polarity, and is typically 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 by a group that leaves under the action of an acid (leaving group). It is preferable that the polarity of the resin (A) increases under the action of an acid, so that its solubility in an alkaline developer increases and its solubility in an organic solvent decreases. Examples of the polar group include a carboxy group, a phenolic hydroxy 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 hydroxy group. Among these, the polar group is preferably a carboxy group, a phenolic hydroxy group, a fluorinated alcohol group (preferably a hexafluoroisopropanol group), or a sulfonic acid group, and more preferably a carboxy group. The repeating unit (a) preferably has a structure in which the carboxy group is protected by a group that is released by the action of an acid.

[0342] Examples of the group that is eliminated by the action of an acid include groups represented by any one of formulas (Y1), (Y2), (Y3) and (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 １ ) (Rn ２ ) (H)

[0343] In formula (Y1) and formula (Y2), Rx １ ~Rx ３ Each of Rx independently represents an alkyl group, a cycloalkyl group, an alkenyl group, an alkynyl group, or an aryl group. １ ~Rx ３ When all of Rx are alkyl groups, １ ~Rx ３ Preferably, at least two of Rx are methyl groups. １ ~Rx ３ Two of Rx may be bonded to form a ring. １ ~Rx ３ The alkyl group represented by the formula (I) 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 Preferred cycloalkyl groups represented by the formula (I) are monocyclic cycloalkyl groups such as a cyclopentyl group and a cyclohexyl group, and polycyclic cycloalkyl groups such as a norbornyl group, a tetracyclodecanyl group, a tetracyclododecanyl group, and an adamantyl group. １ ~Rx ３ The alkenyl group represented by Rx is preferably a vinyl group. １ ~Rx ３ The alkynyl group represented by the formula (I) is preferably an ethynyl group or a propargyl group. １ ~Rx ３ 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 10 carbon atoms. Examples of the aryl group include a phenyl group, a naphthyl group, and an anthryl group.

[0344] Rx １ ~Rx ３ The ring formed by combining two of Rx may be a monocyclic ring or a polycyclic ring. １ ~Rx ３ The ring formed by combining two of Rx is preferably a cycloalkane ring. １ ~Rx ３The cycloalkane ring formed by bonding two of these is preferably a monocyclic cycloalkane ring such as a cyclopentane ring or a cyclohexane ring, or a polycyclic cycloalkane ring such as a norbornane ring, a tetracyclodecane ring, a tetracyclododecane ring, or an adamantane ring, and more preferably a monocyclic cycloalkane ring having 5 to 6 carbon atoms. １ ~Rx ３ In the cycloalkane ring formed by bonding two of the above, one or more methylene groups constituting the ring may be replaced with at least one selected from the group consisting of a heteroatom such as an oxygen atom, a group containing a heteroatom such as a carbonyl group, and a vinylidene group. １ ~Rx ３ In the cycloalkane ring formed by bonding two of the above, one or more of the ethylene groups constituting the ring may be replaced by a vinylene group. １ is a methyl group or an ethyl group, and Rx ２ and Rx ３ and are bonded to form the above-mentioned cycloalkane ring.

[0345] When the composition of the present invention is used as an EUV resist, Rx 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.

[0346] In formula (Y3), R ３６ ~R ３８ R each independently represents a hydrogen atom or a monovalent organic group. ３７ and R ３８ may be bonded to each other to form a ring. ３６ ~R ３８ Examples of the monovalent organic group represented by R include an alkyl group, a cycloalkyl group, an aryl group, an aralkyl group, an alkenyl group, and an alkynyl group. ３６is also preferably a hydrogen atom. The alkyl group, cycloalkyl group, aryl group, alkenyl group, and alkynyl 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. When the resist composition of the present invention is used as an EUV resist, 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.

[0347] In formula (Y4), Rn １ represents an alkenyl group, an alkynyl group, an aryl group, or a heteroaryl group. ２ represents a hydrogen atom, an alkyl group, a cycloalkyl group, an alkenyl group, an alkynyl group, an aryl group, or a heteroaryl group. １ and Rn ２ may be bonded to each other to form a ring. １ Preferably, Rn represents an aryl group. When the composition of the present invention is used as an EUV resist, １ , and Rn ２ The alkyl group, cycloalkyl group, alkenyl group, alkynyl group, aryl group, and heteroaryl group represented by the following formula (I) preferably have a fluorine atom or an iodine atom as a substituent.

[0348] 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.

[0349] 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.

[0350] As the repeating unit (a), a repeating unit represented by formula (AI) and a repeating unit represented by formula (A-II) are also preferred.

[0351]

[0352] 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 ３ are Rx in the above formula (Y1), １ ~Rx ３ In formula (A-II), Xa １ and T are each Xa in formula (AI). １ and T. １ and Rn ２ are Rn in the above formula (Y4), １ and Rn ２ It has the same meaning as:

[0353] Xa １ Examples of the alkyl group represented by the formula (I) which may have a substituent include a methyl group or a —CH ２ -R １１ Examples of the group include a group represented by the following formula: １１ represents a halogen atom (such as a fluorine atom), a hydroxy group, or a monovalent organic group. １１Examples 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.

[0354] Examples of the divalent linking group represented by T include an alkylene group, an aromatic group, a -COO-Rt- group, and a -O-Rt- group. In the formula, Rt represents an alkylene group or a cycloalkylene group. T preferably represents 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 -, -(CH ２ ) ２ - or -(CH ２ ) ３ - is more preferable.

[0355] Rx １ ~Rx ３ The alkyl group represented by the formula (I) 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 represented by the formula (I) 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 alkenyl group represented by Rx is preferably a vinyl group. １ ~Rx ３ The alkynyl group represented by the formula (I) is preferably an ethynyl group or a propargyl group. １ ~Rx ３The 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 10 carbon atoms. Examples of the aryl group include a phenyl group, a naphthyl group, and an anthryl group.

[0356] Rx １ ~Rx ３ The ring formed by combining two of Rx may be a monocyclic ring or a polycyclic ring. １ ~Rx ３ The ring formed by combining two of Rx is preferably a cycloalkane ring. １ ~Rx ３ The cycloalkane ring formed by combining two of these is preferably a monocyclic cycloalkane ring such as a cyclopentane ring or a cyclohexane ring. Polycyclic cycloalkane rings such as a norbornane ring, a tetracyclodecane ring, a tetracyclododecane ring, or an adamantane ring are also preferred. Among these, a monocyclic cycloalkane ring having 5 to 6 carbon atoms is preferred. １ ~Rx ３ In the cycloalkane ring formed by bonding two of the above, for example, one or more methylene groups constituting the ring may be replaced with at least one selected from the group consisting of a heteroatom such as an oxygen atom, a group containing a heteroatom such as a carbonyl group, and a vinylidene group. １ ~Rx ３ In the cycloalkane ring formed by combining two of the above, one or more of the ethylene groups constituting the ring may be replaced with a vinylene group. １ is a methyl group or an ethyl group, and Rx ２ and Rx ３ and are bonded to form the above-mentioned cycloalkane ring.

[0357] When each of the above groups has a substituent, examples of the substituent include an alkyl group (e.g., having 1 to 4 carbon atoms), a halogen atom, a hydroxy group, an alkoxy group (e.g., having 1 to 4 carbon atoms), a carboxy group, and an alkoxycarbonyl group (e.g., having 2 to 6 carbon atoms). The number of carbon atoms in the substituent is preferably 8 or less.

[0358] The repeating unit represented by formula (AI) is preferably 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).

[0359] Specific examples of the repeating unit (a) are shown below, but are not limited to these. Further, for specific examples of the repeating unit (a), reference can be made to the description in paragraphs

[0029] to

[0071] of WO 2022 / 024928, which is incorporated herein by reference. Preferred monomers corresponding to the repeating unit (a) include MA-1 to MA-24 described in the Examples below.

[0360] The monomer corresponding to a repeating unit refers to a repeating unit whose structure is the same as that of the repeating unit when the polymerizable group of the monomer is polymerized; the repeating unit does not necessarily have to be one actually obtained using the monomer (for example, the repeating unit may be obtained by modifying the structure through a chemical reaction after performing a polymerization reaction using another monomer). Examples of the polymerizable group of the monomer include groups containing a carbon-carbon double bond, such as a vinyl group, an allyl group, an acryloyl group, and a methacryloyl group. Examples of the polymerization reaction include an addition polymerization reaction. Examples of repeating units and monomers corresponding to the repeating unit include a repeating unit represented by the following formula (RM-1) and a corresponding monomer represented by the following formula (RM-2).

[0361]

[0362] In formulas (RM-1) and (RM-2), R １００ represents a hydrogen atom or a substituent. １０１ represents a substituent. １ and ※ ２ represents the bond position.

[0363]

[0364] The content of the repeating unit (a) in the resin (A) is 40 mol% or more, preferably 50 mol% or more, and more preferably 55 mol% or more, based on the total repeating units of the resin (A). The content of the repeating unit (a) is preferably less than 100 mol%, more preferably 95 mol% or less, and even more preferably 90 mol% or less, based on the total repeating units of the resin (A). The repeating unit (a) contained in the resin (A) may be one type or two or more types. When the repeating unit (a) contained in the resin (A) is two or more types, it is preferable that the total content thereof is within the above-mentioned suitable content range.

[0365] <Repeating Unit Having an Acid Group> The resin (A) preferably contains a repeating unit having an acid group. The repeating unit having an acid group is preferably a repeating unit different from the repeating unit (a) described above. The repeating unit having an acid group may have a fluorine atom or an iodine atom. The acid group is preferably a carboxy group, a phenolic hydroxy group, a fluorinated alcohol group (preferably a hexafluoroisopropanol group), a sulfonic acid group, a sulfonamide group, or an isopropanol group. The repeating unit having an acid group is particularly preferably a repeating unit having a phenolic hydroxy 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 a -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 A ring containing - may be formed.

[0366] The repeating unit having an acid group is preferably a repeating unit represented by the following formula (b-1): The resin (A) preferably contains a repeating unit represented by the following formula (b-1).

[0367]

[0368] In formula (b-1), R １１ , R １２ and R１３ each independently represents a hydrogen atom, an alkyl group, a halogen atom, a cyano group, or an alkoxycarbonyl group. １ is a single bond, —COO— or —CONR ｍ１ - represents. ｍ１ represents a hydrogen atom or an alkyl group. ｍ１ and R １２ and may be bonded to each other to form a ring. １ represents a single bond or an alkylene group. １ and R １２ may be bonded to each other to form a ring. １ represents an aromatic group. １ and R １２ may be bonded to each other to form a ring, and n represents an integer of 1 to 4.

[0369] In formula (b-1), R １１ , R １２ and R １３ R each independently represents a hydrogen atom, an alkyl group, a halogen atom, a cyano group, or an alkoxycarbonyl group. １１ , R １２ and R １３ The alkyl group represented by the formula (I) may be either linear or branched, and may have a substituent. The number of carbon atoms in the alkyl group is not particularly limited, but is preferably 1 to 10, more preferably 1 to 5, and even more preferably 1 to 3. Examples of the alkyl group include a methyl group, an ethyl group, an n-propyl group, an isopropyl group, an n-butyl group, an isobutyl group, and a t-butyl group. R １１ , R １２ and R １３ Examples of the halogen atom represented by R include a fluorine atom, a chlorine atom, a bromine atom, and an iodine atom, and a fluorine atom or an iodine atom is preferred. １１ , R １２ and R １３ The alkyl group contained in the alkoxycarbonyl group represented by the formula (I) may be either linear or branched. The number of carbon atoms in the alkyl group contained in the alkoxycarbonyl group is not particularly limited, but is preferably 1 to 5, and more preferably 1 to 3. The alkoxycarbonyl group may have a substituent.

[0370] In formula (b-1), X １ is a single bond, —COO— or —CONR ｍ１ - represents. ｍ１ represents a hydrogen atom or an alkyl group. ｍ１ Examples of the alkyl group represented by R include alkyl groups having 20 or less carbon atoms, such as methyl, ethyl, propyl, isopropyl, n-butyl, sec-butyl, hexyl, 2-ethylhexyl, octyl, and dodecyl groups, and alkyl groups having 8 or less carbon atoms are preferred. ｍ１ and R １２ may be bonded to each other to form a ring. ｍ１ and R １２ When R ｍ１ and R １２ may be bonded to via a single bond or a linking group. Examples of the linking group include —O—, —S—, —CO—, and —CO ２ -, -SO-, -SO ２ -, alkylene groups (preferably having 1 to 5 carbon atoms), alkenylene groups (preferably having 2 to 5 carbon atoms), and groups formed by combining two or more of these. The alkylene groups and alkenylene groups may have a substituent.

[0371] In formula (b-1), L １ represents a single bond or an alkylene group. １ The alkylene group represented by the formula (I) 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. The alkylene group may have a substituent. １ and R １２ and may be bonded to each other to form a ring. １ and R １２ When and are bonded to each other, L １ and R １２ may be bonded to via a single bond or a linking group. Examples of the linking group include —O—, —S—, —CO—, and —CO ２ -, -SO-, -SO ２-, alkylene groups (preferably having 1 to 5 carbon atoms), alkenylene groups (preferably having 2 to 5 carbon atoms), and groups formed by combining two or more of these. The alkylene groups and alkenylene groups may have a substituent.

[0372] In formula (b-1), Ar １ represents an aromatic group. １ The aromatic group represented by the formula (I) may be either an aromatic hydrocarbon group or an aromatic heterocyclic group. The aromatic hydrocarbon group is preferably a group containing an aromatic hydrocarbon having 6 to 18 carbon atoms, such as benzene, naphthalene, anthracene, or naphthacene. The aromatic heterocyclic group preferably contains at least one heteroatom selected from a nitrogen atom, an oxygen atom, and a sulfur atom as a ring member. The aromatic heterocyclic group is preferably a group containing an aromatic heterocycle having 4 to 20 ring atoms, such as thiophene, furan, pyridine, pyrrole, benzothiophene, benzofuran, benzopyrrole, triazine, imidazole, benzimidazole, triazole, thiadiazole, or thiazole.

[0373] Ar １ The aromatic group represented by the formula (I) has n hydroxy groups as substituents, and may further have a substituent other than a hydroxy group. Examples of the substituent other than a hydroxy group include a carboxy group, a sulfo group, a cyano group, a halogen atom, a hydrocarbon group, an amino group, a nitro group, and a group formed by combining two or more of these. Examples of the hydrocarbon group include an alkyl group (preferably having 1 to 10 carbon atoms), a cycloalkyl group (preferably having 5 to 15 carbon atoms), and an alkenyl group (preferably having 2 to 10 carbon atoms). The hydrocarbon group may have a substituent. In addition, when the hydrocarbon group is -CH ２ When it contains -, -CH ２ At least one of - is -O-, -CO-, -S- and -SO ２ - may be substituted with at least one selected from the group consisting of. The substituent other than the hydroxy group is preferably a halogen atom or a group having a halogen atom. The halogen atom is preferably a fluorine atom or an iodine atom.

[0374] Ar １and R １２ may be bonded to each other to form a ring. １ and R １２ When Ar and Ar are bonded to each other, １ and R １２ may be bonded to via a single bond or a linking group. Examples of the linking group include —O—, —S—, —CO—, and —CO ２ -, -SO-, -SO ２ -, alkylene groups (preferably having 1 to 5 carbon atoms), alkenylene groups (preferably having 2 to 5 carbon atoms), and groups formed by combining two or more of these. The alkylene groups and alkenylene groups may have a substituent.

[0375] In formula (b-1), n ​​represents an integer of 1 to 4, and may represent an integer of 1 to 3, or may represent 1 or 2.

[0376] Specific examples of the repeating unit having an acid group include the repeating units described in paragraphs

[0079] to

[0110] of WO 2022 / 024928, which are incorporated herein by reference. MC-1 to MC-11 described in the Examples below are also preferred as monomers corresponding to the repeating unit having an acid group.

[0377] 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 is preferably less than 60 mol%, more preferably 50 mol% or less, and even more preferably 45 mol% or less, based on the total repeating units in the resin (A).

[0378] <Repeating unit having a lactone group, a sultone group, or a carbonate group> The resin (A) may have a repeating unit (also referred to as a "repeating 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 the repeating unit Y does not have a hydroxy group or an acid group such as a hexafluoropropanol group.

[0379] 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 lactone structure or a 5- to 7-membered sultone structure. Among these, a 5- to 7-membered lactone structure to which another ring structure is fused in the form of a bicyclo or spiro structure, or a 5- to 7-membered sultone structure to which another ring structure is fused in the form of a bicyclo or spiro structure, is more preferred. For units containing a lactone group or a sultone group, see, for example, paragraphs

[0119] to

[0126] and

[0132] to

[0133] of WO 2022 / 024928, and the above descriptions are incorporated herein.

[0380] 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, which is incorporated herein by reference.

[0381] When the resin (A) contains the repeating unit Y, the content of the repeating unit Y is preferably 1 mol % or more, more preferably 10 mol % or more, based on the total repeating units in the resin (A), and the content of the repeating unit Y is preferably less than 40 mol %, more preferably 35 mol % or less, based on the total repeating units in the resin (A).

[0382] <Repeating unit having a photoacid generating group> The resin (A) may contain a repeating unit having a group that generates an acid upon irradiation (exposure) with actinic rays or radiation (also referred to as a "photoacid generating group"). It is also preferable that the resin (A) does not contain a repeating unit having a photoacid generating group.

[0383] 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, and the above descriptions are incorporated herein by reference.

[0384] 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 even more preferably 5 mol% or more, based on the total repeating units in the resin (A). Also, the content of the repeating unit having a photoacid generating group is preferably less than 40 mol%, more preferably 30 mol% or less, and even more preferably 20 mol% or less, based on the total repeating units in the resin (A).

[0385] <Repeating unit represented by formula (V-1) or formula (V-2)> The resin (A) may have a repeating unit represented by the following formula (V-1) or formula (V-2): The repeating unit represented by the following formula (V-1) or formula (V-2) is preferably a repeating unit different from the repeating units described above.

[0386]

[0387] In formulas (V-1) and (V-2), R ６ and R ７ each independently represents a hydrogen atom, a hydroxy 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 carboxy 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 represents a methylene group, an oxygen atom, or a sulfur atom. Examples of the repeating unit represented by formula (V-1) or (V-2) include the repeating units described in paragraph

[0100] of WO 2018 / 193954, the description of which is incorporated herein by reference.

[0388] <Repeating unit for reducing main chain mobility> The resin (A) preferably has a high glass transition temperature (Tg) in order to suppress excessive diffusion of generated acid or pattern collapse during development. With regard to the repeating unit for reducing main chain mobility, the contents of paragraphs

[0144] to

[0160] of WO 2022 / 024928 are incorporated by reference.

[0389] <Repeating unit having at least one group selected from a lactone group, a sultone group, a carbonate group, a hydroxy 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 hydroxy 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 include the repeating units described above for repeating unit Y. The preferred content is also as described for repeating unit Y.

[0390] The resin (A) may have a repeating unit having a hydroxy group or a cyano group. This improves substrate adhesion. The repeating unit having a hydroxy group or a cyano group is preferably a repeating unit having a saturated hydrocarbon group having a hydroxy group or a cyano group (substituted with a hydroxy group or a cyano group). Alternatively, it may be a repeating unit having an alicyclic hydrocarbon structure substituted with a hydroxy group or a cyano group. The repeating unit having a hydroxy group or a cyano group preferably does not have an acid-decomposable group. Examples of repeating units having a hydroxy group or a cyano group include repeating units described in paragraphs

[0081] to

[0084] of JP 2014-098921 A, and the above descriptions are incorporated herein by reference.

[0391] The resin (A) may have a repeating unit having an alkali-soluble group. Resin (A) containing a repeating unit having an alkali-soluble group enhances resolution in contact hole applications. Examples of the alkali-soluble group include a carboxy 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 carboxy group being preferred. Examples of the repeating unit having an alkali-soluble group include the repeating units described in paragraphs

[0085] and

[0086] of JP 2014-098921 A, the disclosures of which are incorporated herein by reference.

[0392] <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.

[0393] <Repeating Unit Represented by Formula (III) Having Neither a Hydroxy Group nor a Cyano Group> The resin (A) may have a repeating unit represented by formula (III) having neither a hydroxy group nor a cyano group.

[0394]

[0395] In formula (III), R ５ represents a hydrocarbon group having at least one cyclic structure and having neither a hydroxy group nor a cyano group, and Ra represents a hydrogen atom, an alkyl group, or —CH ２ -O-Ra ２ represents a group. ２represents 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 hydroxy group or a cyano group include the repeating units described in paragraphs

[0087] to

[0094] of JP 2014-098921 A, the descriptions of which are incorporated herein by reference.

[0396] <Other Repeating Units> Furthermore, the resin (A) may have other repeating units in addition to the repeating units described above. For example, see paragraphs

[0141] to

[0143] and

[0169] to

[0170] of WO 2022 / 024928, which are incorporated herein by reference.

[0397] 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.

[0398] In a preferred embodiment of the present invention, the resin (A) has at least one selected from the group consisting of a lactone group, a carbonate group, a sultone group, and a saturated hydrocarbon group having a hydroxy group. By having the resin (A) have at least one selected from the group consisting of a lactone group, a carbonate group, a sultone group, and a saturated hydrocarbon group having a hydroxy group, the etching resistance and LWR performance are further improved.

[0399] In a preferred embodiment of the present invention, the resin (A) contains a repeating unit having an iodine atom, which increases the absorption rate of EUV light and the like, reduces the effect of shot noise, and further improves the LWR performance.

[0400] In a preferred embodiment of the present invention, the resin (A) contains a repeating unit having an aromatic ring. The repeating unit having an aromatic ring may be any of the repeating units described above. Furthermore, the resin (A) preferably contains a repeating unit having a hydroxy group bonded to the aromatic ring.

[0401] Resin (A) can be synthesized according to a conventional method (e.g., radical polymerization). The weight average molecular weight (Mw) of resin (A), as a polystyrene equivalent value measured by GPC, is preferably 30,000 or less, more preferably 20,000 or less, even more preferably 1,000 to 20,000, particularly preferably 3,000 to 20,000, and most preferably 5,000 to 15,000. The dispersity (molecular weight distribution, Mw / Mn) of resin (A) is preferably 1.0 to 5.0, more preferably 1.0 to 3.0, even more preferably 1.1 to 2.0, and particularly preferably 1.1 to 1.8. 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.

[0402] The content of resin (A) in the composition of the present invention is preferably 90% by mass or less, more preferably 80% by mass or less, and even more preferably 75% by mass or less, based on the total solid content of the composition of the present invention. Furthermore, the content of resin (A) is preferably 30% by mass or more, more preferably 35% by mass or more, and even more preferably 40% by mass or more, based on the total solid content of the composition of the present invention. The resin (A) contained in the composition of the present invention may be one type or two or more types. When the composition of the present invention contains two or more types of resin (A), the total content thereof is preferably within the above-mentioned preferred content range.

[0403] [Compound (B)] The composition of the present invention contains compound (B) (also simply referred to as "compound (B)") that generates an acid upon irradiation with actinic rays or radiation. Compound (B) is a photoacid generator. Compound (B) is preferably a compound that generates an acid having a pKa of less than 0 upon irradiation (exposure) with actinic rays or radiation. The pKa of the acid generated from compound (B) upon irradiation with actinic rays or radiation is preferably -0.1 or less, more preferably -0.2 or less. Furthermore, the pKa of the acid generated from compound (B) upon irradiation with actinic rays or radiation is preferably -20 or more, more preferably -10 or more, and even more preferably -7 or more.

[0404] Compound (B) may be a low molecular weight compound or a polymeric compound such as a resin. When compound (B) is a low molecular weight compound, the molecular weight of compound (B) is not particularly limited, but is preferably 100 to 3,000, more preferably 150 to 2,500, and even more preferably 200 to 2,000. When compound (B) is a polymeric compound, compound (B) and resin (A) may be the same compound, or compound (B) and resin (A) may be different compounds. When resin (A) contains a repeating unit having a photoacid-generating group, the composition of the present invention may or may not contain compound (B) as a compound different from resin (A).

[0405] Compound (B) is preferably an ionic compound containing a cation and an anion, preferably a cation containing a halogen atom, and preferably an anion containing an iodine atom.

[0406] It is generally considered that the compound containing a cation having a halogen atom or the compound containing an anion having an iodine atom has high solubility in organic solvent.When the compound (B) contains a cation having a halogen atom, or when it contains an anion having an iodine atom, the solubility of the compound (B) in the developer containing an organic solvent is increased, so that it can be prevented from occurring unintended crosslinking reaction in the weakly exposed region and becoming apparent as residue, and it can be further prevented from generating defects.

[0407] Examples of the compound (B) include "M ＋ X － ", and it is preferably a compound that generates an organic acid upon exposure. Examples of the organic acid include sulfonic acids (aliphatic sulfonic acids, aromatic sulfonic acids, camphorsulfonic acids, etc.), carboxylic acids (aliphatic carboxylic acids, aromatic carboxylic acids, aralkyl carboxylic acids, etc.), carbonylsulfonylimido acids, bis(alkylsulfonyl)imido acids, and tris(alkylsulfonyl)methido acids.

[0408] "M ＋ X －In the compound represented by the formula ", M ＋ represents an organic cation. ＋ The organic cation represented by the formula (ZaI) is not particularly limited. The valence of the organic cation may be monovalent or divalent or higher. The organic cation is preferably a cation that decomposes upon irradiation with actinic rays or radiation. The organic cation is preferably an onium cation, and more preferably a sulfonium cation or an iodonium cation. The organic cation is preferably a cation represented by the following formula (ZaI) (hereinafter also referred to as "cation (ZaI)") or a cation represented by the following formula (ZaII) (hereinafter also referred to as "cation (ZaII)"). Cation (ZaI) and cation (ZaII) are preferably cations that decompose upon irradiation with actinic rays or radiation.

[0409]

[0410] 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, 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 listed.

[0411] 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.

[0412] 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, 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.

[0413] 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.

[0414] R ２０１ ~R ２０３ Preferred 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 (preferably fluorine atoms, chlorine atoms, bromine atoms, or iodine atoms), hydroxyl groups, carboxyl groups, ester groups, sulfinyl groups, sulfonyl groups, alkylthio groups, or 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.

[0415] 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 ２０３The 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.

[0416] 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 ２０３ may be further substituted with a halogen atom, an alkoxy group (e.g., having 1 to 5 carbon atoms), a hydroxy 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.

[0417] Next, the cation (ZaI-3b) will be described. The cation (ZaI-3b) is a cation represented by the following formula (ZaI-3b).

[0418]

[0419] 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, a hydroxyl group, a nitro group, an alkylthio group, or an arylthio group. ６ｃ and R ７ｃR each independently represents a hydrogen atom, an alkyl group (for example, a t-butyl group), a cycloalkyl group, a halogen 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.

[0420] 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 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.

[0421] 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 ｘThe 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.

[0422] 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.

[0423] Next, the cation (ZaI-4b) will be described. The cation (ZaI-4b) is a cation represented by the following formula (ZaI-4b).

[0424]

[0425] 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 (preferably a chlorine atom, a bromine atom, or an iodine atom), a hydroxyl group, an alkyl group, a halogenated alkyl group, 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 (preferably a chlorine atom, a bromine atom, or an iodine atom), an alkyl group, a halogenated alkyl group, 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 １４When 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.

[0426] 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.

[0427] 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 ２０５The 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., a methyl group, an ethyl group, a propyl group, a butyl group, or a pentyl group), or a cycloalkyl group having 3 to 10 carbon atoms (e.g., a cyclopentyl group, a cyclohexyl group, or a norbornyl group).

[0428] 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 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 15 carbon atoms), alkoxy groups (e.g., having 1 to 15 carbon atoms), halogen atoms, hydroxyl groups, and phenylthio groups. ２０４ and R ２０５ It is also preferred that the substituents independently form an acid-decomposable group by any combination of the substituents.

[0429] Specific examples of the organic cation are shown below, but are not limited to these.

[0430]

[0431]

[0432] "M ＋ X － In the compound represented by the formula "X － represents an organic anion. The organic anion is not particularly limited, and examples thereof include monovalent or divalent or higher organic anions. As the organic anion, an anion having a significantly low ability to cause a nucleophilic reaction is preferred, and a non-nucleophilic anion is more preferred.

[0433] Examples of non-nucleophilic anions include sulfonate anions (aliphatic sulfonate anions, aromatic sulfonate anions, camphorsulfonate anions, etc.), carboxylate anions (aliphatic carboxylate anions, aromatic carboxylate anions, aralkyl carboxylate anions, etc.), sulfonylimide anions, bis(alkylsulfonyl)imide anions, and tris(alkylsulfonyl)methide anions.

[0434] The aliphatic moiety in the aliphatic sulfonate anion and the aliphatic carboxylate anion may be a linear or branched alkyl group or a cycloalkyl group, and is preferably a linear or branched alkyl group having 1 to 30 carbon atoms or a cycloalkyl group having 3 to 30 carbon atoms. The alkyl group may be, for example, a fluoroalkyl group (which may have a substituent other than a fluorine atom, or may be a perfluoroalkyl group).

[0435] The aryl group in the aromatic sulfonate anion and aromatic carboxylate anion is preferably an aryl group having 6 to 14 carbon atoms, and examples thereof include a phenyl group, a tolyl group, and a naphthyl group.

[0436] The alkyl group, cycloalkyl group, and aryl group mentioned above may have a substituent. The substituent is not particularly limited, but examples thereof include a nitro group, a halogen atom such as a fluorine atom or a chlorine atom, a carboxyl group, a hydroxyl group, an amino group, a cyano group, an alkoxy group (preferably having 1 to 15 carbon atoms), an alkyl group (preferably having 1 to 10 carbon atoms), a cycloalkyl group (preferably having 3 to 15 carbon atoms), an aryl group (preferably having 6 to 14 carbon atoms), an alkoxycarbonyl group (preferably having 2 to 7 carbon atoms), an acyl group (preferably having 2 to 12 carbon atoms), an alkoxycarbonyloxy group (preferably having 2 to 7 carbon atoms), an alkylthio group (preferably having 1 to 15 carbon atoms), an alkylsulfonyl group (preferably having 1 to 15 carbon atoms), an alkyliminosulfonyl group (preferably having 1 to 15 carbon atoms), and an aryloxysulfonyl group (preferably having 6 to 20 carbon atoms).

[0437] The aralkyl group in the aralkyl carboxylate anion is preferably an aralkyl group having 7 to 14 carbon atoms. Examples of the aralkyl group having 7 to 14 carbon atoms include a benzyl group, a phenethyl group, a naphthylmethyl group, a naphthylethyl group, and a naphthylbutyl group.

[0438] An example of the sulfonylimide anion is a saccharin anion.

[0439] The alkyl group in the bis(alkylsulfonyl)imide anion and the tris(alkylsulfonyl)methide anion is preferably an alkyl group having 1 to 5 carbon atoms. Substituents for these alkyl groups include halogen atoms, alkyl groups substituted with halogen atoms, alkoxy groups, alkylthio groups, alkyloxysulfonyl groups, aryloxysulfonyl groups, and cycloalkylaryloxysulfonyl groups, with fluorine atoms or alkyl groups substituted with fluorine atoms being preferred. Furthermore, the alkyl groups in the bis(alkylsulfonyl)imide anion may be bonded to each other to form a ring structure, which increases the acid strength.

[0440] Other non-nucleophilic anions include, for example, phosphorus fluorides (e.g., PF ６ － ), boron fluorides (e.g., BF ４ － ), and antimony fluorides (e.g., SbF ６ － ) are listed.

[0441] The non-nucleophilic anion is also preferably an anion represented by the following formula (AN1).

[0442]

[0443] In formula (AN1), R １ and R ２each independently represents a hydrogen atom or a substituent. The substituent is not particularly limited, but a group that is not an electron-withdrawing group is preferred. Examples of groups that are not electron-withdrawing groups include hydrocarbon groups, hydroxyl groups, oxyhydrocarbon groups, oxycarbonyl hydrocarbon groups, amino groups, hydrocarbon-substituted amino groups, and hydrocarbon-substituted amide groups. Examples of groups that are not electron-withdrawing groups include, each independently, -R', -OH, -OR', -OCOR', -NH ２ , -NR' ２ , —NHR′, or —NHCOR′ is preferred, where R′ is a monovalent hydrocarbon group.

[0444] Examples of the monovalent hydrocarbon group represented by R' include monovalent linear or branched hydrocarbon groups such as alkyl groups such as methyl, ethyl, propyl, and butyl; alkenyl groups such as ethenyl, propenyl, and butenyl; alkynyl groups such as ethynyl, propynyl, and butynyl; cycloalkyl groups such as cyclopropyl, cyclobutyl, cyclopentyl, cyclohexyl, norbornyl, and adamantyl; monovalent alicyclic hydrocarbon groups such as cycloalkenyl groups such as cyclopropenyl, cyclobutenyl, cyclopentenyl, and norbornenyl; aryl groups such as phenyl, tolyl, xylyl, mesityl, naphthyl, methylnaphthyl, anthryl, and methylanthryl; and aralkyl groups such as benzyl, phenethyl, phenylpropyl, naphthylmethyl, and anthrylmethyl. Among these, R １ and R ２ are each independently preferably a hydrocarbon group (preferably a cycloalkyl group) or a hydrogen atom.

[0445] L represents a divalent linking group. Examples of the divalent linking group include -O-CO-O-, -COO-, -CONH-, -CO-, -O-, -S-, -SO-, and -SO ２Examples of the divalent linking group include -, an alkylene group (preferably having 1 to 6 carbon atoms), a cycloalkylene group (preferably having 3 to 15 carbon atoms), an alkenylene group (preferably having 2 to 6 carbon atoms), and a divalent linking group formed by combining a plurality of these groups. Among these, examples of the divalent linking group include -O-CO-O-, -COO-, -CONH-, -CO-, -O-, and -SO ２ -, -O-CO-O-alkylene group-, -COO-alkylene group-, or -CONH-alkylene group- is preferred, and -O-CO-O-, -O-CO-O-alkylene group-, -COO-, -CONH-, or -SO ２ - or -COO-alkylene group- is more preferred.

[0446] As L, for example, a group represented by the following formula (AN1-1) is preferable: ａ - (CR ２ａ ２ ) Ｘ -Q-(CR ２ｂ ２ ) Ｙ -* ｂ (AN1-1)

[0447] In formula (AN1-1), * ａ is R in formula (AN1). ３ Represents the bonding position with * ｂ represents -C(R １ ) (R ２ X and Y each independently represent an integer of 0 to 10, preferably an integer of 0 to 3. R ２ａ and R ２ｂ R each independently represents a hydrogen atom or a substituent. ２ａ and R ２ｂ When there are multiple R ２ａ and R ２ｂ may be the same or different, provided that when Y is 1 or more, -C(R １ ) (R ２ )- and CR directly bonded ２ｂ ２ R in ２ｂ is other than a fluorine atom. Q is * Ａ -O-CO-O-*Ｂ , * Ａ -CO-* Ｂ , * Ａ -CO-O-* Ｂ , * Ａ -O-CO-* Ｂ , * Ａ -O-* Ｂ , * Ａ -S-* Ｂ , or * Ａ -SO ２ -* Ｂ where X+Y in formula (AN1-1) is 1 or more, and R ２ａ and R ２ｂ are all hydrogen atoms, Q is * Ａ -O-CO-O-* Ｂ , * Ａ -CO-* Ｂ , * Ａ -O-CO-* Ｂ , * Ａ -O-* Ｂ , * Ａ -S-* Ｂ , or * Ａ -SO ２ -* Ｂ Represents. Ａ is R in formula (AN1). ３ represents the bonding position on the side, and * Ｂ represents -SO in formula (AN1). ３ － represents the bonding position on the side.

[0448] In formula (AN1), R ３ represents an organic group. The organic group is not particularly limited as long as it has one or more carbon atoms, and may be a linear group (for example, a linear alkyl group), a branched group (for example, a branched alkyl group such as a t-butyl group), or a cyclic group. The organic group may or may not have a substituent. The organic group may or may not have a heteroatom (such as an oxygen atom, a sulfur atom, and / or a nitrogen atom).

[0449] Among them, R ３is preferably an organic group having a cyclic structure. The cyclic structure may be monocyclic or polycyclic and may have a substituent. The ring in the organic group having a cyclic structure is preferably directly bonded to L in formula (AN1). The organic group having a cyclic structure may or may not have a heteroatom (such as an oxygen atom, a sulfur atom, and / or a nitrogen atom). The heteroatom may substitute for one or more of the carbon atoms forming the cyclic structure. The organic group having a cyclic structure is preferably, for example, a hydrocarbon group having a cyclic structure, a lactone group, or a sultone group. Among these, the organic group having a cyclic structure is preferably a hydrocarbon group having a cyclic structure. The hydrocarbon group having a cyclic structure is preferably a monocyclic or polycyclic cycloalkyl group. These groups may have a substituent. The cycloalkyl group may be monocyclic (such as a cyclohexyl group) or polycyclic (such as an adamantyl group), and preferably has 5 to 12 carbon atoms. Examples of the lactone group and sultone group include the lactone group and sultone group described above for the repeating unit Y. The preferred lactone group and sultone group are the same as those explained for the repeating unit Y.

[0450] The non-nucleophilic anion may be a benzenesulfonate anion, and is preferably a benzenesulfonate anion substituted with a branched alkyl group or a cycloalkyl group.

[0451] The non-nucleophilic anion is also preferably an anion represented by the following formula (AN2).

[0452]

[0453] In formula (AN2), o represents an integer of 1 to 3. p represents an integer of 0 to 10. q represents an integer of 0 to 10.

[0454] Xf represents a hydrogen atom, a fluorine atom, an alkyl group substituted with at least one fluorine atom, or an organic group having no fluorine atoms. The number of carbon atoms in this alkyl group is preferably 1 to 10, more preferably 1 to 4. The alkyl group substituted with at least one fluorine atom is preferably a perfluoroalkyl group. Xf is preferably a fluorine atom or a perfluoroalkyl group having 1 to 4 carbon atoms, and is preferably a fluorine atom or CF ３ It is more preferable that both Xf's are fluorine atoms.

[0455] R ４ and R ５ R each independently represents a hydrogen atom, a fluorine atom, an alkyl group, or an alkyl group substituted with at least one fluorine atom. ４ and R ５ If there are multiple R ４ and R ５ may be the same or different. ４ and R ５ The alkyl group represented by the formula (I) preferably has 1 to 4 carbon atoms. The alkyl group may have a substituent. ４ and R ５ is preferably a hydrogen atom.

[0456] L represents a divalent linking group. The description, specific examples, and preferred range of L are the same as those for L in formula (AN1). When a plurality of Ls are present, the plurality of Ls may be the same or different.

[0457] W represents an organic group containing a cyclic structure. Among these, a cyclic organic group is preferred. Examples of the cyclic organic group include an alicyclic group, an aryl group, and a heterocyclic group. The alicyclic group may be monocyclic or polycyclic. Examples of the monocyclic alicyclic group include a monocyclic cycloalkyl group such as a cyclopentyl group, a cyclohexyl group, and a cyclooctyl group. Examples of the polycyclic alicyclic group include a polycyclic cycloalkyl group such as a norbornyl group, a tricyclodecanyl group, a tetracyclodecanyl group, a tetracyclododecanyl group, and an adamantyl group. Among these, alicyclic groups having a bulky structure with 7 or more carbon atoms, such as a norbornyl group, a tricyclodecanyl group, a tetracyclodecanyl group, a tetracyclododecanyl group, and an adamantyl group, are preferred.

[0458] The aryl group may be monocyclic or polycyclic. Examples of the aryl group include a phenyl group, a naphthyl group, a phenanthryl group, and an anthryl group. The heterocyclic group may be monocyclic or polycyclic. In particular, a polycyclic heterocyclic group can further suppress the diffusion of acid. The heterocyclic group may or may not have aromaticity. Examples of heterocyclic rings having aromaticity include a furan ring, a thiophene ring, a benzofuran ring, a benzothiophene ring, a dibenzofuran ring, a dibenzothiophene ring, and a pyridine ring. Examples of heterocyclic rings having no aromaticity include a tetrahydropyran ring, a lactone ring, a sultone ring, and a decahydroisoquinoline ring. The heterocyclic ring in the heterocyclic group is preferably a furan ring, a thiophene ring, a pyridine ring, or a decahydroisoquinoline ring.

[0459] The cyclic organic group may have a substituent. Examples of the substituent include an alkyl group (which may be either linear or branched, and preferably has 1 to 12 carbon atoms), a cycloalkyl group (which may be either monocyclic, polycyclic, or spirocyclic, and preferably has 3 to 20 carbon atoms), an aryl group (which preferably has 6 to 14 carbon atoms), a hydroxyl group, an alkoxy group, an ester group, an amide group, a urethane group, a ureido group, a thioether group, a sulfonamide group, and a sulfonate ester group. The carbon constituting the cyclic organic group (the carbon that contributes to ring formation) may be a carbonyl carbon.

[0460] The anion represented by formula (AN2) is SO ３ － -CF ２ -CH ２ -OCO-(L) ｑ’ -W, SO ３ － -CF ２ -CHF-CH ２ -OCO-(L) ｑ’ -W, SO ３ － -CF ２ -COO-(L) ｑ’ -W, SO ３ － -CF ２ -CF ２ -CH ２ -CH ２ - (L) ｑ -W or SO ３ － -CF ２ -CH(CF ３ ) -OCO-(L) ｑ’ -W is preferred. Here, L, q and W are the same as those in formula (AN2). q' represents an integer of 0 to 10.

[0461] The non-nucleophilic anion is also preferably an aromatic sulfonate anion represented by the following formula (AN3).

[0462]

[0463] In formula (AN3), Ar represents an aryl group (such as a phenyl group) and may further have a substituent other than the sulfonate anion and the -(D-B) group. Examples of the substituent that may further be had include a fluorine atom and a hydroxyl group. n represents an integer of 0 or greater. n is preferably 1 to 4, more preferably 2 to 3, and even more preferably 3.

[0464] D represents a single bond or a divalent linking group. Examples of the divalent linking group include an ether group, a thioether group, a carbonyl group, a sulfoxide group, a sulfone group, a sulfonate ester group, an ester group, and a group formed by combining two or more of these groups.

[0465] B represents a hydrocarbon group. B is preferably an aliphatic hydrocarbon group, more preferably an isopropyl group, a cyclohexyl group, or an aryl group which may further have a substituent (such as a tricyclohexylphenyl group).

[0466] As the non-nucleophilic anion, a disulfonamide anion is also preferred. The disulfonamide anion is, for example, N － (SO ２ -R ｑ ) ２ where R ｑ represents an alkyl group which may have a substituent, preferably a fluoroalkyl group, more preferably a perfluoroalkyl group. ｑ may be bonded to each other to form a ring. ｑ The group formed by bonding together is preferably an alkylene group which may have a substituent, more preferably a fluoroalkylene group, and even more preferably a perfluoroalkylene group. The alkylene group preferably has 2 to 4 carbon atoms.

[0467] Further, examples of the non-nucleophilic anion include anions represented by the following formulas (d1-1) to (d1-4).

[0468]

[0469] In formula (d1-1), R ５１represents a hydrocarbon group (for example, an aryl group such as a phenyl group) which may have a substituent (for example, a hydroxyl group).

[0470] In formula (d1-2), Z ２ｃ represents a hydrocarbon group having 1 to 30 carbon atoms which may have a substituent (provided that the carbon atom adjacent to S is not substituted with a fluorine atom). ２ｃ The hydrocarbon group in the formula (d1-2) may be linear or branched, or may have a cyclic structure. In addition, a carbon atom in the hydrocarbon group (preferably, a carbon atom that is a ring atom when the hydrocarbon group has a cyclic structure) may be a carbonyl carbon (-CO-). Examples of the hydrocarbon group include a group having a norbornyl group that may have a substituent. The carbon atom forming the norbornyl group may be a carbonyl carbon. ２ｃ -SO ３ － " is preferably different from the anions represented by the above formulae (AN1) to (AN3). For example, Z ２ｃ is preferably other than an aryl group. For example, Z ２ｃ In the -SO ３ － The atoms at the α-position and β-position to Z are preferably atoms other than carbon atoms having a fluorine atom as a substituent. ２ｃ is -SO ３ － The atom at the α-position and / or the atom at the β-position to the aryl group is preferably a ring atom in a cyclic group.

[0471] In formula (d1-3), R ５２ represents an organic group (preferably a hydrocarbon group having a fluorine atom), Y ３ represents a linear, branched, or cyclic alkylene group, an arylene group, or a carbonyl group, and Rf represents a hydrocarbon group.

[0472] In formula (d1-4), R ５３ and R ５４ R each independently represents an organic group (preferably a hydrocarbon group having a fluorine atom). ５３ and R ５４may be bonded to each other to form a ring.

[0473] The organic anion may be a divalent or higher anion. For example, the organic anion may have two or more groups represented by any of the following formulae (AA-1) to (AA-3) and (BB-1) to (BB-6). In formulae (AA-1) to (AA-3) and (BB-1) to (BB-6), * represents a bonding position. In formula (AA-2), R Ａ represents a monovalent organic group. Ａ The monovalent organic group represented by the formula (I) is not particularly limited, but examples thereof include a cyano group, a trifluoromethyl group, and a methanesulfonyl group.

[0474]

[0475]

[0476] Specific examples of divalent or higher organic anions are shown below, but are not limited to these.

[0477]

[0478]

[0479] The organic anion may also have a nonionic moiety capable of neutralizing an acid. The nonionic moiety capable of neutralizing an acid is not particularly limited, and is preferably, for example, a moiety containing a group capable of electrostatically interacting with a proton or a functional group having electrons. Examples of the group capable of electrostatically interacting with a proton or the functional group having electrons include functional groups having a macrocyclic structure such as cyclic polyethers, and functional groups having a nitrogen atom with an unshared electron pair that does not contribute to π-conjugation. The nitrogen atom with an unshared electron pair that does not contribute to π-conjugation is, for example, a nitrogen atom having a partial structure shown in the following formula:

[0480]

[0481] Examples of the partial structure of a functional group having a group or electron capable of electrostatically interacting with a proton include a crown ether structure, an azacrown ether structure, a primary amine structure, a secondary amine structure, a tertiary amine structure, a pyridine structure, an imidazole structure, and a pyrazine structure. Of these, a primary amine structure, a secondary amine structure, a tertiary amine structure, and a tertiary amine structure are preferred.

[0482] The organic anions may be used alone or in combination of two or more.

[0483] Compound (B) is also preferably at least one selected from the group consisting of compound (I) and compound (II). Compound (I): A compound having one or more structural moieties Z1 and one or more structural moieties Z2, and satisfying condition (I). When compound (I) has two or more structural moieties Z1, the two or more structural moieties Z1 may be the same or different, and when compound (I) has two or more structural moieties Z2, the two or more structural moieties Z2 may be the same or different. Condition (I): Structural moieties Z1 and Z2 are structural moieties that generate an acid upon irradiation with actinic rays or radiation, and the acid generated from structural moiety Z1 is stronger than the acid generated from structural moiety Z2. Compound (II): A compound having two or more structural moieties Z1 and one or more structural moieties Z3, and generating an acid containing two or more acidic moieties derived from structural moiety Z1 and structural moiety Z3 upon irradiation with actinic rays or radiation. The two or more structural moieties Z1 in the compound (II) may be the same or different. Structural moiety Z3: a nonionic moiety capable of neutralizing an acid

[0484] When compound (B) is at least one selected from the group consisting of compound (I) and compound (II), compound (I) and compound (II) each have a moiety capable of functioning as a photoacid generator (structural moiety Z1) and a moiety capable of functioning as an acid diffusion controller (structural moiety Z2 and structural moiety Z3) in the same molecule, and therefore fluctuations in material distribution are thought to be less likely to occur than when a photoacid generator and an acid diffusion controller are contained separately, which is thought to reduce fluctuations in solubility due to the crosslinking reaction and further suppress the occurrence of defects.

[0485] The pKa of the acid generated from the structural moiety Z1 is smaller than the pKa of the acid generated from the structural moiety Z2. The pKa of the acid generated from the structural moiety Z1 is preferably less than 0, preferably −0.1 or less, more preferably −1.0 or less, and even more preferably −1.5 or less. The pKa of the acid generated from the structural moiety Z1 is preferably −20 or more, more preferably −10 or more, and even more preferably −7 or more. The pKa of the acid generated from the structural moiety Z2 is preferably 20 or less, more preferably 15 or less, and even more preferably 10 or less. The pKa of the acid generated from the structural moiety Z2 is preferably −4 or more, more preferably −3 or more, and even more preferably −1.4 or more. The difference (absolute value) between the pKa of the acid generated from the structural moiety Z1 and the pKa of the acid generated from the structural moiety Z2 is preferably 0.1 or more, more preferably 0.5 or more, and even more preferably 1.0 or more. The upper limit of the difference (absolute value) between the pKa of the acid generated from the structural moiety Z1 and the pKa of the acid generated from the structural moiety Z2 is not particularly limited, but may be, for example, 16 or less, or 10 or less.

[0486] Compound (I) is preferably compound (I-1) below. Compound (II) is preferably compound (II-1) below. Compound (B) is also preferably at least one selected from the group consisting of compound (I-1) below and compound (II-1) below. Compound (I-1): Compound (I-1) is a compound having one or more structural moieties X below and one or more structural moieties Y below, which generates an acid containing a first acidic moiety derived from structural moiety X below and a second acidic moiety derived from structural moiety Y below upon irradiation with actinic rays or radiation, and satisfies condition I-1 below. Structural moiety X: anionic moiety A １ － and the cationic moiety M １ ＋ and by irradiation with actinic rays or radiation, HA １ Structural moiety Y: anionic moiety A, which forms a first acidic moiety represented by the formula: ２ － and the cationic moiety M ２ ＋ and by irradiation with actinic rays or radiation, HA２ The compound (I-1) satisfies the following condition I-1. Condition I-1: The cationic moiety M in the structural moiety X １ ＋ and the cationic moiety M in the structural moiety Y ２ ＋ H ＋ The compound PI in which the cationic moiety M in the structural moiety X is １ ＋ H ＋ HA is replaced by １ and the cationic moiety M in the structural moiety Y. ２ ＋ H ＋ HA is replaced by ２ and an acid dissociation constant a2 derived from the acidic moiety represented by the following formula: wherein the acid dissociation constant a2 is greater than the acid dissociation constant a1. Compound (II-1): Compound (II-1) is a compound having two or more of the above structural moieties X and one or more of the following structural moieties Z, and is a compound that generates an acid containing two or more of the first acidic moieties derived from the structural moiety X and the structural moiety Z upon irradiation with actinic rays or radiation. Structural moiety Z: a ​​nonionic moiety capable of neutralizing an acid

[0487] For example, when compound (I-1) is an acid-generating compound having one first acidic site derived from structural site X and one second acidic site derived from structural site Y, compound PI is "HA １ and H.A. ２ When the acid dissociation constant of compound PI is calculated, if compound PI is found to have the following structure, １ － and H.A. ２ The pKa at which the compound becomes "a compound having １ － and H.A. ２ "A compound having １ － and A ２ － The pKa at which the compound becomes "a compound having the above formula (I)" is the acid dissociation constant a2.

[0488] For example, when compound (I-1) is an acid-generating compound having two first acidic sites derived from structural site X and one second acidic site derived from structural site Y, compound PI is defined as "two HAs １ and one HA ２ When the acid dissociation constant of compound PI is calculated, compound PI corresponds to "a compound having one A １ － and one HA １ and one HA ２ and the acid dissociation constant when "a compound having one A １ － and one HA １ and one HA ２ "Compound having two A １ － and one HA ２ The acid dissociation constant when the compound is a compound having two A's corresponds to the acid dissociation constant a1. １ － and one HA ２ "Compound having two A １ － and A ２ － In other words, in the case of compound PI, the acid dissociation constant when the compound becomes a compound having the cation moiety M １ ＋ H ＋ HA is replaced by １ When the compound PI has a plurality of acid dissociation constants derived from the acidic moiety represented by the formula (I), the value of the acid dissociation constant a2 is larger than the largest value of the plurality of acid dissociation constants a1. １ － and one HA １ and one HA ２ The acid dissociation constant when the compound is aa is defined as "a compound having one A １ － and one HA １ and one HA ２ "Compound having two A １ － and one HA ２When the acid dissociation constant when the compound becomes "a compound having the formula (I)" is ab, the relationship between aa and ab satisfies aa<ab.

[0489] The acid dissociation constant a1 and the acid dissociation constant a2 are determined by the above-mentioned method for measuring an acid dissociation constant. Compound PI corresponds to the acid generated when compound (I-1) is irradiated with actinic rays or radiation. When compound (I-1) has two or more structural moieties X, the structural moieties X may be the same or different. In addition, when two or more of the above A １ － and two or more of the above M １ ＋ In compound (I-1), the above A １ － and the above A ２ － , and the above M １ ＋ and the above M ２ ＋ may be the same or different, but １ － and the above A ２ － are preferably different from each other.

[0490] In the compound PI, the difference (absolute value) between the acid dissociation constant a1 (the maximum value when there are multiple acid dissociation constants a1) and the acid dissociation constant a2 is preferably 0.1 or more, more preferably 0.5 or more, and even more preferably 1.0 or more. The upper limit of the difference (absolute value) between the acid dissociation constant a1 (the maximum value when there are multiple acid dissociation constants a1) and the acid dissociation constant a2 is not particularly limited, and may be, for example, 16 or less, or 10 or less.

[0491] In the compound PI, the acid dissociation constant a2 is preferably 20 or less, more preferably 15 or less, and even more preferably 10 or less. The lower limit of the acid dissociation constant a2 is preferably −4 or more, more preferably −3 or more, and even more preferably −1.4 or more.

[0492] In the compound PI, the acid dissociation constant a1 is preferably less than 0, preferably −0.1 or less, more preferably −1.0 or less, and even more preferably −1.5 or less. The lower limit of the acid dissociation constant a1 is preferably −20 or more, more preferably −10 or more, and even more preferably −7 or more.

[0493] Anion site A １ － and anionic moiety A ２ － is a structural moiety containing a negatively charged atom or atomic group, and examples thereof include structural moieties selected from the group consisting of formulae (AA-1) to (AA-3) and formulae (BB-1) to (BB-6) shown above. １ － As the anionic moiety A, those capable of forming an acidic moiety with a small acid dissociation constant are preferred, and among these, any of formulas (AA-1) to (AA-3) is more preferred, and any of formulas (AA-1) and (AA-3) is even more preferred. ２ － As the anion moiety A １ － Preferably, it is one that can form an acidic site having a larger acid dissociation constant than the above, more preferably one of formulas (BB-1) to (BB-6), and even more preferably one of formulas (BB-1) and (BB-4).

[0494] Cationic moiety M １ ＋ and cationic moiety M ２ ＋ is a structural moiety containing a positively charged atom or atomic group, and examples thereof include monovalent organic cations. Examples of organic cations include the above-mentioned M ＋ Examples of the organic cation include those represented by the following formula:

[0495] In compound (II-1), the definition of the structural moiety X and A １ － and M １ ＋ The definition of the structural moiety X in the compound (I-1) is the same as that of the structural moiety A. １ － and M １＋ The definition and preferred embodiments are also the same.

[0496] The cationic moiety M in the structural moiety X of compound (II-1) １ ＋ H ＋ In the compound PII, the cationic moiety M in the structural moiety X is replaced by １ ＋ H ＋ HA is replaced by １ The preferred range of the acid dissociation constant a1 derived from the acidic moiety represented by the formula (II-1) is the same as the acid dissociation constant a1 in the compound PI. For example, when the compound (II-1) is an acid-generating compound having two first acidic moieties derived from the structural moiety X and the structural moiety Z, the compound PII is a compound having two HAs １ When the acid dissociation constant of this compound PII was calculated, it was found that the compound PII has "one A １ － and one HA １ and the acid dissociation constant when "a compound having one A １ － and one HA １ "Compound having two A １ － The acid dissociation constant when the compound (II-1) becomes a compound having the formula "A" corresponds to the acid dissociation constant a1. The acid dissociation constant a1 can be determined by the above-mentioned method for measuring an acid dissociation constant. The compound PII corresponds to the acid generated when the compound (II-1) is irradiated with actinic rays or radiation. The two or more structural moieties X may be the same or different. １ － , and two or more M １ ＋ may be the same or different.

[0497] The nonionic moiety capable of neutralizing an acid in the structural moiety Z is not particularly limited, and is preferably, for example, a moiety containing the above-described group capable of electrostatically interacting with a proton or the above-described functional group having an electron.

[0498] Specific examples of compound (B) include B-1-B-34 described in the Examples below, but the present invention is not limited to these.

[0499] The content of compound (B) is not particularly limited, but is preferably 0.5% by mass or more, more preferably 1% by mass or more, and even more preferably 5% by mass or more, based on the total solid content of the composition of the present invention.Furthermore, the content of compound (B) is preferably 60% by mass or less, more preferably 55% by mass or less, and even more preferably 50% by mass or less, based on the total solid content of the composition of the present invention.Only one type of compound (B) may be used, or two or more types may be used.When two or more types of compound (B) are used, it is preferable that the total content is within the above-mentioned suitable content range.

[0500] Compound (B) may be compound (BA) having no fluorinated alkyl group. Specific examples of compound (BA) include those described in paragraphs

[0333] to

[0334] of WO 2024 / 143131, paragraphs

[0374] to

[0376] of WO 2024 / 185543, and paragraphs

[0340] to

[0344] of WO 2025 / 069991.

[0501] [Crosslinking Agent] The composition of the present invention contains a crosslinking agent. The crosslinking agent is a compound having a crosslinkable group. Examples of the crosslinkable group include a group having an ethylenically unsaturated double bond such as a vinyl group, a thiol group, a methylol group, an alkoxymethyl group, an epoxy group, an oxetanyl group, an amino group, and a hydroxy group. The crosslinking agent is preferably a compound having an acid crosslinkable group. The acid crosslinkable group is a group that can induce a crosslinking reaction under acidic conditions. Examples of the acid crosslinkable group include a methylol group, an alkoxymethyl group, an epoxy group, an oxetanyl group, an amino group, and a hydroxy group. A methylol group or an alkoxymethyl group is preferred, and a methylol group or a methoxymethyl group is more preferred. The crosslinking agent preferably has at least one group selected from the group consisting of a methylol group and a methoxymethyl group, and more preferably has at least two groups selected from the group consisting of a methylol group and a methoxymethyl group.

[0502] The crosslinking agent may be a low molecular weight compound or a high molecular weight compound such as a resin. When the crosslinking agent is a low molecular weight compound, the molecular weight of the crosslinking agent is not particularly limited, but is preferably 3,000 or less, more preferably 2,000 or less, and even more preferably 1,200 or less. The molecular weight of the crosslinking agent may be 50 or more, or 100 or more. When the crosslinking agent is a high molecular weight compound, the crosslinking agent and the resin (A) may be the same compound, or the crosslinking agent and the resin (A) may be different compounds.

[0503] First, we will explain the case where the crosslinking agent is a low molecular weight compound. The crosslinking agent is preferably a hydroxymethylated or alkoxymethylated phenol compound, an alkoxymethylated melamine compound, an alkoxymethyl glycoluril compound, or an alkoxymethylated urea compound. The crosslinking agent is particularly preferably a phenol derivative or alkoxymethyl glycoluril derivative containing 3 to 5 benzene rings in the molecule, and further having a total of two or more methylol groups or alkoxymethyl groups, and having a molecular weight of 1,200 or less. As the alkoxymethyl group, a methoxymethyl group or an ethoxymethyl group is preferred.

[0504] Phenol derivatives having a methylol group can be obtained by reacting a corresponding phenol compound having no methylol group with formaldehyde in the presence of a base catalyst, while phenol derivatives having an alkoxymethyl group can be obtained by reacting a corresponding phenol derivative having a hydroxymethyl group with an alcohol in the presence of an acid catalyst.

[0505] Further, other preferred examples of the crosslinking agent include compounds having an N-hydroxymethyl group or an N-alkoxymethyl group, such as alkoxymethylated melamine-based compounds, alkoxymethylglycoluril-based compounds, and alkoxymethylated urea-based compounds.

[0506] Examples of such compounds include hexamethoxymethylmelamine, hexaethoxymethylmelamine, tetramethoxymethylglycoluril, 1,3-bismethoxymethyl-4,5-bismethoxyethyleneurea, and bismethoxymethylurea, and these are disclosed in EP 0,133,216A, West German Patent Nos. 3,634,671 and 3,711,264, and EP 0,212,482A.

[0507] Specific examples of the crosslinking agent include, but are not limited to, the following.

[0508]

[0509] In the above formulas (FL-1) to (FL-14), L ｆ１ ~L ｆ８ each independently represents a hydrogen atom, a methylol group, a methoxymethyl group, an ethoxymethyl group, or an alkyl group having 1 to 6 carbon atoms.

[0510] The content of the crosslinking agent in the composition of the present invention (based on the entire composition of the present invention) is preferably 0.5% by mass or less, more preferably 0.3% by mass or less. Furthermore, the content of the crosslinking agent in the composition of the present invention (based on the entire composition of the present invention) is preferably 0.01% by mass or more. Only one type of crosslinking agent may be used, 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 preferred content range.

[0511] Next, a case where the crosslinking agent is a polymeric compound will be described. The crosslinking agent may be a resin containing a repeating unit having an acid crosslinking group. In such an embodiment, the crosslinking group is contained within the molecular unit of the repeating unit, resulting in high crosslinking reactivity. Therefore, a hard film can be formed, and acid diffusibility and dry etching resistance can be controlled. As a result, acid diffusibility in areas exposed to actinic rays or radiation such as electron beams or extreme ultraviolet rays is significantly suppressed, resulting in excellent resolution, pattern shape, and LER in fine patterns. Furthermore, when the reactive site of the resin and the reactive site of the crosslinking group are close to each other, as in the repeating unit represented by the following formula (1), sensitivity during pattern formation can be improved. When a crosslinking agent is included as the resin containing a repeating unit having an acid crosslinking group, its content is preferably 3.0% by mass or less, more preferably 2.0% by mass or less, relative to the composition of the present invention (based on the entire composition of the present invention). Furthermore, it is preferably 0.01% by mass or more relative to the composition of the present invention (based on the entire composition of the present invention).

[0512] The crosslinking agent may be, for example, a resin containing a repeating unit represented by the following formula (1).

[0513]

[0514] In formula (1), E １ represents a hydrogen atom, a methyl group or a halogen atom. ２ and E ３ Each of M independently represents a hydrogen atom, an alkyl group, or a cycloalkyl group. １ represents a divalent linking group or a single bond. １ represents a substituent. １ represents a hydrogen atom or a substituent. s represents an integer of 0 to 4. w represents an integer of 1 to 5. s+w is 5 or less. When s is 2 or more, a plurality of Y １ may be the same or different. １ may be bonded to each other via a single bond or a linking group to form a ring. ２ may be the same or different, and a plurality of E ３may be the same or different, and multiple Z １ may be the same or different. １ , E ２ , E ３ and Z １ Two or more of these may be bonded to each other to form a ring.

[0515] Preferred examples of the repeating unit represented by formula (1) include the repeating units described in paragraphs

[0176] to

[0183] of JP-A-2018-189758, the disclosure of which is incorporated herein by reference.

[0516] [Acid Diffusion Controller] The composition of the present invention may contain an acid diffusion controller. The acid diffusion controller traps excess acid generated from the photoacid generator (compound (B)) upon irradiation with actinic rays or radiation, and acts as a quencher that suppresses the reaction of the resin (A) in unexposed areas due to the excess acid. Examples of the acid diffusion controller include basic compounds (CA), low-molecular-weight compounds (CB) having a nitrogen atom and a group that is cleaved by the action of an acid, and compounds (CC) whose acid diffusion control ability is reduced or eliminated upon irradiation with actinic rays or radiation (hereinafter also referred to as "photodegradable bases"). Examples of the compound (CC) include onium salt compounds (CD) of acids that are weaker acids than the acid generated from the photoacid generator, and basic compounds (CE) whose basicity is reduced or eliminated upon 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 onium salt compounds (CD) of acids that are weaker acids than the acid generated from the photoacid generator include those described in paragraphs

[0305] to

[0314] of WO 2020 / 158337. The pKa of the acid that is weaker acids than the acid generated from the photoacid generator is preferably 20 or less, more preferably 15 or less, and even more preferably 10 or less. The pKa of the acid that is weaker acids than the acid generated from the photoacid generator is preferably -4 or more, more preferably -3 or more, and even more preferably -1.4 or more.

[0517] In addition to the above, for example, the 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, paragraphs

[0259] to

[0328] of U.S. Patent Application Publication No. 2016 / 0274458A1, paragraphs

[0395] to

[0397] of WO 2024 / 185543, and paragraphs

[0335] to

[0337] of WO 2025 / 069991 can be suitably used as the acid diffusion controller.

[0518] The molecular weight of the acid diffusion controller is not particularly limited, but is preferably from 100 to 3,000, more preferably from 150 to 2,500, and even more preferably from 200 to 2,000.

[0519] When the composition of the present invention contains an acid diffusion controller, the content of the acid diffusion controller is not particularly limited, but may be 0.001 to 30% by mass, 0.01 to 20% by mass, or 0.1 to 10% by mass relative to the total solids content of the composition of the present invention. Only one acid diffusion controller may be used, 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 preferred content range. It is also preferable that the composition of the present invention does not contain an acid diffusion controller.

[0520] [Hydrophobic Resin] The composition of the present invention may contain a hydrophobic resin different from the resin (A). The hydrophobic resin is preferably designed so as 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 it does not necessarily have to contribute to uniform mixing of the polar substance and the non-polar substance.

[0521] The hydrophobic resin contains 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. ３It is preferable to have one or more of the partial structures, and more preferably two or more. In addition, the hydrophobic resin 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 hydrophobic resins include the compounds described in paragraphs

[0275] to

[0279] of WO 2020 / 004306 and paragraphs

[0352] to

[0358] of WO 2024 / 185674, and the above descriptions are incorporated herein.

[0522] When the composition of the present invention contains a hydrophobic resin, the content of the hydrophobic resin is preferably 0.01 to 20.0 mass%, more preferably 0.1 to 10.0 mass%, and even more preferably 0.1 to 5.0 mass%, based on the total solid content of the composition of the present invention. Only one hydrophobic resin may be used, or two or more hydrophobic resins may be used. When two or more hydrophobic resins are used, the total content thereof is preferably within the above-mentioned preferred content range.

[0523] [Surfactant] The composition of the present invention may contain a surfactant. When the composition of the present invention contains a surfactant, it is possible to form a pattern with better adhesion and fewer development defects. 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.

[0524] 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. One type of surfactant may be used, 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.

[0525] [Solvent] The composition of the present invention 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). Details of components (M1) and (M2) are described in paragraphs

[0218] to

[0226] of WO 2020 / 004306, the contents of which are incorporated herein by reference. The content of the solvent in the composition of the present invention is not particularly limited, but is preferably determined so that the solids concentration of the composition of the present invention is 0.5 to 30% by mass, more preferably 1 to 20% by mass. 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.

[0526] [Other Additives] The composition of the present invention may further contain, as other additives, a dissolution inhibiting compound, a dye, a plasticizer, a photosensitizer, a light absorber, and a compound that promotes solubility in a developer (for example, a phenolic compound having a molecular weight of 1,000 or less, or an alicyclic or aliphatic compound containing a carboxy group). The "dissolution inhibiting compound" is a compound having a molecular weight of 3,000 or less that decomposes under the action of an acid and thereby reduces its solubility in an organic developer.

[0527] The content of the other additives is not particularly limited, but may be 20.0 mass% or less, 10.0 mass% or less, or 5.0 mass% or less, based on the total solid content of the composition of the present invention. Only one type of the other additives may be used, or two or more types may be used. When two or more types are used, it is preferable that the total content is within the above-mentioned preferred content range.

[0528] The composition of the present invention may also contain water as an impurity. When water is contained as an impurity, the smaller the content of water, the more preferable, but the water content may be 1 to 30,000 ppm by mass relative to the entire composition of the present invention. The composition of the present invention may also contain residual monomers as impurities (for example, monomers derived from raw material monomers used in the synthesis of the resin). When residual monomers are contained as impurities, the smaller the content of residual monomers, the more preferable, but the water content may be 1 to 30,000 ppm by mass relative to the total solid content of the composition of the present invention.

[0529] [Resist Film, Pattern Forming Method] The present invention also relates to a resist film formed using the composition of the present invention. The pattern forming method of the present invention includes step (1) of forming a resist film using the composition of the present invention, step (2) of exposing the resist film, and step (3) of developing the exposed resist film with a developer. In the pattern forming method of the present invention, the developer preferably contains an organic solvent, and the pattern formed is a negative pattern. A negative pattern is a pattern formed by removing unexposed areas of a resist film and leaving exposed areas. Each of the above steps will be described in detail below.

[0530] [Step (1)] Step (1) is a step of forming a resist film using the composition of the present invention. Details of the composition of the present invention used in step (1) are as described above. Step (1) is preferably a step of forming a resist film on a substrate using the composition of the present invention. An example of a method for forming a resist film on a substrate using the composition of the present invention is a method of applying the composition of the present invention (also referred to as a "resist composition") to a substrate. If necessary, it is preferable to filter the resist composition before application. The pore size of the filter is preferably 0.1 μm or less, more preferably 0.03 μm or less, even more preferably 0.01 μm or less, and particularly preferably 0.005 μm or less. The lower limit of the pore size of the filter is not particularly limited, but may be 0.001 μm or more. The material of the filter is not particularly limited, but when it is a polymer, it preferably includes polyolefins (including high density and ultra-high molecular weight) such as polyethylene (PE) and polypropylene (PP); polyamides such as nylon 6 and nylon 66; polyimides (PI); polyamideimides; polyesters such as polyethylene terephthalate; polyethersulfone; cellulose; polyfluorocarbons such as polytetrafluoroethylene (PTFE) and perfluoroalkoxyalkanes; derivatives of the above polymers; and more preferably at least one selected from the group consisting of polyolefins, polyamides, polyimides, polyamideimides, polyesters, polysulfones, cellulose, polyfluorocarbons, and derivatives thereof. In addition to resins, diatomaceous earth, glass, etc. may also be used.

[0531] The resist composition may be filtered using one filter or a combination of two or more filters. When two or more filters are used, they may be the same or different. The resist composition may be circulated and repeatedly filtered using the same filter.

[0532] The resist composition can be applied onto a substrate (e.g., silicon, silicon coated with silicon dioxide, etc.) 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 when spin application using a spinner is preferably 1000 to 3000 rpm (rotations per minute). After application of the resist composition, the substrate may be dried to form a resist film. If necessary, various undercoating films (inorganic film, organic film, anti-reflective film, etc.) may be formed below the resist film.

[0533] An example of a drying method is a method of drying by heating. Heating can be performed by means provided in at least one of a normal exposure machine and a developing machine, and may be performed using a hot plate or the like. The heating temperature is not particularly limited, but is preferably 80 to 150°C, more preferably 80 to 140°C, and even more preferably 80 to 130°C. The heating time is not particularly limited, but is preferably 30 to 1,000 seconds, more preferably 60 to 800 seconds, and even more preferably 60 to 600 seconds.

[0534] 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. Furthermore, 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.

[0535] A top coat may be formed on the resist film using a top coat composition. For example, it is preferable to form a top coat containing a basic compound such as that described in JP 2013-61648 A on the resist film. Specific examples of the basic compound that may be contained in the top coat include basic compounds that may be contained in the resist composition.

[0536] [Step (2)] Step (2) is a step of exposing the resist film formed in step (1). 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, and preferably far ultraviolet light with a wavelength of 250 nm or less, more preferably 220 nm or less, and particularly preferably 1 to 200 nm, specifically KrF excimer laser (248 nm), ArF excimer laser (193 nm), F ２ These include excimer laser (157 nm), EUV (13.5 nm), X-ray, and electron beam.

[0537] After exposure, it is preferable to bake (heat) the film before developing. This step is also called post-exposure baking. Baking promotes the reaction of the exposed areas, resulting in better sensitivity and pattern shape. The heating temperature for baking is not particularly limited, but is preferably 80 to 150°C, more preferably 80 to 140°C, and even more preferably 80 to 130°C. The heating time for baking is not particularly limited, but 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 a means provided in at least one of a conventional exposure machine and a developing machine, and may be performed using a hot plate or the like.

[0538] [Step (3)] Step (3) is a step of developing the resist film exposed in step (2) using a developer to form a pattern. By performing step (3), a resist pattern (also simply referred to as a "pattern") is formed. The developer used in step (3) may be an alkaline developer or a developer containing an organic solvent (also referred to as an "organic developer"). Examples of development methods include a method of immersing a substrate in a tank filled with the developer for a certain period of time (dip method), a method of piling the developer on the surface of the substrate by surface tension and leaving it to stand for a certain period of time (puddle method), a method of spraying the developer onto the substrate surface (spray method), and a method of continuously discharging the developer while scanning a developer discharge nozzle at a constant speed onto a substrate rotating at a constant speed (dynamic dispense method). The development time 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. In step (3), a step of stopping the development while replacing the solvent with another solvent may be carried out.

[0539] 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.

[0540] 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.

[0541] The organic solvents may be mixed in plural, or may be mixed with a solvent other than the organic solvents or water. The water content of the organic 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 organic developer.

[0542] The organic developer preferably contains butyl acetate (n-butyl acetate), and more preferably contains butyl acetate and a hydrocarbon having from 9 to 12 carbon atoms. The organic developer may contain only one or more hydrocarbons having from 9 to 12 carbon atoms. The hydrocarbon having from 9 to 12 carbon atoms is preferably at least one selected from the group consisting of alkanes, alkenes, alkynes, and cycloalkanes, more preferably an alkane, still more preferably at least one selected from the group consisting of nonane, decane, undecane, and dodecane, particularly preferably at least one selected from the group consisting of undecane and dodecane, and most preferably undecane. The hydrocarbon having from 9 to 12 carbon atoms may contain a structural isomer.

[0543] The content of butyl acetate in the organic developer is preferably 65% ​​by mass or more and 99% by mass or less, more preferably 70% by mass or more and 95% by mass or less, and even more preferably 75% by mass or more and 90% by mass or less, based on 100% by mass of the entire organic developer. The content of hydrocarbons having 9 to 12 carbon atoms in the organic developer (the total amount when multiple hydrocarbons having 9 to 12 carbon atoms are contained) is preferably 1% by mass or more and 35% by mass or less, more preferably 5% by mass or more and 30% by mass or less, and even more preferably 10% by mass or more and 25% by mass or less, based on 100% by mass of the entire organic developer.

[0544] The mass ratio of butyl acetate to hydrocarbon having from 9 to 12 carbon atoms in the organic developer (butyl acetate content / hydrocarbon content having from 9 to 12 carbon atoms) is preferably from 60 / 40 to 95 / 5, more preferably from 70 / 30 to 95 / 5, still more preferably from 80 / 20 to 90 / 10, and particularly preferably 90 / 10.

[0545] The organic developer may contain other components in addition to butyl acetate and hydrocarbons having from 9 to 12 carbon atoms. Examples of other components include water, organic solvents other than butyl acetate and hydrocarbons having from 9 to 12 carbon atoms, surfactants, antioxidants, basic compounds, and the like.

[0546] [Rinsing Step] After step (3) is performed, rinsing may be performed. The rinsing solution is not particularly limited as long as it does not dissolve the pattern, and a solution containing a common solvent can be used. The rinsing solution preferably contains at least one organic solvent selected from the group consisting of hydrocarbon solvents, ketone solvents, ester solvents, alcohol solvents, amide solvents, and ether solvents.

[0547] The rinsing method is not particularly limited, and examples thereof include a method in which a rinse liquid 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 rinse liquid for a certain period of time (dip method), and a method in which a rinse liquid is sprayed onto the surface of the substrate (spray method).

[0548] The pattern formation method of the present invention may also include a heating step (post-bake) after step (3). This step removes the developer and rinse solution remaining between and within the pattern. This step also has the effect of annealing the resist pattern and improving the surface roughness of the pattern. The heating step after step (3) may be performed, for example, at 40 to 250°C (preferably 90 to 200°C) for 10 seconds to 3 minutes (preferably 30 to 120 seconds).

[0549] 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 not particularly limited, but oxygen plasma etching is preferred.

[0550] The developer, resist composition, and other various materials (e.g., solvent, rinse, anti-reflective coating-forming composition, top coat-forming composition, etc.) used in the pattern formation method of the present invention 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 (parts per trillion) or less, particularly preferably 10 mass ppt or less, and most preferably 1 mass ppt or less. The lower limit of the impurity content is not particularly limited and may be 0 mass ppt or more. 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.

[0551] Methods for reducing impurities such as metals contained in various materials include, for example, selecting raw materials with low metal content as raw materials for the various materials, filtering the raw materials for the various materials, and lining the inside of the apparatus with Teflon (registered trademark) to perform distillation under conditions that minimize contamination. Details of filtration using a filter are described in paragraph

[0321] of WO 2020 / 004306.

[0552] 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 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 a content of 0 ppt by mass or more is preferred.

[0553] [Method for Manufacturing an Electronic Device] This specification also relates to a method for manufacturing an electronic device, including the pattern formation method of the present invention described above, and an electronic device manufactured by this manufacturing method. Preferred embodiments of the electronic device of this specification include those installed in electrical and electronic equipment (such as home appliances, office automation (OA), media-related equipment, optical equipment, and communication equipment).

[0554] (Examples of the first aspect of the present invention) The first aspect of the present invention will be described in more detail below based on examples. The materials, amounts used, ratios, treatment details, and treatment procedures shown in the following examples can be changed as appropriate 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 examples shown below.

[0555] [Examples 1 to 33, Comparative Examples 1 to 4] <Synthesis Example 1A: Synthesis of Polymer Q-1>

[0556]

[0557] Propylene glycol monomethyl ether acetate (22 g) was heated to 85°C under a nitrogen stream. While stirring this liquid, a mixed solution of a monomer represented by M-a-1A (10 g), a monomer represented by M-c-1 (26 g), a monomer represented by M-b-5 (15 g), propylene glycol monomethyl ether acetate (84 g), and dimethyl 2,2'-azobisisobutyrate [V-601, Fujifilm Wako Pure Chemical Industries, Ltd.] (2.8 g) was added dropwise over 6 hours. After completion of the dropwise addition, the reaction solution was stirred at 85°C for an additional 2 hours to obtain a polymerized solution. The obtained polymerized solution contained a polymer Q-1 containing repeating units corresponding to the monomer represented by M-a-1A, repeating units corresponding to the monomer represented by M-c-1, and repeating units corresponding to the monomer represented by M-b-5.

[0558]

[0559] Synthesis Example 1B Synthesis of Polymer P-1 Methanol (100 g) and triethylamine (16 g) were added to the obtained polymerization solution, and the mixture was stirred at 80°C for 10 hours. After stirring, the solution was allowed to cool to room temperature (20°C), and then ethyl acetate (650 g) and a 0.2 mol / L aqueous hydrochloric acid solution (400 mL) were added and stirred for 30 minutes to extract the organic layer. The extracted organic layer was washed five times with distilled water (400 mL). The washed organic layer was reprecipitated with a mixed solvent of heptane / ethyl acetate = 9 / 1 (mass ratio) and then filtered. The obtained solid was vacuum dried to obtain 35 g of Polymer P-1. The weight average molecular weight (Mw: polystyrene equivalent) of Polymer P-1 determined by GPC (carrier: tetrahydrofuran (THF)) was 10,000, and the dispersity (Mw / Mn) was 1.60. １３The repeating unit content was determined by C-NMR (nuclear magnetic resonance). Polymer P-1 contains a repeating unit represented by the following structural formula: Polymer Q-1 was decomposed by the action of triethylamine to obtain polymer P-1. More specifically, a leaving group in a repeating unit corresponding to a monomer represented by M-a-1A in polymer Q-1 was eliminated by the action of triethylamine to become a repeating unit represented by a-1, thereby obtaining polymer P-1. With respect to all repeating units in polymer P-1, the content of repeating units represented by a-1 was 20 mol %, the content of repeating units corresponding to a monomer represented by M-c-1 was 60 mol %, and the content of repeating units corresponding to a monomer represented by M-b-5 was 20 mol %.

[0560]

[0561] Synthesis Example 2A: Synthesis of Polymer Q-2

[0562]

[0563] Propylene glycol monomethyl ether acetate (22 g) was heated to 85°C under a nitrogen stream. While stirring this liquid, a mixed solution of a monomer represented by M-a-1C (11 g), a monomer represented by M-c-2 (29 g), a monomer represented by M-b-2 (10 g), propylene glycol monomethyl ether acetate (84 g), and dimethyl 2,2'-azobisisobutyrate [V-601, Fujifilm Wako Pure Chemical Industries, Ltd.] (2.8 g) was added dropwise over 6 hours. After completion of the dropwise addition, the reaction solution was stirred at 85°C for an additional 2 hours to obtain a polymerized solution. The obtained polymerized solution contained a polymer Q-2 containing repeating units corresponding to the monomer represented by M-a-1C, repeating units corresponding to the monomer represented by M-c-2, and repeating units corresponding to the monomer represented by M-b-2.

[0564]

[0565] Synthesis Example 2B Synthesis of Polymer P-2 To the obtained polymerization solution, 80 g of a 3% by mass aqueous solution of p-toluenesulfonic acid was added, and the mixture was stirred at room temperature (20°C) for 3 hours. After stirring was completed, ethyl acetate (650 g) and distilled water (400 mL) were added, and the mixture was stirred for 30 minutes to extract the organic layer. The extracted organic layer was washed five times with distilled water (400 mL). The washed organic layer was reprecipitated with a mixed solvent of heptane / ethyl acetate = 9 / 1 (mass ratio) and then filtered. The obtained solid was dried in a vacuum to obtain 33 g of Polymer P-2. The weight average molecular weight (Mw: polystyrene equivalent) of Polymer P-2 determined by GPC (carrier: tetrahydrofuran (THF)) was 12,000, and the dispersity (Mw / Mn) was 1.55. １３ The repeating unit content was determined by C-NMR (nuclear magnetic resonance). Polymer P-2 contains a repeating unit represented by the following structural formula: Polymer Q-2 was decomposed by the action of p-toluenesulfonic acid to obtain polymer P-2. More specifically, the leaving group in the repeating unit corresponding to the monomer represented by M-a-1C in polymer Q-2 was eliminated by the action of p-toluenesulfonic acid to become the repeating unit represented by a-1, thereby obtaining polymer P-2. With respect to all repeating units in polymer P-2, the content of the repeating unit represented by a-1 was 20 mol %, the content of the repeating unit corresponding to the monomer represented by M-c-2 was 60 mol %, and the content of the repeating unit corresponding to the monomer represented by M-b-2 was 20 mol %.

[0566]

[0567] Synthesis Example 3: Synthesis of Polymer P-1X

[0568]

[0569] Propylene glycol monomethyl ether acetate (22 g) was heated to 85°C under a nitrogen stream. While stirring this liquid, a mixed solution of a monomer represented by M-a-1 (8 g), a monomer represented by M-c-1 (27 g), a monomer represented by M-b-5 (16 g), propylene glycol monomethyl ether acetate (84 g), and dimethyl 2,2'-azobisisobutyrate [V-601, manufactured by Fujifilm Wako Pure Chemical Industries, Ltd.] (2.8 g) was added dropwise over 6 hours. After completion of the dropwise addition, the reaction solution was stirred at 85°C for an additional 2 hours to obtain a polymerization solution. The obtained polymerization solution was reprecipitated with a mixed solvent of heptane / ethyl acetate = 9 / 1 (mass ratio) and then filtered. The obtained solid was dried under vacuum to obtain 40 g of polymer P-1X. The weight average molecular weight (Mw: polystyrene equivalent) of polymer P-1X determined by GPC (carrier: tetrahydrofuran (THF)) was 10,000, and the dispersity (Mw / Mn) was 1.60. １３ The repeating unit contents were measured by C-NMR (nuclear magnetic resonance), and it was found that, relative to all repeating units in polymer P-1X, the content of repeating units corresponding to the monomer represented by M-a-1 (repeating units represented by a-1) was 20 mol %, the content of repeating units corresponding to the monomer represented by M-c-1 was 60 mol %, and the content of repeating units corresponding to the monomer represented by M-b-5 was 20 mol %.

[0570] <Synthesis of Polymers Q-3 to Q-31> Polymerization solutions containing polymers Q-3 to Q-31 were obtained in the same manner as in Synthesis Example 1A above, except that the monomers used and their amounts were changed. The repeating units contained in polymers Q-3 to Q-31 and the content of each repeating unit are shown in Tables 1 and 2. Table 1 also shows the same for polymers Q-1 and Q-2 described above. The "type" column for each repeating unit in the table lists the corresponding monomer.

[0571]

[0572]

[0573] The structural formula of the monomer corresponding to the repeating unit is shown below.

[0574]

[0575]

[0576]

[0577]

[0578]

[0579] <Synthesis of Polymers P-3 to P-31> Polymers P-3 to P-31 were synthesized in the same manner as in Synthesis Example 1B or Synthesis Example 2B above, except that a polymerization solution containing polymers Q-3 to Q-31 was used. The leaving groups contained in the repeating units of polymers Q-3 to Q-31 listed as "repeating unit 1" and "repeating unit 2" in Tables 1 and 2 were eliminated by the action of triethylamine or p-toluenesulfonic acid, resulting in the repeating units listed as "repeating unit 1" and "repeating unit 2" in Tables 3 and 4, respectively. When triethylamine was used in the same manner as in Synthesis Example 1B above, the "elimination conditions" in Tables 3 and 4 were listed as "base." When p-toluenesulfonic acid was used in the same manner as in Synthesis Example 2B above, the "elimination conditions" in Tables 3 and 4 were listed as "acid."

[0580] The repeating units contained in polymers P-3 to P-31, the content of each repeating unit, and the weight average molecular weights (Mw) a...

Claims

1. (1) a step of polymerizing at least a compound represented by formula (i) and a monomer having an acid-decomposable group to obtain a polymer (Q); In formula (i), X １ represents a hydrogen atom or a substituent. １ represents a single bond or a divalent linking group. Ar represents an aromatic ring group. R Ｘ represents a group that is eliminated by the action of an acid or a base. n1 represents an integer of 1 or more. When n1 represents an integer of 2 or more, a plurality of R Ｘ may be the same or different, and multiple R Ｘ may be bonded to form a ring. Ｘ R in Ｘ is another -O-R Ｘ R in Ｘ (2) a step of decomposing the polymer (Q) by the action of an acid or a base to obtain a polymer (P) having a repeating unit represented by formula (ii); In formula (ii), X １ , L １ , Ar and n1 are each X in formula (i). １ , L １ , Ar and n1 have the same meaning as Ar and n2. A pattern forming method comprising: (3) a step of obtaining an actinic ray-sensitive or radiation-sensitive resin composition containing the polymer (P), a photoacid generator and a solvent, (4) a step of forming a film using the actinic ray-sensitive or radiation-sensitive resin composition, (5) a step of exposing the film, and (6) a step of developing the exposed film with an organic treatment liquid containing butyl acetate and a hydrocarbon having from 9 to 12 carbon atoms.

2. L in the formulas (i) and (ii) １ The pattern formation method according to claim 1 , wherein represents a single bond.

3. The pattern formation method according to claim 1, wherein in the step (2), the polymer (Q) is decomposed by the action of a base to obtain the polymer (P).

4. R in the formula (i) Ｘ The pattern forming method according to claim 1 , wherein represents an acyl group.

5. The pattern formation method according to claim 1, wherein in the step (2), the polymer (Q) is decomposed by the action of an acid to obtain the polymer (P).

6. R in the formula (i) Ｘ The pattern formation method according to claim 1, wherein Rx represents a group represented by any one of formulas (Y1) to (Y4): 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 １ In formula (Y1) and formula (Y2), Rx １ ~Rx ３ Rx each independently represents an alkyl group, a cycloalkyl group, an alkenyl group, or an aryl group. １ ~Rx ３ In formula (Y3), two of R may be bonded to form a ring. ３６ ~R ３８ R each independently represents a hydrogen atom or a monovalent organic group. ３７ and R ３８ may be bonded to form a ring. １ represents an aromatic ring group. Rn represents an alkyl group, a cycloalkyl group, or an aryl group. Rn and Ar １ may be bonded to form a non-aromatic ring.

7. The pattern forming method according to claim 1, wherein the polymer (Q) contains a repeating unit having at least one group selected from the group consisting of a lactone group, a sultone group, a carbonate group, a sulfonyl group, an alcoholic hydroxyl group, and a carboxy group.

8. The pattern forming method according to claim 1, wherein the content of the photoacid generator is 10% by mass or more based on the total solid content of the actinic ray-sensitive or radiation-sensitive resin composition.

9. The pattern forming method according to claim 1, wherein the polymer (P) contains repeating units having an acid-decomposable group in an amount of more than 50 mol % based on the total repeating units.

10. The pattern formation method according to claim 1, wherein the photoacid generator contains a fluorine atom or an iodine atom.

11. The pattern formation method according to claim 1, wherein the photoacid generator contains a cation having a fluorine atom.

12. The pattern formation method according to claim 1, wherein the photoacid generator contains an anion having an iodine atom.

13. A method for manufacturing an electronic device, comprising the pattern formation method according to any one of claims 1 to 12.

14. An actinic ray-sensitive or radiation-sensitive resin composition containing a resin (A) containing a repeating unit (a) having an acid-decomposable group, a compound (B) that generates an acid upon irradiation with actinic rays or radiation, a solvent, and a crosslinking agent, wherein the content of the repeating unit (a) in the resin (A) is 40 mol% or more based on the total repeating units of the resin (A).

15. The actinic ray-sensitive or radiation-sensitive resin composition according to claim 14, wherein the content of the repeating unit (a) in the resin (A) is 50 mol % or more based on the total repeating units of the resin (A).

16. The actinic ray-sensitive or radiation-sensitive resin composition according to claim 14, wherein the content of the repeating unit (a) in the resin (A) is 55 mol % or more based on the total repeating units of the resin (A).

17. The actinic ray-sensitive or radiation-sensitive resin composition according to claim 14, wherein the repeating unit (a) has a structure in which a carboxy group is protected with a group that is cleaved by the action of an acid.

18. The actinic ray-sensitive or radiation-sensitive resin composition according to claim 14, wherein the resin (A) contains a repeating unit represented by the following formula (b-1): In formula (b-1), R １１ , R １２ and R １３ each independently represents a hydrogen atom, an alkyl group, a halogen atom, a cyano group, or an alkoxycarbonyl group. １ is a single bond, —COO— or —CONR ｍ１ - represents. ｍ１ represents a hydrogen atom or an alkyl group. ｍ１ and R １２ and may be bonded to each other to form a ring. １ represents a single bond or an alkylene group. １ and R １２ may be bonded to each other to form a ring. １ represents an aromatic group. １ and R １２ may be bonded to each other to form a ring, and n represents an integer of 1 to 4.

19. The actinic ray- or radiation-sensitive resin composition according to claim 14, wherein the compound (B) contains a cation having a halogen atom.

20. The actinic ray- or radiation-sensitive resin composition according to claim 14, wherein the compound (B) contains an anion having an iodine atom.

21. The actinic ray-sensitive or radiation-sensitive resin composition according to claim 14, wherein the content of the resin (A) is 75 mass% or less based on the total solid content in the actinic ray-sensitive or radiation-sensitive resin composition.

22. The actinic ray-sensitive or radiation-sensitive resin composition according to claim 14, wherein the compound (B) is at least one selected from the group consisting of the following compound (I) and the following compound (II): Compound (I): A compound having one or more structural moieties Z1 and one or more structural moieties Z2, which satisfies the following condition (I). When compound (I) has two or more structural moieties Z1, the two or more structural moieties Z1 may be the same or different, and when compound (I) has two or more structural moieties Z2, the two or more structural moieties Z2 may be the same or different. Condition (I): Structural moieties Z1 and Z2 are structural moieties that generate an acid upon irradiation with actinic rays or radiation, and the acid generated from structural moiety Z1 is stronger than the acid generated from structural moiety Z2. Compound (II): A compound having two or more structural moieties Z1 and one or more structural moieties Z3, which generates an acid containing two or more acidic moieties derived from structural moiety Z1 and structural moiety Z3 upon irradiation with actinic rays or radiation. The two or more structural moieties Z1 in the compound (II) may be the same or different. Structural moiety Z3: a nonionic moiety capable of neutralizing an acid 23. The actinic ray-sensitive or radiation-sensitive resin composition according to claim 14, wherein the weight-average molecular weight of the resin (A) is 20,000 or less.

24. The actinic ray- or radiation-sensitive resin composition according to claim 14, wherein the crosslinking agent has at least one group selected from the group consisting of a methylol group and a methoxymethyl group.

25. The actinic ray- or radiation-sensitive resin composition according to claim 14, wherein the crosslinking agent has at least two groups selected from the group consisting of methylol groups and methoxymethyl groups.

26. The actinic ray-sensitive or radiation-sensitive resin composition according to claim 14, wherein the content of the crosslinking agent is 0.5 mass % or less based on the actinic ray-sensitive or radiation-sensitive resin composition.

27. The actinic ray-sensitive or radiation-sensitive resin composition according to claim 14, wherein the content of the crosslinking agent is 0.3 mass % or less based on the actinic ray-sensitive or radiation-sensitive resin composition.

28. A resist film formed using the actinic ray-sensitive or radiation-sensitive resin composition according to any one of claims 14 to 27.

29. A pattern formation method comprising the steps of forming a resist film using the actinic ray-sensitive or radiation-sensitive resin composition according to any one of claims 14 to 27, exposing the resist film to light, and developing the exposed resist film with a developer.

30. The pattern forming method according to claim 29, wherein the developer contains an organic solvent and the pattern formed is a negative pattern.

31. A method for manufacturing an electronic device, comprising the pattern formation method according to claim 29.

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