Active-ray-sensitive or radiation-sensitive resin composition, resist film, pattern formation method, and electronic device production method

Abstract

Provided are: an active-ray-sensitive or radiation-sensitive resin composition that contains a resin (X) having a repeating unit (u1) which generates acid upon irradiation with an activity ray or radiation, wherein the repeating unit (u1) includes a cation and an anion which is bonded to the molecular chain of the resin (X) and the repeating unit (u1) content is not less than 80 mass% with respect to the total amount of resin contained in the active-ray-sensitive or radiation-sensitive resin composition; a resist film that uses the active-ray-sensitive or radiation-sensitive resin composition; a pattern formation method; and an electronic device production method.

Description

Actinic ray- 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- 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- or radiation-sensitive resin composition that can be suitably used in ultra-microlithography processes 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, and to a resist film, a pattern forming method, and a method for manufacturing an electronic device using the actinic ray- or radiation-sensitive resin composition.

[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] Various compositions are known as actinic ray- or radiation-sensitive resin compositions. Patent Document 1 describes a photoresist composition containing a first polymer having a specific structure containing 50 to 100 mol % of photoacid-generating repeating units, based on 100 mol % of all repeating units, and a second polymer that exhibits a change in solubility in an alkaline developer under the action of acid. Patent Document 2 also describes a pattern formation method in which a resist pattern is formed by generating an acid from a radiation-sensitive acid-generating group-containing resin contained as a resin component of a radiation-sensitive resin composition upon irradiation with actinic rays or radiation, thereby increasing the solubility of the radiation-sensitive acid-generating group-containing resin in a developer.

[0005] Japanese Patent Publication No. 2016-81053 Japanese Patent Publication No. 2007-328060

[0006] Recently, the performance required of resist compositions has become increasingly higher. In particular, further improvements are required in terms of resolution and reduction of defects when forming fine patterns (e.g., 1:1 line and space patterns with line widths of 20 nm or less).

[0007] An object of the present invention is to provide an actinic ray-sensitive or radiation-sensitive resin composition that has excellent resolution and reduces defects. Another object of the present invention is to provide a resist film, a pattern formation method, and a method for manufacturing an electronic device that use the actinic ray-sensitive or radiation-sensitive resin composition.

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

[0009] [1] An actinic ray-sensitive or radiation-sensitive resin composition containing a solvent and a resin (X) having a repeating unit (u1) that generates an acid upon irradiation with actinic rays or radiation, wherein the repeating unit (u1) contains a cation and an anion bonded to a molecular chain of the resin (X), and the content of the repeating unit (u1) is 80% by mass or more relative to the total amount of resins contained in the actinic ray-sensitive or radiation-sensitive resin composition. [2] The actinic ray-sensitive or radiation-sensitive resin composition according to [1], wherein the content of the repeating unit (u1) is 90% by mass or more relative to the total amount of resins contained in the actinic ray-sensitive or radiation-sensitive resin composition. [3] The actinic ray-sensitive or radiation-sensitive resin composition according to [1] or [2], wherein the content of the repeating unit (u1) is 95% by mass or more relative to the total amount of resins contained in the actinic ray-sensitive or radiation-sensitive resin composition. [4] The actinic ray-sensitive or radiation-sensitive resin composition according to any one of [1] to [3], wherein the pKa of the acid generated from the repeating unit (u1) is 2.0 or less. [5] The actinic ray-sensitive or radiation-sensitive resin composition according to any one of [1] to [4], wherein the acid generated from the repeating unit (u1) is a sulfonic acid. [6] The actinic ray-sensitive or radiation-sensitive resin composition according to any one of [1] to [4], wherein the repeating unit (u1) is represented by the following formula (UA1):

[0010]

[0011] In formula (UA1), R ａ１ , R ａ２ and R ａ３ each independently represents a hydrogen atom, an alkyl group, a cycloalkyl group, a halogen atom, a cyano group, or an alkoxycarbonyl group. ａ１ represents a single bond or a divalent linking group. １ － represents an anion. ＋ represents a cation. [7] The actinic ray-sensitive or radiation-sensitive resin composition according to any one of [1] to [4], wherein the repeating unit (u1) is represented by the following formula (UA2):

[0012]

[0013] In formula (UA2), R ａ１ , R ａ２ and R ａ３ each independently represents a hydrogen atom, an alkyl group, a cycloalkyl group, a halogen atom, a cyano group, or an alkoxycarbonyl group. ａ２ represents a single bond or a divalent linking group. １ represents an aromatic group. ａ４ represents a substituent other than a fluorine atom. k1 represents an integer of 1 or more. k2 represents an integer of 0 or more. E １ － represents an anion. ＋ represents a cation. [8] The actinic ray-sensitive or radiation-sensitive resin composition according to any one of [1] to [5], wherein the repeating unit (u1) is represented by the following formula (UA3):

[0014]

[0015] In formula (UA3), R ａ１ , R ａ２ and R ａ３ each independently represents a hydrogen atom, an alkyl group, a cycloalkyl group, a halogen atom, a cyano group, or an alkoxycarbonyl group. ａ２ represents a single bond or a divalent linking group. ＋ [9] The actinic ray-sensitive or radiation-sensitive resin composition according to any one of [1] to [8], wherein the cation is at least one selected from the group consisting of a cation represented by the following formula (ZaI) and a cation represented by the following formula (ZaII):

[0016]

[0017] In the formula (ZaI), R ２０１ , R ２０２ and R ２０３ R each independently represents an organic group. ２０１ , R ２０２ and R ２０３ In formula (ZaII), at least two of R may be bonded to form a ring. ２０４ and R ２０５ R each independently represents an organic group. ２０４ and R２０５ may be bonded to form a ring.

[10] The actinic ray-sensitive or radiation-sensitive resin composition according to any one of [1] to [9], wherein the content of the resin (X) is 60 to 100 mass% based on the total solid content in the actinic ray-sensitive or radiation-sensitive resin composition.

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

[10] .

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

[10] , exposing the resist film to light, and developing the exposed resist film using a developer.

[13] A method for producing an electronic device, comprising the pattern formation method according to

[12] .

[0018] The present invention provides an actinic ray-sensitive or radiation-sensitive resin composition that is excellent in resolution and can reduce defects. The present invention also provides a resist film, a pattern forming method, and a method for manufacturing an electronic device that use the actinic ray-sensitive or radiation-sensitive resin composition.

[0019] The present invention will be described in detail below. The following description of the components will be based on representative embodiments of the present invention, but the present invention is not limited to such embodiments.

[0020] 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, electron beams (EB), and the like. 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, EUV, and the like, 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.

[0021] 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.

[0022] 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).

[0023] 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:

[0024] (Substituent T) Examples of the substituent T include halogen atoms such as a fluorine atom, a chlorine atom, a bromine atom, and an iodine atom; alkoxy groups such as a methoxy group, an ethoxy group, and a tert-butoxy group; a cycloalkyloxy group; an aryloxy group such as a phenoxy group and a p-tolyloxy group; an alkoxycarbonyl group such as a methoxycarbonyl group and a butoxycarbonyl group; a cycloalkyloxycarbonyl group; an aryloxycarbonyl group such as a phenoxycarbonyl group; an acyloxy group such as an acetoxy group, a propionyloxy group, and a benzoyloxy group; an acetyl group, a benzoyl group, an isobutyryl group, Examples of the substituent T include acyl groups such as acryloyl, methacryloyl, and methoxalyl; sulfanyl groups; alkylsulfanyl groups such as methylsulfanyl and tert-butylsulfanyl; arylsulfanyl groups such as phenylsulfanyl and p-tolylsulfanyl; alkyl groups; alkenyl groups; cycloalkyl groups; aryl groups; aromatic heterocyclic groups; hydroxy groups; carboxyl groups; formyl groups; sulfo groups; cyano groups; alkylaminocarbonyl groups; arylaminocarbonyl groups; sulfonamide groups; silyl groups; amino groups; 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 (e.g., monoalkylamino groups, dialkylamino groups, arylamino groups, trifluoromethyl groups, etc.). However, when R in formula (N1) １ｂ and R ２ｂ In the case where it is described as not having a fluorine atom, such as "a substituent not having a fluorine atom," the above substituent T does not include a fluorine atom.

[0025] 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".

[0026] 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).

[0027] 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.

[0028] 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.

[0029] In this specification, "solid content" refers to components that form an actinic ray-sensitive or radiation-sensitive film (or a resist film when the actinic ray-sensitive or radiation-sensitive film is a resist composition), and does not include solvents. Furthermore, any component 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.

[0030] <Actinic ray-sensitive or radiation-sensitive resin composition> The actinic ray-sensitive or radiation-sensitive resin composition of the present invention (also referred to as "the composition of the present invention") is an actinic ray-sensitive or radiation-sensitive resin composition containing a solvent and a resin (X) having a repeating unit (u1) that generates an acid upon irradiation with actinic rays or radiation, wherein the repeating unit (u1) contains a cation and an anion bonded to a molecular chain of the resin (X), and the content of the repeating unit (u1) is 80 mass% or more relative to the total amount of resins contained in the actinic ray-sensitive or radiation-sensitive resin composition.

[0031] The composition of the present invention is typically a resist composition, and may be a positive resist composition or a negative resist composition. The composition of the present invention may be a resist composition for alkali development or a resist composition for organic solvent development. An actinic ray-sensitive or radiation-sensitive film can be formed using the composition of the present invention. The actinic ray-sensitive or radiation-sensitive film formed using the composition of the present invention is typically a resist film. First, the various components of the composition of the present invention will be described in detail below.

[0032] [Resin (X)] Resin (X) is a resin having a repeating unit (u1) that generates an acid upon irradiation with actinic rays or radiation. Resin (X) is a compound that generates an acid upon irradiation with actinic rays or radiation (also referred to as a "photoacid generator"). Resin (X) may be a linear polymer or a non-linear polymer (for example, a polymer having a branched, graft, comb, star, cyclic, or network structure).

[0033] The resin (X) may have a repeating unit other than the repeating unit (u1) in addition to the repeating unit (u1), or may have only the repeating unit (u1) (it may be a resin consisting only of the repeating unit (u1)).

[0034] (Repeating Unit (u1)) The repeating unit (u1) is a repeating unit that generates an acid upon irradiation with actinic rays or radiation (also referred to as a "photoacid-generating repeating unit"). The repeating unit (u1) contains a cation and an anion bonded to the molecular chain of the resin (X). The molecular chain of the resin (X) is a group formed by covalent bonds between multiple atoms, and when the resin (X) is a linear polymer, examples of the molecular chain include the main chain and side chain. Furthermore, when the resin (X) is a non-linear polymer (for example, a polymer having a branched, grafted, comb-shaped, star-shaped, cyclic, or network structure), examples of the molecular chain include a molecular chain that forms at least a part of the structure of the non-linear polymer. The anion contained in the repeating unit (u1) is preferably covalently bonded to the molecular chain of the resin (X). The repeating unit (u1) may have only one anion bonded to the molecular chain of the resin (X), or may have two or more anions bonded to the molecular chain of the resin (X). When two or more anions are present, the anions may be the same or different.

[0035] The anion is not particularly limited, but examples thereof include anions represented by any of the following formulae (an1) to (an7), and the anion represented by the following formula (an1) is particularly preferred.

[0036]

[0037] In formulas (an1) to (an7), * represents the bonding position with the molecular chain of resin (X). Ａ Each of the two R in formula (an3) independently represents an organic group. Ａ may be the same or different.

[0038] R Ａ The organic group represented by is not particularly limited, but examples thereof include organic groups having 1 to 20 carbon atoms, and organic groups having 1 to 10 carbon atoms are preferred. The organic group may contain a heteroatom such as an oxygen atom, a sulfur atom, or a nitrogen atom. Preferred examples of the organic group include a cyano group, an alkyl group, a cycloalkyl group, and an aryl group. The organic group may have a substituent, and examples of the substituent include, but are not particularly limited to, a halogen atom, a hydroxy group, and a fluorine atom is preferred.

[0039] The anion represented by any one of formulas (an1) to (an7) may be bonded to an aliphatic group or an aromatic group contained in the molecular chain of resin (X). When the anion represented by any one of formulas (an1) to (an7) is bonded to an aliphatic group contained in the molecular chain of resin (X), the aliphatic group may have a substituent and preferably has a fluorine atom. When the anion represented by formulas (an1) to (an7) is bonded to an aromatic group contained in the molecular chain of resin (X), the aromatic group may have a substituent and preferably has a fluorine atom.

[0040] The repeating unit (u1) contains a cation. The cation contained in the repeating unit (u1) is preferably not covalently bonded to the molecular chain of the resin (X). The cation contained in the repeating unit (u1) is not particularly limited, but is preferably an organic cation, more preferably a sulfonium cation or an iodonium cation. The valence of the cation may be monovalent or divalent or higher. The cation is preferably at least one selected from the group consisting of a cation represented by the following formula (ZaI) (also referred to as "cation (ZaI)") and a cation represented by the following formula (ZaII) (also referred to as "cation (ZaII)"):

[0041]

[0042] In the formula (ZaI), R ２０１ , R ２０２ and R ２０３ R each independently represents an organic group. ２０１ , R ２０２ and R ２０３ In formula (ZaII), at least two of R may be bonded to form a ring. ２０４ and R ２０５ R each independently represents an organic group. ２０４ and R ２０５ may be bonded to form a ring.

[0043] R in formula (ZaI) ２０１ , R ２０２ and R ２０３R 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 ２０２ and R ２０３ At least two of these may be bonded to form a ring, and the ring may contain at least one of an oxygen atom, a sulfur atom, an ester group, an amide group, and a carbonyl group. ２０１ , R ２０２ and R ２０３ Examples of the group formed by bonding at least two of the above include an alkylene group (e.g., a butylene group, a pentylene group, etc.), —CH ２ -CH ２ -O-CH ２ -CH ２ --etc.

[0044] Suitable embodiments of the cation represented by formula (ZaI) include cation (ZaI-1), cation (ZaI-2), cation (ZaI-3b), and cation (ZaI-4b) described below.

[0045] First, the cation (ZaI-1) will be described. The cation (ZaI-1) is R in the above formula (ZaI). ２０１ ~R ２０３ is an arylsulfonium cation, in which at least one of R is an aryl group. ２０１ ~R ２０３ may all be aryl groups, or R ２０１ ~R ２０３ A part of R may be an aryl group, and the rest may be an alkyl group or a cycloalkyl group. ２０１ ~R ２０３ is an aryl group, and R ２０１ ~R ２０３ The remaining two of R may be bonded to form a ring structure, and the ring may contain an oxygen atom, a sulfur atom, an ester group, an amide group, or a carbonyl group. ２０１ ~R ２０３Examples of groups formed by combining two of the above include alkylene groups in which one or more methylene groups may be substituted with at least one of an oxygen atom, a sulfur atom, an ester group, an amide group, and 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.

[0046] 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.

[0047] 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 term "acid-decomposable group" is the same as that described in the "repeating unit having an acid-decomposable group" of the example of repeating unit (u2) described below.

[0048] 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 having no 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.

[0049] 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.

[0050] Next, the cation (ZaI-3b) will be described. The cation (ZaI-3b) is a cation represented by the following formula (ZaI-3b).

[0051]

[0052] 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.

[0053] 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.

[0054] 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.

[0055] 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.

[0056] Next, the cation (ZaI-4b) will be described. The cation (ZaI-4b) is a cation represented by the following formula (ZaI-4b).

[0057]

[0058] 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.

[0059] 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.

[0060] Next, formula (ZaII) will be described. R in formula (ZaII) ２０４ and R ２０５ R each independently represents an organic group, and preferably represents an aryl group, a heteroaryl 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 heteroaryl group may be a heteroaryl group having a heteroatom such as an oxygen atom, a nitrogen atom, or a sulfur atom. Examples of the skeleton of the heteroaryl group include pyrrole, furan, thiophene, indole, benzofuran, and benzothiophene. ２０４ and R ２０５ The alkyl group and cycloalkyl group are preferably a linear alkyl group having 1 to 10 carbon atoms or a branched alkyl group having 3 to 10 carbon atoms (e.g., methyl, ethyl, propyl, butyl, pentyl, etc.), or a cycloalkyl group having 3 to 10 carbon atoms (e.g., cyclopentyl, cyclohexyl, norbornyl, etc.).

[0061] R ２０４ and R ２０５ The aryl group, heteroaryl group, alkyl group and cycloalkyl group in R may each independently have a substituent. ２０４ and R ２０５Examples of the substituent that the aryl group, heteroaryl group, alkyl group, and cycloalkyl group may have include an alkyl group (e.g., having 1 to 15 carbon atoms), a cycloalkyl group (e.g., having 3 to 15 carbon atoms), an aryl group (e.g., having 6 to 15 carbon atoms), an alkoxy group (e.g., having 1 to 15 carbon atoms), a halogen atom, a hydroxy group, and a phenylthio group. ２０４ and R ２０５ It is also preferred that the substituents independently form an acid-decomposable group by any combination of the substituents.

[0062] Specific examples of cations are shown below, but are not limited to these.

[0063]

[0064]

[0065] The repeating unit (u1) is preferably represented by the following formula (UA1).

[0066]

[0067] In formula (UA1), R ａ１ , R ａ２ and R ａ３ each independently represents a hydrogen atom, an alkyl group, a cycloalkyl group, a halogen atom, a cyano group, or an alkoxycarbonyl group. ａ１ represents a single bond or a divalent linking group. １ － represents an anion. ＋ represents a cation.

[0068] R in formula (UA1) ａ１ , R ａ２ and R ａ３ R each independently represents a hydrogen atom, an alkyl group, a cycloalkyl group, a halogen atom, a cyano group, or an alkoxycarbonyl group. ａ１ , R ａ２ and R ａ３The alkyl group in R 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. ａ１ , R ａ２ and R ａ３ The number of carbon atoms in the cycloalkyl group is not particularly limited, but is preferably 3 to 20, and more preferably 5 to 15. ａ１ , R ａ２ and R ａ３ The cycloalkyl group in R 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. ａ１ , R ａ２ and R ａ３ Examples of the halogen atom in 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. ａ１ , R ａ２ and R ａ３ The alkyl group contained in the alkoxycarbonyl group 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 10, more preferably 1 to 5, and particularly preferably 1 to 3.

[0069] L in formula (UA1) ａ１ represents a single bond or a divalent linking group. ａ１ The divalent linking group represented by is —CO—, —O—, —S—, —SO—, —SO ２ -, -NR Ｂ -, an aliphatic group, an aromatic group, and a linking group in which a plurality of these groups are linked together. Ｂ represents a hydrogen atom or an organic group.

[0070] L ａ１ The aliphatic group represented by is preferably an aliphatic group having 1 to 20 carbon atoms, and examples thereof include an alkylene group, a cycloalkylene group, and an alkenylene group. ａ１The alkylene group represented by may be linear or branched. The alkylene group preferably has 1 to 20 carbon atoms, more preferably 1 to 10 carbon atoms, and even more preferably 1 to 5 carbon atoms. ａ１ The number of carbon atoms in the cycloalkylene group represented by is not particularly limited, but is preferably 3 to 20, and more preferably 5 to 15. ａ１ The cycloalkylene group represented by may be a monocyclic cycloalkylene group or a polycyclic cycloalkylene group. ａ１ The alkenylene group represented by may be linear or branched. The alkenylene group preferably has 2 to 20 carbon atoms, more preferably 2 to 10 carbon atoms, and even more preferably 2 to 5 carbon atoms. ａ１ The aromatic group represented by may be an aromatic hydrocarbon group or an aromatic heterocyclic group. Examples of aromatic hydrocarbon groups include arylene groups having 6 to 18 carbon atoms, such as a phenylene group, a tolylene group, a naphthylene group, and an anthracenylene group. A phenylene group or a naphthylene group is particularly preferred, and a phenylene group is most preferred. Examples of aromatic heterocyclic groups include groups containing a heterocycle such as a thiophene ring, a furan ring, a pyrrole ring, a benzothiophene ring, a benzofuran ring, a benzopyrrole ring, a triazine ring, an imidazole ring, a benzimidazole ring, a triazole ring, a thiadiazole ring, and a thiazole ring. The aliphatic group and the aromatic group may have a substituent. The substituent is not particularly limited, but examples include an alkyl group, a cycloalkyl group, an aryl group, an alkoxy group, a halogen atom, and a hydroxy group, and a fluorine atom is preferred.

[0071] L ａ１ Preferably, the group contains an arylene group, more preferably an arylene group having a fluorine atom.

[0072] R Ｂ The organic group represented by is not particularly limited, and examples thereof include organic groups having 1 to 20 carbon atoms. The organic group may contain a heteroatom such as an oxygen atom, a sulfur atom, or a nitrogen atom. Preferred examples of the organic group include a cyano group, an alkyl group, a cycloalkyl group, and an aryl group.

[0073] E in formula (UA1) １ －represents an anion. １ － As the anion, for example, an anion represented by any one of the above formulas (an1) to (an7) is preferred, and the anion represented by the above formula (an1) is particularly preferred.

[0074] M in formula (UA1) ＋ represents a cation. The explanation, specific examples, and preferred ranges of the cation are the same as those described above.

[0075] The repeating unit (u1) is preferably represented by the following formula (UA2).

[0076]

[0077] In formula (UA2), R ａ１ , R ａ２ and R ａ３ each independently represents a hydrogen atom, an alkyl group, a cycloalkyl group, a halogen atom, a cyano group, or an alkoxycarbonyl group. ａ２ represents a single bond or a divalent linking group. １ represents an aromatic group. ａ４ represents a substituent other than a fluorine atom. k1 represents an integer of 1 or more. k2 represents an integer of 0 or more. E １ － represents an anion. ＋ represents a cation.

[0078] R in formula (UA2) ａ１ , R ａ２ , R ａ３ , E １ － and M ＋ The explanation, specific examples and preferred ranges of R in the above formula (UA1) are as follows: ａ１ , R ａ２ , R ａ３ , E １ － and M ＋ is the same as

[0079] L in formula (UA2) ａ２ represents a single bond or a divalent linking group. ａ２ The divalent linking group represented by is —CO—, —O—, —S—, —SO—, —SO ２-, an aliphatic group, an aromatic group, and a linking group in which a plurality of these groups are linked together. ａ２ The divalent linking group represented by is —COO—, —O—, —SO ３ -, an aliphatic group, an aromatic group, or a linking group in which a plurality of these groups are linked is preferred.

[0080] L ａ２ The explanation, specific examples and preferred ranges of the aliphatic group and aromatic group represented by are respectively described in the above formula (UA1) L ａ１ The explanations, specific examples and preferred ranges of the aliphatic group and aromatic group represented by are the same as those of the aliphatic group and aromatic group represented by the formula (I).

[0081] Ar in formula (UA2) １ represents an aromatic group. １ The aromatic group represented by may be an aromatic hydrocarbon group or an aromatic heterocyclic group. Examples of the aromatic hydrocarbon group include arylene groups having 6 to 18 carbon atoms, such as a phenylene group, a tolylene group, a naphthylene group, and an anthracenylene group. A phenylene group or a naphthylene group is particularly preferred, and a phenylene group is most preferred. Examples of the aromatic heterocyclic group include groups containing a heterocycle, such as a thiophene ring, a furan ring, a pyrrole ring, a benzothiophene ring, a benzofuran ring, a benzopyrrole ring, a triazine ring, an imidazole ring, a benzimidazole ring, a triazole ring, a thiadiazole ring, and a thiazole ring.

[0082] R in formula (UA2) ａ４ represents a substituent other than a fluorine atom. ａ４ The substituent represented by is not particularly limited as long as it is not a fluorine atom, and examples thereof include an alkyl group, a cycloalkyl group, an aryl group, an alkoxy group, and a hydroxy group.

[0083] In formula (UA2), k1 represents an integer of 1 or more. １ represents the number of fluorine atoms substituted on the aromatic group represented by Ar. １ It depends on the type of aromatic group represented by Ar. １ When represents a phenylene group, k1 preferably represents an integer of 1 to 4.

[0084] In formula (UA2), k2 represents an integer of 0 or more.１ represents the number of substituents other than fluorine atoms that can be substituted on the aromatic group represented by Ar １ It depends on the type of aromatic group represented by Ar. １ When represents a phenylene group, k2 preferably represents an integer of 0 to 3.

[0085] The repeating unit (u1) is preferably represented by the following formula (UA3).

[0086]

[0087] In formula (UA3), R ａ１ , R ａ２ and R ａ３ each independently represents a hydrogen atom, an alkyl group, a cycloalkyl group, a halogen atom, a cyano group, or an alkoxycarbonyl group. ａ２ represents a single bond or a divalent linking group. ＋ represents a cation.

[0088] R in formula (UA2) ａ１ , R ａ２ , R ａ３ , L ａ２ and M ＋ The explanation, specific examples and preferred ranges of R in the above formula (UA2) are as follows: ａ１ , R ａ２ , R ａ３ , L ａ２ and M ＋ is the same as

[0089] The acid generated from the repeating unit (u1) is preferably a sulfonic acid.

[0090] The pKa of the acid generated from the repeating unit (u1) is preferably 2.0 or less, more preferably 1.0 or less, and even more preferably 0.0 or less. The pKa of the acid generated from the repeating unit (u1) may be -20.0 or more. The pKa of the acid generated from the repeating unit (u1) is determined by the above-mentioned method for the corresponding monomer. For example, when the repeating unit (u1) is X-1u shown below (M ＋represents a cation), the acid generated from the repeating unit (u1) is the following X-1a, and the pKa of the following X-1m, which is a monomer corresponding to the following X-1a, is determined by the above-mentioned method, and this is used as the pKa of the acid generated from the following X-1u.

[0091]

[0092] The content of the repeating unit (u1) is preferably 80% by mass or more, more preferably 85% by mass or more, even more preferably 90% by mass or more, particularly preferably 95% by mass or more, and most preferably 100% by mass, based on the total repeating units in the resin (X). The repeating unit (u1) contained in the resin (X) may be of one type or two or more types. When the repeating unit (u1) contained in the resin (X) is of two or more types, the total content thereof is preferably within the above-mentioned preferred content range.

[0093] Specific examples of the repeating unit (u1) are shown below, but the present invention is not limited to these.

[0094]

[0095]

[0096] The content of the repeating unit (u1) is 80% by mass or more, preferably 85% by mass or more, more preferably 90% by mass or more, even more preferably 95% by mass or more, and particularly preferably 100% by mass, relative to the total amount of resins contained in the composition of the present invention. When the composition of the present invention contains two or more types of repeating unit (u1), the total content thereof preferably falls within the above-mentioned preferred content range. The total amount of resins contained in the composition of the present invention means the total mass of all resins contained in the composition of the present invention. In this specification, the term "resin" refers to a compound having a repeating structure in which two or more structural units derived from one or more types of monomers are linked together and having a weight-average molecular weight of 1,000 or more. Therefore, the term "resin" may include not only resin (X) but also resins other than resin (X), such as resin (A), hydrophobic resins, and surfactants, which will be described later.

[0097] Although the reason why the composition of the present invention has excellent resolution and reduced defects is unclear, the inventors have hypothesized the following mechanism. However, the present invention is not limited in any way by the hypothesized mechanism below. When irradiated with actinic rays or radiation, the repeating unit (u1) contained in the resin (X) undergoes cation decomposition to generate an acid, resulting in a greater polarity than before irradiation with actinic rays or radiation (a polarity conversion occurs). In the present invention, by setting the content of the repeating unit (u1) to 80 mass% or more of the total amount of resin contained in the composition of the present invention, it is believed that a pattern can be formed mainly by utilizing the polarity conversion caused by the decomposition of the repeating unit (u1). The mechanism for forming a pattern in the present invention differs from the mechanism of Patent Document 1, which mainly utilizes polarity conversion caused by an elimination reaction of an acid-decomposable resin catalyzed by an acid generated from a photoacid generator. When a resist film formed using the composition of the present invention is exposed and developed, the polarity of the exposed areas becomes greater than that of the unexposed areas. Therefore, when an alkaline developer is used as the developer, the exposed areas dissolve, forming a pattern (positive). When an organic developer is used as the developer, the unexposed areas dissolve, forming a pattern (negative). In the present invention, by adjusting the content of the repeating unit (u1) to 80% by mass or more relative to the total amount of resin contained in the composition of the present invention, the solubility of the exposed areas in the alkaline developer (resistance to solubility in an organic developer) can be significantly improved, and resolution can be improved. Furthermore, the resin (X) having the repeating unit (u1) is a photoacid generator. By adjusting the content of the repeating unit (u1) to 80% by mass or more relative to the total amount of resin contained in the composition of the present invention, the distribution of the photoacid generator is made uniform (variation is suppressed), and defects during pattern formation can be reduced. In the present invention, it is intended to form a pattern mainly by utilizing polarity conversion due to decomposition of the repeating unit (u1). Therefore, the content of the repeating unit (u1) is expressed as a mass fraction relative to the total amount of resin in the composition of the present invention.Furthermore, the composition of the present invention is considered to be a non-chemically amplified resist composition because it mainly utilizes polarity conversion due to decomposition of the repeating unit (u1) described above. However, the present invention also includes cases in which the resin (X) has a repeating unit having an acid-decomposable group, or cases in which the resin (X) contains the resin (A) described below. Therefore, the composition may utilize polarity conversion due to an elimination reaction of the acid-decomposable group catalyzed by an acid generated from a photoacid generator, or may be a chemically amplified resist composition.

[0098] (Other Repeating Units) The resin (X) may have another repeating unit in addition to the repeating unit (u1). The other repeating unit is also referred to as "repeating unit (u2)." The repeating unit (u2) is a repeating unit different from the repeating unit (u1). The content of the repeating unit (u2) may be 0% by mass or more and 40% by mass or less, based on all repeating units in the resin (X). When the resin (X) has the repeating unit (u2), the content of the repeating unit (u2) may be 1% by mass or more, 5% by mass or more, or even 10% by mass or more, based on all repeating units in the resin (X). Furthermore, the content of the repeating unit (u2) may be 30% by mass or less, or 20% by mass or less, based on all repeating units in the resin (X). It is particularly preferable that the content of the repeating unit (u2) is 0% by mass, based on all repeating units in the resin (X) (it is particularly preferable that the resin (X) does not have the repeating unit (u2)). The resin (X) may have only one type of repeating unit (u2), or may have two or more types. When the resin (X) has two or more types of repeating unit (u2), it is preferable that the total content thereof is within the above-mentioned suitable content range.

[0099] ((Repeating unit having an acid-decomposable group)) The repeating unit (u2) may be a repeating unit having an acid-decomposable group. The repeating unit having an acid-decomposable group may be a repeating unit having an acid-decomposable group containing an unsaturated bond. The acid-decomposable group refers to a group that decomposes under the action of an acid to generate a polar group. The acid-decomposable group preferably has a structure in which the polar group is protected with a group that leaves under the action of an acid (leaving group). The polar group is preferably an alkali-soluble group, such as a carboxyl group, a phenolic hydroxyl group, a fluorinated alcohol group, a sulfonic acid group, a phosphate group, a sulfonamide group, a sulfonylimide group, a (alkylsulfonyl) (alkylcarbonyl) methylene group, a (alkylsulfonyl) (alkylcarbonyl) imide group, a bis(alkylcarbonyl) methylene group, a bis(alkylcarbonyl) imide group, a bis(alkylsulfonyl) methylene group, a bis(alkylsulfonyl) imide group, a tris(alkylcarbonyl) methylene group, and an acidic group such as a tris(alkylsulfonyl) methylene group, and an alcoholic hydroxyl group. Among these, the polar group is preferably a carboxyl group, a phenolic hydroxyl group, a fluorinated alcohol group (preferably a hexafluoroisopropanol group), or a sulfonic acid group.

[0100] Examples of the group that is eliminated by the action of an acid include groups represented by formulae (Y1) to (Y4). Formula (Y1): —C(Rx １ ) (Rx ２ ) (Rx ３ ) Formula (Y2): -C(=O)OC(Rx １ ) (Rx ２ ) (Rx ３ ) Formula (Y3): -C(R ３６ ) (R ３７ ) (OR ３８ ) Formula (Y4): -C(Rn)(H)(Ar)

[0101] In formula (Y1) and formula (Y2), Rx １ ~Rx ３ Rx each independently represents an alkyl group (linear or branched), a cycloalkyl group (monocyclic or polycyclic), an alkenyl group (linear or branched), or an aryl group (monocyclic or polycyclic).１ ~Rx ３ When all of Rx are alkyl groups (linear or branched), １ ~Rx ３ At least two of Rx are preferably methyl groups. １ ~Rx ３ each independently preferably represents a linear or branched alkyl group, and Rx １ ~Rx ３ More preferably, Rx each independently represents a linear alkyl group. １ ~Rx ３ may be bonded to form a monocyclic or polycyclic ring. １ ~Rx ３ The alkyl group of Rx is preferably an alkyl group having 1 to 5 carbon atoms, such as a methyl group, an ethyl group, an n-propyl group, an isopropyl group, an n-butyl group, an isobutyl group, or a t-butyl group. １ ~Rx ３ The cycloalkyl group 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. １ ~Rx ３ The aryl group in Rx is preferably an aryl group having 6 to 10 carbon atoms, and examples thereof include a phenyl group, a naphthyl group, and an anthryl group. １ ~Rx ３ The alkenyl group of Rx is preferably a vinyl group. １ ~Rx ３ The ring formed by combining the two is preferably a cycloalkyl group. １ ~Rx ３ The cycloalkyl group formed by bonding the two is preferably a monocyclic cycloalkyl group such as a cyclopentyl group or a cyclohexyl group, or a polycyclic cycloalkyl group such as a norbornyl group, a tetracyclodecanyl group, a tetracyclododecanyl group, or an adamantyl group, and more preferably a monocyclic cycloalkyl group having 5 to 6 carbon atoms. １ ~Rx ３In the cycloalkyl group formed by bonding these two, one of the methylene groups constituting the ring may be replaced with a heteroatom such as an oxygen atom, a group containing a heteroatom such as a carbonyl group, or a vinylidene group. In these cycloalkyl groups, one or more of the ethylene groups constituting the cycloalkane ring may be replaced with a vinylene group. The group represented by formula (Y1) or formula (Y2) can be, for example, Rx １ is a methyl group or an ethyl group, and Rx ２ and Rx ３ and Rx are preferably bonded to form the above-mentioned cycloalkyl group. When the composition of the present invention is, for example, a resist composition for EUV exposure, １ ~Rx ３ an alkyl group, a cycloalkyl group, an alkenyl group, an aryl group, and Rx １ ~Rx ３ The ring formed by bonding these two groups preferably further has a fluorine atom or an iodine atom as a substituent.

[0102] 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. Examples of the monovalent organic group include an alkyl group, a cycloalkyl group, an aryl group, an aralkyl group, and an alkenyl group. ３６ is also preferably a hydrogen atom. The alkyl group, cycloalkyl group, aryl group, and aralkyl group may contain a heteroatom such as an oxygen atom and / or a group containing a heteroatom such as a carbonyl group. For example, in the alkyl group, cycloalkyl group, aryl group, and aralkyl group, one or more methylene groups may be replaced with a heteroatom such as an oxygen atom and / or a group containing a heteroatom such as a carbonyl group. R ３８ may bond with another substituent on the main chain of the repeating unit to form a ring. ３８The group formed by bonding together R and another substituent on the main chain of the repeating unit is preferably an alkylene group such as a methylene group. ３６ ~R ３８ and a monovalent organic group represented by R ３７ and R ３８ It is also preferable that the ring formed by bonding these groups together further has a fluorine atom or an iodine atom as a substituent.

[0103] Formula (Y3) is preferably a group represented by the following formula (Y3-1).

[0104]

[0105] Here, L １ and L ２ Each independently represents a hydrogen atom, an alkyl group, a cycloalkyl group, an aryl group, or a group combining these (for example, a group combining an alkyl group and an aryl group). M represents a single bond or a divalent linking group. Q represents an alkyl group that may contain a heteroatom, a cycloalkyl group that may contain a heteroatom, an aryl group that may contain a heteroatom, an amino group, an ammonium group, a mercapto group, a cyano group, an aldehyde group, or a group combining these (for example, a group combining an alkyl group and a cycloalkyl group). In the alkyl group and the cycloalkyl group, for example, one of the methylene groups may be replaced with a heteroatom such as an oxygen atom, or a group containing a heteroatom such as a carbonyl group. In addition, L １ and L ２ It is preferred that one of Q, M, and L is a hydrogen atom, and the other is an alkyl group, a cycloalkyl group, an aryl group, or a group in which an alkylene group and an aryl group are combined. １ At least two of the groups may be bonded to form a ring (preferably a 5- or 6-membered ring). ２is preferably a secondary or tertiary alkyl group, and more preferably a tertiary alkyl group. Examples of secondary alkyl groups include an isopropyl group, a cyclohexyl group, and a norbornyl group, and examples of tertiary alkyl groups include a tert-butyl group and an adamantane group. In these embodiments, the Tg (glass transition temperature) and activation energy are increased, thereby ensuring film strength and suppressing fogging.

[0106] When the composition of the present invention is, for example, a resist composition for EUV exposure, L １ and L ２ It is also preferable that the alkyl group, cycloalkyl group, aryl group, and combinations thereof represented by the formula (I) further have a fluorine atom or an iodine atom as a substituent. The alkyl group, cycloalkyl group, aryl group, and aralkyl group preferably contain a heteroatom such as an oxygen atom in addition to the fluorine atom and iodine atom. Specifically, in the alkyl group, cycloalkyl group, aryl group, and aralkyl group, for example, one of the methylene groups may be replaced with a heteroatom such as an oxygen atom, or a group containing a heteroatom such as a carbonyl group. When the composition of the present invention is, for example, a resist composition for EUV exposure, in the alkyl group which may contain a heteroatom, cycloalkyl group which may contain a heteroatom, aryl group which may contain a heteroatom, amino group, ammonium group, mercapto group, cyano group, aldehyde group, and combinations thereof represented by Q, the heteroatom is preferably selected from the group consisting of a fluorine atom, an iodine atom, and an oxygen atom.

[0107] In formula (Y4), Ar represents an aromatic ring group. Rn represents an alkyl group, a cycloalkyl group, or an aryl group. Rn and Ar may be bonded to each other to form a non-aromatic ring. Ar is preferably an aryl group. When the composition of the present invention is, for example, a resist composition for EUV exposure, it is also preferable that the aromatic ring group represented by Ar and the alkyl group, cycloalkyl group, and aryl group represented by Rn have a fluorine atom or an iodine atom as a substituent.

[0108] 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.

[0109] 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.

[0110] The repeating unit having an acid-decomposable group is also preferably a repeating unit represented by formula (A).

[0111]

[0112] L １ represents a divalent linking group which may have a fluorine atom or an iodine atom, R １ represents a hydrogen atom, a fluorine atom, an iodine atom, an alkyl group which may have a fluorine atom or an iodine atom, or an aryl group which may have a fluorine atom or an iodine atom; R ２ represents a leaving group which is eliminated by the action of an acid and may have a fluorine atom or an iodine atom. １ , R １ , and R ２ At least one of L has a fluorine atom or an iodine atom. １ Examples of the divalent linking group which may have a fluorine atom or an iodine atom and is represented by the formula: ２ -, hydrocarbon groups which may have a fluorine atom or an iodine atom (for example, alkylene groups, cycloalkylene groups, alkenylene groups, arylene groups, etc.), and linking groups in which a plurality of these groups are linked together. １As the alkylene group, -CO-, an arylene group, or -arylene group-alkylene group having a fluorine atom or an iodine atom- is preferred, and -CO- or -arylene group-alkylene group having a fluorine atom or an iodine atom- is more preferred. As the arylene group, a phenylene group is preferred. The alkylene group may be linear or branched. The number of carbon atoms in the alkylene group is not particularly limited, but is preferably 1 to 10, and more preferably 1 to 3. The total number of fluorine atoms and iodine atoms contained in the alkylene group having a fluorine atom or an iodine atom is not particularly limited, but is preferably 2 or more, more preferably 2 to 10, and even more preferably 3 to 6.

[0113] R １ The alkyl group represented by R may be linear or branched. The number of carbon atoms in the alkyl group is not particularly limited, but is preferably 1 to 10, and more preferably 1 to 3. １ The total number of fluorine atoms and iodine atoms contained in the alkyl group having a fluorine atom or an iodine atom, represented by the formula (I), is not particularly limited, but is preferably 1 or more, more preferably 1 to 5, and even more preferably 1 to 3. １ The alkyl group represented by the formula (I) may contain a heteroatom other than a halogen atom, such as an oxygen atom.

[0114] R ２ Examples of the leaving group represented by the formulae (Y1) to (Y4) above, which may have a fluorine atom or an iodine atom, include leaving groups represented by the formulae (Y1) to (Y4) above, which have a fluorine atom or an iodine atom.

[0115] The repeating unit having an acid-decomposable group is also preferably a repeating unit represented by formula (AI).

[0116]

[0117] In formula (AI), Xa １ represents a hydrogen atom or an alkyl group which may have a substituent. T represents a single bond or a divalent linking group. Rx １ ~Rx ３each independently represents an alkyl group (linear or branched), a cycloalkyl group (monocyclic or polycyclic), an alkenyl group (linear or branched), or an aryl group (monocyclic or polycyclic). １ ~Rx ３ When all of Rx are alkyl groups (linear or branched), １ ~Rx ３ Preferably, at least two of Rx are methyl groups. １ ~Rx ３ may be bonded to form a monocyclic or polycyclic ring (such as a monocyclic or polycyclic cycloalkyl group).

[0118] Xa １ Examples of the alkyl group represented by the formula (I) which may have a substituent include a methyl group or —CH ２ -R １１ Examples of the group include a group represented by R １１ represents a halogen atom (such as a fluorine atom), a hydroxyl group, or a monovalent organic group. １１ Examples of the monovalent organic group represented by the formula (I) include an alkyl group having 5 or less carbon atoms which may be substituted with a halogen atom, an acyl group having 5 or less carbon atoms which may be substituted with a halogen atom, and an alkoxy group having 5 or less carbon atoms which may be substituted with a halogen atom, and an alkyl group having 3 or less carbon atoms is preferred, and a methyl group is more preferred. １ is preferably a hydrogen atom, a methyl group, a trifluoromethyl group, or a hydroxymethyl group.

[0119] Examples of the divalent linking group for T include an alkylene group, an aromatic ring group, a -COO-Rt- group, and a -O-Rt- group. In the formula, Rt represents an alkylene group or a cycloalkylene group. T is preferably a single bond or a -COO-Rt- group. When T represents a -COO-Rt- group, Rt is preferably an alkylene group having 1 to 5 carbon atoms, and is preferably a -CH ２ - group, -(CH ２ ) ２ - group, or -(CH ２ ) ３ The - group is more preferred.

[0120] Rx １ ~Rx ３The alkyl group of Rx is preferably an alkyl group having 1 to 4 carbon atoms, such as a methyl group, an ethyl group, an n-propyl group, an isopropyl group, an n-butyl group, an isobutyl group, or a t-butyl group. １ ~Rx ３ The cycloalkyl group of Rx is preferably a monocyclic cycloalkyl group such as a cyclopentyl group or a cyclohexyl group, or a polycyclic cycloalkyl group such as a norbornyl group, a tetracyclodecanyl group, a tetracyclododecanyl group, or an adamantyl group. １ ~Rx ３ The aryl group in Rx is preferably an aryl group having 6 to 10 carbon atoms, and examples thereof include a phenyl group, a naphthyl group, and an anthryl group. １ ~Rx ３ The alkenyl group of Rx is preferably a vinyl group. １ ~Rx ３ As the cycloalkyl group formed by combining the above two, a monocyclic cycloalkyl group such as a cyclopentyl group or a cyclohexyl group is preferred. Polycyclic cycloalkyl groups such as a norbornyl group, a tetracyclodecanyl group, a tetracyclododecanyl group, and an adamantyl group are also preferred. Among these, a monocyclic cycloalkyl group having 5 to 6 carbon atoms is preferred. Rx １ ~Rx ３ The cycloalkyl group formed by bonding these two may have, for example, one of the methylene groups constituting the ring replaced with a heteroatom such as an oxygen atom, a group containing a heteroatom such as a carbonyl group, or a vinylidene group. Furthermore, in these cycloalkyl groups, one or more of the ethylene groups constituting the cycloalkane ring may be replaced with a vinylene group. The repeating unit represented by formula (AI) can be, for example, Rx １ is a methyl group or an ethyl group, and Rx ２ and Rx ３ and are preferably bonded to form the above-mentioned cycloalkyl group.

[0121] 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.

[0122] The repeating unit represented by formula (AI) may be an acid-decomposable (meth)acrylic acid tertiary alkyl ester repeating unit (Xa １ represents a hydrogen atom or a methyl group, and T represents a single bond).

[0123] The resin (X) may have a repeating unit having an acid-decomposable group containing an unsaturated bond as the repeating unit having an acid-decomposable group. The repeating unit having an acid-decomposable group containing an unsaturated bond is preferably a repeating unit represented by formula (B):

[0124]

[0125] In formula (B), Xb represents a hydrogen atom, a halogen atom, or an alkyl group which may have a substituent. L represents a single bond or a divalent linking group which may have a substituent. Ry １ ~Ry ３ each independently represents a linear or branched alkyl group, a monocyclic or polycyclic cycloalkyl group, an alkenyl group, an alkynyl group, or a monocyclic or polycyclic aryl group, provided that Ry １ ~Ry ３ At least one of R represents an alkenyl group, an alkynyl group, a monocyclic or polycyclic cycloalkenyl group, or a monocyclic or polycyclic aryl group. １ ~Ry ３ may be bonded to form a monocyclic or polycyclic ring (such as a monocyclic or polycyclic cycloalkyl group or cycloalkenyl group).

[0126] The alkyl group represented by Xb, which may have a substituent, is, for example, a methyl group or —CH ２ -R １１ Examples of the group include a group represented by R １１represents a halogen atom (such as a fluorine atom), a hydroxyl group, or a monovalent organic group, and examples thereof include an alkyl group having 5 or less carbon atoms which may be substituted with a halogen atom, an acyl group having 5 or less carbon atoms which may be substituted with a halogen atom, and an alkoxy group having 5 or less carbon atoms which may be substituted with a halogen atom, preferably an alkyl group having 3 or less carbon atoms, and more preferably a methyl group. Xb is preferably a hydrogen atom, a fluorine atom, a methyl group, a trifluoromethyl group, or a hydroxymethyl group.

[0127] Examples of the divalent linking group for L include a -Rt- group, a -CO- group, a -COO-Rt- group, a -COO-Rt-CO- group, a -Rt-CO- group, and a -O-Rt- group. In the formula, Rt represents an alkylene group, a cycloalkylene group, or an aromatic ring group, and an aromatic ring group is preferable. L is preferably a -Rt- group, a -CO- group, a -COO-Rt-CO- group, or a -Rt-CO- group. Rt may have a substituent such as a halogen atom, a hydroxyl group, or an alkoxy group.

[0128] Ry １ ~Ry ３ The alkyl group of Ry is preferably an alkyl group having 1 to 4 carbon atoms, such as a methyl group, an ethyl group, an n-propyl group, an isopropyl group, an n-butyl group, an isobutyl group, or a t-butyl group. １ ~Ry ３ The cycloalkyl group of Ry is preferably a monocyclic cycloalkyl group such as a cyclopentyl group or a cyclohexyl group, or a polycyclic cycloalkyl group such as a norbornyl group, a tetracyclodecanyl group, a tetracyclododecanyl group, or an adamantyl group. １ ~Ry ３ The aryl group in Ry is preferably an aryl group having 6 to 10 carbon atoms, and examples thereof include a phenyl group, a naphthyl group, and an anthryl group. １ ~Ry ３ The alkenyl group in Ry is preferably a vinyl group. １ ~Ry ３ The alkynyl group in Ry is preferably an ethynyl group. １ ~Ry ３The cycloalkenyl group of Ry is preferably a monocyclic cycloalkyl group such as a cyclopentyl group or a cyclohexyl group, which has a double bond in part thereof. １ ~Ry ３ The cycloalkyl group formed by combining the above two groups is preferably a monocyclic cycloalkyl group such as a cyclopentyl group or a cyclohexyl group, or a polycyclic cycloalkyl group such as a norbornyl group, a tetracyclodecanyl group, a tetracyclododecanyl group, or an adamantyl group. Among these, a monocyclic cycloalkyl group having 5 to 6 carbon atoms is more preferred. １ ~Ry ３ The cycloalkyl group or cycloalkenyl group formed by bonding two of the above is, for example, a group in which one of the methylene groups constituting the ring is substituted with a heteroatom such as an oxygen atom, a carbonyl group, or —SO ２ - group and -SO ３ The repeating unit represented by formula (B) may be substituted with a group containing a hetero atom such as a - group, a vinylidene group, or a combination thereof. In addition, in these cycloalkyl groups or cycloalkenyl groups, one or more ethylene groups constituting the cycloalkane ring or cycloalkene ring may be substituted with a vinylene group. １ is a methyl group, an ethyl group, a vinyl group, an allyl group, or an aryl group, and Ry ２ and Ry ３ and are bonded to form the above-mentioned cycloalkyl group or cycloalkenyl group.

[0129] 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.

[0130] The repeating unit represented by formula (B) is preferably an acid-decomposable (meth)acrylic acid tertiary ester repeating unit (a repeating unit in which Xb represents a hydrogen atom or a methyl group and L represents a -CO- group), an acid-decomposable hydroxystyrene tertiary alkyl ether repeating unit (a repeating unit in which Xb represents a hydrogen atom or a methyl group and L represents a phenyl group), or an acid-decomposable styrene carboxylic acid tertiary ester repeating unit (a repeating unit in which Xb represents a hydrogen atom or a methyl group and L represents a -Rt-CO- group (Rt is an aromatic group)). Specific examples of repeating units having an acid-decomposable group containing an unsaturated bond include the repeating units described in paragraphs

[0067] to

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

[0131] For repeating units having an acid-decomposable group, the description in paragraphs

[0029] to

[0075] of WO 2022 / 024928 can be used. The above description is incorporated herein by reference.

[0132] Specific examples of repeating units having an acid-decomposable group are shown below, but are not limited to these.

[0133]

[0134] ((Repeating unit having an acid group)) The repeating unit (u2) may be a repeating unit having an acid group. The acid group is preferably an acid group having a pKa of 13 or less. The pKa of the acid group is more preferably 3 to 13, and even more preferably 5 to 10. The acid group is preferably, for example, a carboxyl group, a phenolic hydroxyl group, a fluorinated alcohol group (preferably a hexafluoroisopropanol group), a sulfonic acid group, a sulfonamide group, or an isopropanol group. In the hexafluoroisopropanol group, one or more (preferably one or 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)—CF２ - may form a ring containing the repeating unit. The repeating unit having an acid group is preferably a repeating unit different from the repeating unit having a structure in which a polar group is protected by a group that is cleaved by the action of an acid described above, and the repeating unit having a lactone group, a sultone group, or a carbonate group described below. The repeating unit having an acid group may have a fluorine atom or an iodine atom. Specific examples of the repeating unit having an acid group include the repeating units described in paragraphs

[0088] to

[0089] and

[0103] to

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

[0135] The repeating unit having an acid group is preferably a repeating unit having a phenolic hydroxyl group. The repeating unit having a phenolic hydroxyl group is preferably a repeating unit different from the repeating unit having an acid-decomposable group described above. The repeating unit having a phenolic hydroxyl group is preferably a repeating unit represented by the following formula (Pa2):

[0136]

[0137] In formula (Pa2), R １０１ , R １０２ and R １０３ R each independently represents a hydrogen atom, an alkyl group, a cycloalkyl group, a halogen atom, a cyano group, or an alkoxycarbonyl group. １０２ is Ar Ａ may be bonded to form a ring, in which case R １０２ represents a single bond or an alkylene group. Ａ represents a single bond or a divalent linking group. Ａ represents an aromatic ring group, and k represents an integer of 1 to 5.

[0138] R in formula (Pa2) １０１ , R １０２ and R １０３ R each independently represents a hydrogen atom, an alkyl group, a cycloalkyl group, a halogen atom, a cyano group, or an alkoxycarbonyl group. １０１ , R １０２ and R １０３The alkyl group in R 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. １０１ , R １０２ and R １０３ The number of carbon atoms in the cycloalkyl group is not particularly limited, but is preferably 3 to 20, and more preferably 5 to 15. １０１ , R １０２ and R １０３ The cycloalkyl group of R 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. １０１ , R １０２ and R １０３ Examples of the halogen atom in 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. １０１ , R １０２ and R １０３ The alkyl group contained in the alkoxycarbonyl group 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.

[0139] Ar in formula (Pa2) Ａrepresents an aromatic ring group, more specifically, a (k+1)-valent aromatic ring group. When k is 1, the divalent aromatic ring group is preferably an arylene group having 6 to 18 carbon atoms, such as a phenylene group, a tolylene group, a naphthylene group, or an anthracenylene group, or a divalent aromatic ring group containing a heterocycle, such as a thiophene ring, a furan ring, a pyrrole ring, a benzothiophene ring, a benzofuran ring, a benzopyrrole ring, a triazine ring, an imidazole ring, a benzimidazole ring, a triazole ring, a thiadiazole ring, or a thiazole ring. The aromatic ring group may have a substituent. When k is an integer of 2 or more, specific examples of the (k+1)-valent aromatic ring group include groups obtained by removing any (k-1) hydrogen atoms from the above-mentioned specific examples of the divalent aromatic ring group. The (k+1)-valent aromatic ring group may further have a substituent. The substituent that the (k+1)-valent aromatic ring group may have is not particularly limited, and examples thereof include alkyl groups such as methyl, ethyl, propyl, isopropyl, n-butyl, sec-butyl, hexyl, 2-ethylhexyl, octyl, and dodecyl; alkoxy groups such as methoxy, ethoxy, hydroxyethoxy, propoxy, hydroxypropoxy, and butoxy; and aryl groups such as phenyl. Ａ preferably represents an aromatic ring group having 6 to 18 carbon atoms, and more preferably represents a benzene ring group, a naphthalene ring group or a biphenylene ring group.

[0140] L in formula (Pa2) Ａ represents a single bond or a divalent linking group. Ａ The divalent linking group represented by is not particularly limited, but examples thereof include —COO—, —CONR １０４ -, an alkylene group, or a group formed by combining two or more of these groups. １０４ 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. R １０４When represents an alkyl group, examples of the alkyl group include alkyl groups having 20 or less carbon atoms, such as a methyl group, an ethyl group, a propyl group, an isopropyl group, an n-butyl group, a sec-butyl group, a hexyl group, a 2-ethylhexyl group, an octyl group, and a dodecyl group, and alkyl groups having 8 or less carbon atoms are preferred.

[0141] The repeating unit represented by formula (Pa2) preferably has a hydroxystyrene structure. Ａ preferably represents a benzene ring group. k preferably represents an integer of 1 to 3, and more preferably represents 1 or 2.

[0142] Specific examples of repeating units having an acid group are shown below, but are not limited to these. １ and G ２ each independently represents a hydrogen atom, a methyl group, a fluorine atom, a chlorine atom, a trifluoromethyl group, a cyano group, a hydroxy group, or a hydroxymethyl group. f1 represents an integer of 1 to 3.

[0143]

[0144] ((Repeating unit having neither an acid-decomposable group nor an acid group, and having a fluorine atom, a bromine atom, or an iodine atom)) The repeating unit (u2) may be a repeating unit having neither an acid-decomposable group nor an acid group, and having a fluorine atom, a bromine atom, or an iodine atom (hereinafter also referred to as "unit X").

[0145] The unit X is preferably a repeating unit represented by formula (C).

[0146]

[0147] L ５ represents a single bond or an ester group. ９ represents a hydrogen atom or an alkyl group which may have a fluorine atom or an iodine atom. １０represents a hydrogen atom, an alkyl group which may have a fluorine atom or an iodine atom, a cycloalkyl group which may have a fluorine atom or an iodine atom, an aryl group which may have a fluorine atom or an iodine atom, or a group combining these. Specific examples of repeating units having a fluorine atom or an iodine atom include the repeating units described in paragraphs

[0116] to

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

[0148] ((Repeating unit having a lactone group, a sultone group, or a carbonate group)) The repeating unit (u2) may be a repeating unit having a lactone group, a sultone group, or a carbonate group (hereinafter also referred to as "unit Y"). It is also preferable that unit Y does not have a hydroxy group or an acid group such as a hexafluoropropanol group.

[0149] 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. Of these, a 5- to 7-membered lactone structure to which another ring structure is fused, forming a bicyclo or spiro structure, or a 5- to 7-membered sultone structure to which another ring structure is fused, forming a bicyclo or spiro structure, is more preferred. The carbonate group is preferably a cyclic carbonate ester group. For repeating units having a cyclic carbonate ester group, see, for example, paragraphs

[0127] to

[0133] of WO 2022 / 024928. The above descriptions are incorporated herein by reference.

[0150] The repeating unit (u2) may be a repeating unit having a lactone group, a sultone group, or a carbonate group obtained by removing one or more hydrogen atoms from a ring member atom of a lactone structure represented by any of the following formulas (LC1-1) to (LC1-22), a sultone structure represented by any of the following formulas (SL1-1) to (SL1-3), or a cyclic carbonate ester structure represented by any of the following formulas (CC1-1) to (CC1-2). Furthermore, the lactone group, sultone group, or carbonate group of the repeating unit (u2) may be directly bonded to the main chain. For example, the ring member atom of the lactone group, sultone group, or carbonate group may constitute the main chain of the resin (X). The lactone group, sultone group, and carbonate group may have a substituent.

[0151] R in the following structural formula Ｌ represents a substituent. Ｌ If there are multiple R Ｌ may be the same or different. Ｌ Examples of R include an alkyl group having 1 to 8 carbon atoms, a cycloalkyl group having 4 to 10 carbon atoms, an alkoxy group having 1 to 8 carbon atoms, an alkoxycarbonyl group having 2 to 8 carbon atoms, a carboxyl group, a halogen atom, a cyano group, and an acid-decomposable group. e1 represents an integer of 0 to 4. When multiple e1s are present, the multiple e1s may be the same or different. When e1 is 2 or more, the multiple R Ｌ may be the same or different, and multiple R Ｌ They may be bonded to each other to form a ring.

[0152]

[0153] Examples of repeating units having a lactone group, a sultone group, or a carbonate group include repeating units represented by the following formula (AI-2).

[0154]

[0155] In formula (AI-2), Rb ０ represents a hydrogen atom, a halogen atom, or an alkyl group having 1 to 4 carbon atoms. ０ The alkyl group of Rb may have a substituent. ０Examples of the substituent that the alkyl group of Rb may have include a hydroxyl group and a halogen atom. ０ Examples of the halogen atom in Rb include a fluorine atom, a chlorine atom, a bromine atom, and an iodine atom. ０ is preferably a hydrogen atom or a methyl group. Ab represents a single bond, an alkylene group, a divalent linking group having a monocyclic or polycyclic alicyclic hydrocarbon structure, an ether group, an ester group, a carbonyl group, or a divalent linking group formed by combining these. Among these, Ab is preferably a single bond or -Ab １ -CO ２ A linking group represented by - is preferred. １ is a linear or branched alkylene group, or a monocyclic or polycyclic cycloalkylene group, and is preferably a methylene group, an ethylene group, a cyclohexylene group, an adamantylene group, or a norbornylene group. V is a group obtained by removing one hydrogen atom from a ring member atom of a lactone structure represented by any of formulas (LC1-1) to (LC1-22), a group obtained by removing one hydrogen atom from a ring member atom of a sultone structure represented by any of formulas (SL1-1) to (SL1-3), or a group obtained by removing one hydrogen atom from a ring member atom of a cyclic carbonate structure represented by any of formulas (CC1-1) to (CC1-2).

[0156] ((Repeating unit represented by formula (V-1) or formula (V-2)) The repeating unit (u2) may be a repeating unit represented by the following formula (V-1) or formula (V-2). It is preferable that the repeating unit represented by the following formula (V-1) and the repeating unit represented by the following formula (V-2) are different from the above-mentioned respective repeating units.

[0157]

[0158] In formulas (V-1) and (V-2), R ６ and R ７each independently represents a hydrogen atom, a hydroxyl group, an alkyl group, an alkoxy group, an acyloxy group, a cyano group, a nitro group, an amino group, a halogen atom, an ester group (-OCOR or -COOR: R is an alkyl group or a fluorinated alkyl group having 1 to 6 carbon atoms), or a carboxyl group. As the alkyl group, a linear, branched, or cyclic alkyl group having 1 to 10 carbon atoms is preferred. ３ represents an integer of 0 to 6. ４ represents an integer of 0 to 4. ４ represents a methylene group, an oxygen atom, or a sulfur atom. Examples of the repeating unit represented by formula (V-1) or formula (V-2) include the repeating units described in paragraph

[0100] of WO 2018 / 193954.

[0159] The resin (X) can be synthesized by a conventional method (for example, radical polymerization).

[0160] The weight average molecular weight (Mw) of the resin (X), 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 (molecular weight distribution, Pd, Mw / Mn) of the resin (X) is preferably 1 to 5, more preferably 1 to 3, even more preferably 1.0 to 3.0, and particularly preferably 1.1 to 2.0.

[0161] The content of resin (X) in the composition of the present invention is not particularly limited, but is preferably 40 to 100 mass% relative to the total solid content in the composition of the present invention, more preferably 50 to 100 mass%, even more preferably 60 to 100 mass%, and particularly preferably 70 to 100 mass%. Resin (X) may be used alone or in combination with two or more types. When two or more types of resin (X) are used, it is preferable that the total content thereof is within the above-mentioned preferred content range.

[0162] The composition of the present invention may contain other components in addition to the resin (X).

[0163] [Resin (A) whose polarity increases under the action of acid] The composition of the present invention may contain a resin (also referred to as "resin (A)") whose polarity increases under the action of acid, which is different from resin (X). Resin (A) is a resin that does not have the repeating unit (u1) described above. Resin (A) contains a group that decomposes under the action of acid to increase polarity (acid-decomposable group), and preferably contains a repeating unit having an acid-decomposable group.

[0164] The "repeating unit having an acid-decomposable group" that the resin (A) may have is the same as the "repeating unit having an acid-decomposable group" exemplified above for the repeating unit (u2).

[0165] The content of the repeating units having an acid-decomposable group is preferably 15 mol% or more, more preferably 20 mol% or more, and even more preferably 30 mol% or more, based on the total repeating units in the resin (A), and the upper limit thereof is preferably 90 mol% or less, more preferably 80 mol% or less, even more preferably 70 mol% or less, and particularly preferably 60 mol% or less, based on the total repeating units in the resin (A).

[0166] Resin (A) may contain at least one repeating unit selected from the group consisting of Group A below, and / or at least one repeating unit selected from the group consisting of Group B below. Group A: A group consisting of the following repeating units (20) to (24). (20) A repeating unit having an acid group; (21) A repeating unit having neither an acid-decomposable group nor an acid group, and having a fluorine atom, a bromine atom, or an iodine atom; (22) A repeating unit having a lactone group, a sultone group, or a carbonate group; (23) A repeating unit represented by formula (V-1) or formula (V-2); (24) A repeating unit for reducing main chain mobility. The repeating units represented by formulas (A) to (E), which will be described later, correspond to (24) A repeating unit for reducing main chain mobility. Group B: A group consisting of the following repeating units (30) to (32). (30) A repeating unit having at least one group selected from a lactone group, a sultone group, a carbonate group, a hydroxyl group, a cyano group, and an alkali-soluble group. (31) A repeating unit having an alicyclic hydrocarbon structure and not exhibiting acid decomposition. (32) A repeating unit represented by formula (III) having neither a hydroxyl group nor a cyano group.

[0167] The "repeating unit having an acid group," "repeating unit having neither an acid-decomposable group nor an acid group and having a fluorine atom, a bromine atom or an iodine atom," "repeating unit having a lactone group, a sultone group or a carbonate group," and "repeating unit represented by formula (V-1) or (V-2)" that the resin (A) may have are the same as the "repeating unit having an acid group," "repeating unit having neither an acid-decomposable group nor an acid group and having a fluorine atom, a bromine atom or an iodine atom," "repeating unit having a lactone group, a sultone group or a carbonate group," and "repeating unit represented by formula (V-1) or (V-2)" listed above for the repeating unit (u2), respectively.

[0168] When the resin (A) contains a repeating unit having an acid group, the content of the repeating unit having an acid group is preferably 10 mol% or more, more preferably 15 mol% or more, based on the total repeating units in the resin (A), and the upper limit thereof is preferably 70 mol% or less, more preferably 65 mol% or less, and even more preferably 60 mol% or less, based on the total repeating units in the resin (A).

[0169] The content of repeating units having neither an acid-decomposable group nor an acid group but having a fluorine atom, a bromine atom, or an iodine atom is preferably 0 mol% or more, more preferably 5 mol% or more, and even more preferably 10 mol% or more, based on all repeating units in the resin (A), and the upper limit thereof is preferably 50 mol% or less, more preferably 45 mol% or less, and even more preferably 40 mol% or less, based on all repeating units in the resin (A).

[0170] When the resin (A) contains a repeating unit having a lactone group, a sultone group, or a carbonate group, the content of the repeating unit having a lactone group, a sultone group, or a carbonate group is preferably 1 mol% or more, more preferably 10 mol% or more, based on all repeating units in the resin (A), and the upper limit thereof is preferably 85 mol% or less, more preferably 80 mol% or less, even more preferably 70 mol% or less, and particularly preferably 60 mol% or less, based on all repeating units in the resin (A).

[0171] (Repeating Unit for Reducing Mobility of Main Chain) Resin (A) preferably has a high glass transition temperature (Tg) in order to suppress excessive diffusion of generated acid or pattern collapse during development. Tg is preferably higher than 90°C, more preferably higher than 100°C, even more preferably higher than 110°C, and particularly preferably higher than 125°C. In order to achieve an excellent dissolution rate in a developer, Tg is preferably 400°C or lower, more preferably 350°C or lower. In this specification, the glass transition temperature (Tg) of a polymer such as resin (A) (hereinafter referred to as "Tg of repeating unit") is calculated by the following method. First, the Tg of a homopolymer consisting of only each repeating unit contained in the polymer is calculated using the Bicerano method. Next, the mass proportion (%) of each repeating unit relative to all repeating units in the polymer is calculated. Next, the Tg at each mass ratio is calculated using the Fox formula (described in Materials Letters 62 (2008) 3152, etc.), and the sum of these values ​​is used to determine the Tg (°C) of the polymer. The Bicerano method is described in "Prediction of Polymer Properties," Marcel Dekker Inc., New York (1993). Calculation of Tg by the Bicerano method can be performed using polymer property estimation software MDL Polymer (MDL Information Systems, Inc.).

[0172] In order to increase the Tg of resin (A) (preferably to make the Tg greater than 90°C), it is preferable to reduce the mobility of the main chain of resin (A). Methods for reducing the mobility of the main chain of resin (A) include the following methods (a) to (e): (a) Introduction of a bulky substituent into the main chain; (b) Introduction of multiple substituents into the main chain; (c) Introduction of a substituent that induces interactions between resins (A) near the main chain; (d) Formation of a main chain with a cyclic structure; (e) Linking of a cyclic structure to the main chain. It is preferable that resin (A) has a repeating unit that exhibits a homopolymer Tg of 130°C or higher. The type of repeating unit that exhibits a homopolymer Tg of 130°C or higher is not particularly limited, and it is sufficient that the repeating unit exhibits a homopolymer Tg of 130°C or higher as calculated by the Bicerano method. It is to be noted that depending on the type of functional group in the repeating units represented by formulas (A) to (E) described below, it may be considered a repeating unit that exhibits a homopolymer Tg of 130°C or higher.

[0173] One example of a specific means for achieving the above (a) is to introduce a repeating unit represented by formula (A) into resin (A).

[0174]

[0175] Formula (A), R Ａ represents a group containing a polycyclic structure. ｘ represents a hydrogen atom, a methyl group, or an ethyl group. A group containing a polycyclic structure is a group containing multiple ring structures, and the multiple ring structures may be condensed or not condensed. Specific examples of the repeating unit represented by formula (A) include those described in paragraphs

[0107] to

[0119] of WO 2018 / 193954.

[0176] One example of a specific means for achieving the above (b) is to introduce a repeating unit represented by formula (B) into resin (A).

[0177]

[0178] In formula (B), R ｂ１ ~R ｂ４ each independently represents a hydrogen atom or an organic group; R ｂ１ ~R ｂ４At least two of the above represent organic groups. When at least one of the organic groups is a group in which a ring structure is directly linked to the main chain in the repeating unit, the type of the other organic groups is not particularly limited. Furthermore, when none of the organic groups is a group in which a ring structure is directly linked to the main chain in the repeating unit, at least two of the organic groups are substituents having three or more constituent atoms excluding hydrogen atoms. Specific examples of the repeating unit represented by formula (B) include those described in paragraphs

[0113] to

[0115] of WO 2018 / 193954.

[0179] One example of a specific means for achieving the above (c) is to introduce a repeating unit represented by formula (C) into resin (A).

[0180]

[0181] In formula (C), R ｃ１ ~R ｃ４ each independently represents a hydrogen atom or an organic group; R ｃ１ ~R ｃ４ At least one of the repeating units represented by formula (C) is a group containing a hydrogen-bonding hydrogen atom within three atoms from the main chain carbon. In particular, in order to induce interactions between the main chains of resin (A), it is preferable to have a hydrogen-bonding hydrogen atom within two atoms (closer to the main chain). Specific examples of the repeating unit represented by formula (C) include those described in paragraphs

[0119] to

[0121] of WO 2018 / 193954.

[0182] One example of a specific means for achieving the above (d) is to introduce a repeating unit represented by formula (D) into resin (A).

[0183]

[0184] In formula (D), "Cyclic" represents a group that forms a main chain with a cyclic structure. The number of constituent atoms of the ring is not particularly limited. Specific examples of the repeating unit represented by formula (D) include those described in paragraphs

[0126] to

[0127] of WO 2018 / 193954.

[0185] One example of a specific means for achieving the above (e) is to introduce a repeating unit represented by formula (E) into resin (A).

[0186]

[0187] In formula (E), Re each independently represents a hydrogen atom or an organic group. Examples of the organic group include an alkyl group, a cycloalkyl group, an aryl group, an aralkyl group, and an alkenyl group, each of which may have a substituent. "Cyclic" refers to a cyclic group containing carbon atoms in the main chain. The number of atoms contained in the cyclic group is not particularly limited. Specific examples of the repeating unit represented by formula (E) include those described in paragraphs

[0131] to

[0133] of WO 2018 / 193954.

[0188] (Repeating unit having at least one group selected from a lactone group, a sultone group, a carbonate group, a hydroxyl group, a cyano group, and an alkali-soluble group) The resin (A) may have a repeating unit having at least one group selected from a lactone group, a sultone group, a carbonate group, a hydroxyl group, a cyano group, and an alkali-soluble group. Examples of the repeating unit having a lactone group, a sultone group, or a carbonate group contained in the resin (A) include the repeating units described above in <Repeating unit having a lactone group, a sultone group, or a carbonate group>. The preferred content is also as described above in <Repeating unit having a lactone group, a sultone group, or a carbonate group>.

[0189] The resin (A) may have a repeating unit having a hydroxyl group or a cyano group. This improves substrate adhesion and developer affinity. The repeating unit having a hydroxyl group or a cyano group is preferably a repeating unit having an alicyclic hydrocarbon structure substituted with a hydroxyl group or a cyano group. The repeating unit having a hydroxyl group or a cyano group preferably does not have an acid-decomposable group. Examples of repeating units having a hydroxyl group or a cyano group include those described in paragraphs

[0081] to

[0084] of JP 2014-098921 A.

[0190] The resin (A) may have a repeating unit having an alkali-soluble group. Examples of the alkali-soluble group include a carboxyl group, a sulfonamide group, a sulfonylimide group, a bissulfonylimide group, and an aliphatic alcohol group (e.g., a hexafluoroisopropanol group) substituted at the α-position with an electron-withdrawing group, with a carboxyl group being preferred. When the resin (A) contains a repeating unit having an alkali-soluble group, the resolution in contact hole applications is improved. Examples of repeating units having an alkali-soluble group include those described in paragraphs

[0085] and

[0086] of JP 2014-098921 A.

[0191] (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.

[0192] (Repeating Unit Represented by Formula (III) Having Neither a Hydroxyl Group nor a Cyano Group) The resin (A) may have a repeating unit represented by formula (III) having neither a hydroxyl group nor a cyano group.

[0193]

[0194] In formula (III), R ５ represents a hydrocarbon group having at least one cyclic structure and having neither a hydroxyl group nor a cyano group. Ra represents a hydrogen atom, an alkyl group, or a —CH ２ -O-Ra ２ represents a group. ２ represents a hydrogen atom, an alkyl group, or an acyl group. Examples of the repeating unit represented by formula (III) that does not have either a hydroxyl group or a cyano group include those described in paragraphs

[0087] to

[0094] of JP 2014-098921 A.

[0195] Resin (A) can be synthesized according to a conventional method (e.g., radical polymerization). The weight average molecular weight (Mw) of resin (A), as measured by GPC in terms of polystyrene, is preferably 30,000 or less, more preferably 1,000 to 30,000, even more preferably 3,000 to 30,000, and particularly preferably 5,000 to 15,000. The dispersity (molecular weight distribution, Mw / Mn) of resin (A) is preferably 1 to 5, more preferably 1 to 3, even more preferably 1.2 to 3.0, and particularly preferably 1.2 to 2.0. The smaller the dispersity, the better the resolution and resist shape, and furthermore, the smoother the sidewalls of the resist pattern and the better the roughness.

[0196] The content of resin (A) in the composition of the present invention is preferably 0 to 20 mass %, more preferably 0 to 10 mass %, and even more preferably 0 mass % relative to the total solid content of the composition of the present invention (it is even more preferable that the composition of the present invention does not contain resin (A)). Resin (A) may be used alone or in combination of two or more types. When two or more types are used, it is preferable that the total content thereof is within the above-mentioned preferred content range.

[0197] [Compound (B) that generates an acid upon irradiation with actinic rays or radiation] The composition of the present invention may contain a compound (B) that generates an acid upon irradiation with actinic rays or radiation and is different from the resin (X). The compound (B) is a compound that does not have the repeating unit (u1) described above. The compound (B) is preferably in the form of a low molecular weight compound. The molecular weight of the compound (B) is preferably 5,000 or less, more preferably 4,000 or less, and even more preferably 3,000 or less. There is no particular lower limit for the molecular weight of the compound (B), but it is preferably 100 or more.

[0198] 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.), carbonylsulfonylimide acids, bis(alkylsulfonyl)imide acids, and tris(alkylsulfonyl)methide acids.

[0199] "M ＋ X － In the compound represented by the formula ", M ＋ represents a cation, and preferably represents an organic cation. ＋ Specific examples and preferred ranges of are the same as the specific examples and preferred ranges of the cation contained in the repeating unit (u1) described above.

[0200] "M ＋ X － In the compound represented by the formula "X － represents an anion, preferably an organic anion. The organic anion is not particularly limited, and examples thereof include monovalent or divalent or higher organic anions. The organic anion is preferably an anion having a significantly low ability to cause a nucleophilic reaction, and more preferably a non-nucleophilic anion.

[0201] 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.

[0202] 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).

[0203] 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.

[0204] 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).

[0205] 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.

[0206] An example of the sulfonylimide anion is a saccharin anion.

[0207] 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.

[0208] 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.

[0209] The non-nucleophilic anion is also preferably an anion represented by the following formula (AN1).

[0210]

[0211] In formula (AN1), R １ 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.

[0212] 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.

[0213] 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 ２ Examples 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.

[0214] As L, for example, a group represented by the following formula (AN1-1) is preferable: ａ - (CR２ａ ２ ) Ｘ -Q-(CR ２ｂ ２ ) Ｙ -* ｂ (AN1-1)

[0215] 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.

[0216] 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).

[0217] 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 (LC1-21) and the structures represented by the above-mentioned formulae (SL1-1) to (SL1-3) is preferred.

[0218] 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.

[0219] The non-nucleophilic anion is also preferably an anion represented by the following formula (AN2).

[0220]

[0221] 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.

[0222] 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.

[0223] 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 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.

[0224] L represents a divalent linking group, and is defined the same as L in formula (AN1).

[0225] 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.

[0226] 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.

[0227] 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.

[0228] 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.

[0229] The non-nucleophilic anion is also preferably an aromatic sulfonate anion represented by the following formula (AN3).

[0230]

[0231] 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.

[0232] 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.

[0233] B represents a hydrocarbon group. B is preferably an aliphatic hydrocarbon group, and more preferably an isopropyl group, a cyclohexyl group, or an aryl group which may further have a substituent (such as a tricyclohexylphenyl group).

[0234] 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.

[0235] It is also preferable that the compound (B) is at least one selected from the group consisting of the compounds (I) to (II).

[0236] (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:

[0237] 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.

[0238] 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 following structure." More specifically, when the acid dissociation constant of the compound PI is calculated, the acid dissociation constant a1 and the acid dissociation constant a2 of the compound PI correspond to "a compound having the following structure." 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.

[0239] 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 described above. 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.

[0240] 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 an 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.

[0241] 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.

[0242] 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.

[0243] 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.

[0244] 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.

[0245]

[0246]

[0247] 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 the organic cation include those represented by the following formula:

[0248] (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

[0249] In compound (II), the definition of the structural moiety X and A １ － and M １ ＋ The definition of the structural moiety X in the compound (I) and the definition of A １ － and M １ ＋ The definition and preferred embodiments are also the same.

[0250] 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.

[0251] The acid dissociation constant a1 is determined by the above-mentioned method for measuring an acid dissociation constant. The compound PII corresponds to the acid generated when the 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.

[0252] 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:

[0253]

[0254] 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.

[0255] Examples of moieties other than cations that Compound (I) and Compound (II) may have are shown below.

[0256]

[0257]

[0258] Specific examples of compound (B) include the compounds described in paragraphs

[0320] to

[0321] of WO 2022 / 172715. The above descriptions are incorporated herein by reference.

[0259] The content of compound (B) in the composition of the present invention is preferably 0 to 20 mass %, more preferably 0 to 10 mass %, and even more preferably 0 mass % relative to the total solid content of the composition of the present invention (it is even more preferable that the composition of the present invention does not contain compound (B)). Compound (B) 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.

[0260] [Acid Diffusion Controller] The composition of the present invention may contain an acid diffusion controller. 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) that is a weaker acid relative to the photoacid generator, and a basic compound (DE) whose basicity is reduced or eliminated by irradiation with actinic rays or radiation. 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. Specific examples of low molecular weight compounds (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 photoacid generator include those described in paragraphs

[0305] to

[0314] of WO 2020 / 158337.

[0261] 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.

[0262] The content of the acid diffusion controller in the composition of the present invention is preferably 0 to 20% by mass, more preferably 0 to 10% by mass, based on the total solid content of the composition of the present invention. The acid diffusion controller may be used alone, or two or more types may be used. When two or more types are used, the total content thereof preferably falls within the above-mentioned preferred content range.

[0263] [Hydrophobic Resin] The composition of the present invention may contain a hydrophobic resin (also referred to as "hydrophobic resin (D)") different from resin (X) and resin (A). The hydrophobic resin (D) 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 polar and non-polar substances. Effects of adding hydrophobic resin (D) include control of the static and dynamic contact angles of water on the resist film surface and suppression of outgassing.

[0264] The hydrophobic resin (D) 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 the hydrophobic resin (D) include the compounds described in paragraphs

[0275] to

[0279] of WO 2020 / 004306.

[0265] The content of the hydrophobic resin (D) in the composition of the present invention is preferably 0 to 20 mass %, more preferably 0 to 10 mass %, and even more preferably 0 mass % relative to the total solid content of the composition of the present invention (it is even more preferable that the composition of the present invention does not contain a hydrophobic resin (D)). The hydrophobic resin (D) may be used alone or in combination of two or more. When two or more types are used, it is preferable that the total content thereof is within the above-mentioned preferred content range.

[0266] [Surfactant] The composition of the present invention may contain a surfactant. When a surfactant is contained, a pattern with better adhesion and fewer development defects can be formed. The surfactant is a compound different from the resin (X). 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.

[0267] The content of the surfactant in the composition of the present invention is preferably 0 to 5 mass %, more preferably 0 to 1 mass %, and even more preferably 0 mass % relative to the total solid content of the composition of the present invention (it is even more preferable that the composition of the present invention does not contain a surfactant). One type of surfactant 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 preferred content range.

[0268] [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).

[0269] Combining the above-mentioned solvent with the above-mentioned resin is preferable in terms of improving the coatability of the composition of the present invention and reducing the number of development defects in the pattern. The above-mentioned solvent has a good balance of the solubility, boiling point, and viscosity of the above-mentioned resin, and therefore can suppress unevenness in the film thickness of the resist film and the occurrence of precipitates during spin coating. Details of component (M1) and component (M2) are described in paragraphs

[0218] to

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

[0270] 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.

[0271] The content of the solvent in the composition of the present invention is preferably determined so that the solids concentration is 0.5 to 30% by mass, more preferably 1 to 20% by mass, which further improves the coatability of the composition of the present invention.

[0272] [Other Additives] The composition of the present invention may further contain a dissolution inhibiting compound, a dye, a plasticizer, a photosensitizer, a light absorber, and / or a compound that promotes solubility in a developer (for example, a phenol compound having a molecular weight of 1,000 or less, or an alicyclic or aliphatic compound containing a carboxyl group).

[0273] The "dissolution inhibiting compound" is a compound having a molecular weight of 3,000 or less, which is decomposed by the action of an acid and has a reduced solubility in an organic developer.

[0274] The composition of the present invention is also suitable as a photosensitive composition for EUV exposure.

[0275] <Actinic ray- or radiation-sensitive film, pattern forming method> The present invention also relates to an actinic ray- or radiation-sensitive film formed from the composition of the present invention. The actinic ray- or radiation-sensitive film of the present invention is preferably a resist film. The procedure of the pattern forming method using the composition of the present invention is not particularly limited, but preferably includes the following steps: Step 1: forming a resist film on a substrate using the composition of the present invention; Step 2: exposing the resist film; Step 3: developing the exposed resist film using a developer. The procedure of each of the above steps will be described in detail below.

[0276] (Step 1: Resist Film Forming Step) Step 1 is a step of forming a resist film on a substrate using the composition of the present invention.

[0277] A method for forming a resist film on a substrate using the composition of the present invention includes, for example, applying the composition of the present invention to a substrate. It is preferable to filter the composition of the present invention before application, if necessary. The pore size of the filter is preferably 0.1 μm or less, more preferably 0.05 μm or less, and even more preferably 0.03 μm or less. The filter is preferably made of polytetrafluoroethylene, polyethylene, or nylon.

[0278] The composition of the present invention can be applied onto a substrate (e.g., silicon, silicon coated with silicon dioxide) such as those used in the manufacture of integrated circuit elements by an appropriate application method such as a spinner or coater. Spin application using a spinner is preferred. The rotation speed during spin application using a spinner is preferably 1,000 to 3,000 rpm (rotations per minute). After application of the composition of the present invention, the substrate may be dried to form a resist film. If necessary, various underlayer films (inorganic film, organic film, anti-reflective film) may be formed below the resist film.

[0279] An example of a drying method is a method of drying by heating. Heating can be performed by means provided in a normal exposure machine and / or developing machine, and may also be performed using a hot plate or the like. The heating temperature is preferably 80 to 150°C, more preferably 80 to 140°C, and even more preferably 80 to 130°C. The heating time is preferably 30 to 1,000 seconds, more preferably 60 to 800 seconds, and even more preferably 60 to 600 seconds.

[0280] The thickness of the resist film is not particularly limited, but is preferably 10 to 120 nm from the viewpoint of forming a finer pattern with higher precision. In particular, when EUV exposure is used, the thickness of the resist film is more preferably 10 to 65 nm, and even more preferably 15 to 50 nm. When ArF immersion exposure is used, the thickness of the resist film is more preferably 10 to 120 nm, and even more preferably 15 to 90 nm.

[0281] A top coat may be formed on the resist film using a top coat composition. It is preferable that the top coat composition does not mix with the resist film and can be uniformly applied to the resist film. The top coat is not particularly limited, and a conventionally known top coat can be formed by a conventionally known method. For example, a top coat can be formed based on the description in paragraphs

[0072] to

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

[0282] (Step 2: Exposure Step) Step 2 is a step of exposing the resist film to light. Examples of exposure methods include irradiating the formed resist film with actinic rays or radiation through a predetermined mask. Examples of actinic rays or radiation include infrared rays, visible rays, ultraviolet rays, far ultraviolet rays, extreme ultraviolet rays, X-rays, and electron beams. The wavelength of the actinic rays or radiation is preferably 250 nm or less, more preferably 220 nm or less, and particularly preferably 1 to 200 nm. Specific examples of preferred actinic rays or radiation include KrF excimer laser (248 nm), ArF excimer laser (193 nm), and F ２ These are excimer laser (157 nm), EUV (13.5 nm), X-rays, and electron beams.

[0283] After exposure, it is preferable to bake (heat) the film before developing. Baking promotes the reaction of the exposed areas, resulting in better sensitivity and pattern shape. The heating temperature is preferably 80 to 150°C, more preferably 80 to 140°C, and even more preferably 80 to 130°C. The heating time is preferably 10 to 1,000 seconds, more preferably 10 to 180 seconds, and even more preferably 30 to 120 seconds. Heating can be performed using means provided in a typical exposure machine and / or development machine, and may also be performed using a hot plate or the like. This process is also called post-exposure baking.

[0284] (Step 3: Development Step) Step 3 is a step of developing the exposed resist film with a developer to form a pattern. The developer may be an alkaline developer or a developer containing an organic solvent (hereinafter also referred to as an organic developer).

[0285] Examples of development methods include a method in which a substrate is immersed in a tank filled with a developer for a certain period of time (dip method), a method in which a developer is piled up on the surface of a substrate by surface tension and left to stand for a certain period of time for development (puddle method), a method in which a developer is sprayed onto the surface of the substrate (spray method), and a method in which a developer is continuously dispensed onto a substrate rotating at a constant speed while a developer dispense nozzle is scanned at a constant speed (dynamic dispense method). Furthermore, after the development step, a step of stopping development while replacing the solvent with another solvent may be carried out. The development time is not particularly limited as long as it is long enough to sufficiently dissolve the resin in the unexposed areas, and is preferably 10 to 300 seconds, more preferably 20 to 120 seconds. The temperature of the developer is preferably 0 to 50°C, more preferably 15 to 35°C.

[0286] 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.

[0287] 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.

[0288] The above-mentioned solvents may be mixed in plural, or may be mixed with a solvent other than the above or water. The water content of the developer as a whole is preferably less than 50% by mass, more preferably less than 20% by mass, even more preferably less than 10% by mass, and particularly preferably substantially free of water. The content of the organic solvent in the organic developer is preferably 50% by mass or more and 100% by mass or less, more preferably 80% by mass or more and 100% by mass or less, even more preferably 90% by mass or more and 100% by mass or less, and particularly preferably 95% by mass or more and 100% by mass or less, based on the total amount of the developer.

[0289] (Other Steps) The pattern formation method preferably includes, after step 3, a step of cleaning with a rinse liquid.

[0290] The rinse liquid used in the rinse step after the development step using an alkaline developer can be, for example, pure water. A suitable amount of surfactant may be added to the pure water. A suitable amount of surfactant may be added to the rinse liquid.

[0291] The rinse liquid used in the rinse step after the development step using an organic developer is not particularly limited as long as it does not dissolve the pattern, and a solution containing a general organic solvent can be used. The rinse liquid is preferably a rinse liquid containing at least one organic solvent selected from the group consisting of hydrocarbon solvents, ketone solvents, ester solvents, alcohol solvents, amide solvents, and ether solvents.

[0292] The method for the rinsing step is not particularly limited, and examples include a method in which a rinsing solution is continuously discharged onto a substrate rotating at a constant speed (spin coating method), a method in which a substrate is immersed in a tank filled with the rinsing solution for a certain period of time (dipping method), and a method in which the rinsing solution is sprayed onto the substrate surface (spray method). The pattern formation method may also include a heating step (post-bake) after the rinsing step. This step removes the developer and rinsing solution remaining between and within the pattern by baking. This step also has the effect of annealing the resist pattern and improving the surface roughness of the pattern. The heating step after the rinsing step is typically performed at 40 to 250°C (preferably 90 to 200°C) for typically 10 seconds to 3 minutes (preferably 30 to 120 seconds).

[0293] Alternatively, the substrate may be etched using the formed pattern as a mask. That is, the substrate (or the underlayer film and the substrate) may be processed using the pattern formed in step 3 as a mask to form a pattern on the substrate. The method for processing the substrate (or the underlayer film and the substrate) is not particularly limited, but a method of forming a pattern on the substrate by dry etching the substrate (or the underlayer film and the substrate) using the pattern formed in step 3 as a mask is preferred. The dry etching is preferably oxygen plasma etching.

[0294] (Preferred embodiment of pattern forming method) The pattern forming method using the composition of the present invention preferably includes the following steps: Step A: forming a resist film on a substrate using the composition of the present invention; Step B: irradiating the resist film with a first actinic ray or radiation; Step C: irradiating the resist film after the irradiation with the first actinic ray or radiation with a second actinic ray or radiation; and Step D: developing the resist film after the irradiation with the second actinic ray or radiation using a developer.

[0295] (Step A: Resist Film Forming Step) Step A is a step of forming a resist film on a substrate using the composition of the present invention. Step A is the same as step 1 described above.

[0296] (Step B: First Exposure Step) Step B is a step of irradiating the resist film with first actinic rays or radiation. 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 (first actinic rays or radiation) used in step B include infrared rays, visible rays, ultraviolet rays, far ultraviolet rays, extreme ultraviolet rays, X-rays, and electron beams. The wavelength of the first actinic rays or radiation is preferably shorter than the wavelength of the second actinic rays or radiation. The wavelength of the first actinic rays or radiation is preferably 250 nm or less, more preferably 220 nm or less, and even more preferably 1 to 200 nm. Specific examples of the first actinic rays or radiation include KrF excimer laser (248 nm), ArF excimer laser (193 nm), F ２ Excimer laser (157 nm), extreme ultraviolet light (13.5 nm), X-rays or electron beams are preferred, and electron beams or extreme ultraviolet light are more preferred.

[0297] After exposure, it is preferable to bake (heat) the film before developing. Baking promotes the reaction of the exposed areas, resulting in better sensitivity and pattern shape. The heating temperature is preferably 23 to 130°C, more preferably 23 to 110°C, and even more preferably 23 to 90°C. The heating time is preferably 10 to 1,000 seconds, more preferably 10 to 180 seconds, and even more preferably 30 to 120 seconds. Heating can be performed using means provided in a typical exposure machine and / or development machine, and may also be performed using a hot plate or the like. This process is also called post-exposure baking.

[0298] (Step C: Second Exposure Step) Step C is a step of irradiating the resist film after irradiation with the first actinic ray or radiation with a second actinic ray or radiation. Examples of the exposure method include a method of irradiating the entire surface of the resist film after irradiation with the first actinic ray or radiation with actinic ray or radiation. Examples of the actinic ray or radiation (second actinic ray or radiation) used in Step C include infrared light, visible light, ultraviolet light, and far ultraviolet light, and ultraviolet light is preferred. The wavelength of the second actinic ray or radiation is preferably 350 nm to 450 nm.

[0299] After exposure, it is preferable to bake (heat) the film before developing. Baking promotes the reaction of the exposed areas, resulting in better sensitivity and pattern shape. The heating temperature is preferably 70 to 150°C, more preferably 70 to 140°C, and even more preferably 70 to 130°C. The heating time is preferably 10 to 1,000 seconds, more preferably 10 to 180 seconds, and even more preferably 30 to 120 seconds. Heating can be carried out using means provided in a normal exposure machine and / or development machine, and may also be carried out using a hot plate or the like. This process is also called post-exposure baking.

[0300] (Step D: Development Step) Step D is a step of developing the resist film after irradiation with the second actinic ray or radiation using a developer. By performing Step D, a pattern is formed. Step D is the same as Step 3 described above.

[0301] The composition of the present invention and various materials used in the pattern formation method (e.g., solvents, developers, rinse solutions, anti-reflective coating compositions, top coat compositions, etc.) preferably do not contain impurities such as metals. The content of impurities contained in these materials is preferably 1 mass ppm (parts per million) or less, more preferably 10 mass ppb (parts per billion) or less, even more preferably 100 mass ppt or less, particularly preferably 10 mass ppt or less, and most preferably 1 mass ppt or less. There is no particular lower limit, and 0 mass ppt or more is preferred. Here, examples of metal impurities include Na, K, Ca, Fe, Cu, Mg, Al, Li, Cr, Ni, Sn, Ag, As, Au, Ba, Cd, Co, Pb, Ti, V, W, and Zn.

[0302] 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.

[0303] 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).

[0304] In addition to filter filtration, impurities may be removed using an adsorbent, or a combination of filter filtration and an adsorbent may be used. Known adsorbents can be used as the adsorbent, including inorganic adsorbents such as silica gel and zeolite, and organic adsorbents such as activated carbon. In order to reduce impurities such as metals contained in the various materials, it is necessary to prevent the incorporation of metal impurities during the manufacturing process. Whether metal impurities have been sufficiently removed from the manufacturing equipment can be confirmed by measuring the content of metal components contained in the cleaning solution used to clean the manufacturing equipment. The content of metal components contained in the used cleaning solution is preferably 100 parts per trillion (ppt) by mass or less, more preferably 10 ppt by mass or less, and even more preferably 1 ppt by mass or less. There is no particular lower limit, and 0 ppt by mass or more is preferred.

[0305] A conductive compound may be added to an organic processing liquid such as a rinse solution to prevent breakdown of the chemical solution piping and various parts (filters, O-rings, tubes, etc.) due to static charging and subsequent electrostatic discharge. The conductive compound is not particularly limited, but examples include methanol. The amount added is not particularly limited, but in order to maintain favorable development or rinsing characteristics, it is preferably 10% by mass or less, more preferably 5% by mass or less. There is no particular lower limit, but 0.01% by mass or more is preferred. For the chemical solution piping, for example, stainless steel (SUS), or various piping coated with antistatically treated polyethylene, polypropylene, or fluororesin (such as polytetrafluoroethylene or perfluoroalkoxy resin), can be used. Similarly, for the filters and O-rings, antistatically treated polyethylene, polypropylene, or fluororesin (such as polytetrafluoroethylene or perfluoroalkoxy resin), can be used.

[0306] <Method for manufacturing an electronic device> The present invention also relates to a method for manufacturing an electronic device, including the above-mentioned pattern formation method, and an electronic device manufactured by this manufacturing method. A preferred embodiment of the electronic device of the present invention is one that is installed in electrical and electronic equipment (such as home appliances, office automation (OA), media-related equipment, optical equipment, and communication equipment).

[0307] The present invention will be described in more detail below with reference to the following examples. The materials, amounts used, ratios, treatment details, and treatment procedures shown in the following examples can be appropriately changed without departing from the spirit of the present invention. Therefore, the scope of the present invention should not be construed as being limited by the following examples.

[0308] The various components used in the resist compositions of the examples and comparative examples are shown below.

[0309] <Resin (X)> X-1 to X-37 were used as resin (X). The structural formula of each resin (structural formula of the repeating unit contained in each resin) is shown below.

[0310]

[0311]

[0312]

[0313]

[0314]

[0315]

[0316]

[0317]

[0318] For each resin, the content (mass %; corresponding from left to right) of each repeating unit relative to the total repeating units contained, the weight average molecular weight (Mw), the dispersity (Mw / Mn), and the pKa of the acid generated from the repeating unit (u1) are shown in Table 1 below. The weight average molecular weight (Mw) and the dispersity (Mw / Mn) were measured by the above-mentioned method. The content of each repeating unit is １３Measurement was performed by C-NMR (Nuclear Magnetic Resonance).

[0319]

[0320] A synthesis example of resin (X) is shown below.

[0321] (Synthesis Example 1: Synthesis of X-1) <Synthesis of X-1-A>

[0322]

[0323] X-1-1 (15.0 g), X-1-2 (39.4 g), and cesium carbonate (60.3 g) were dissolved in acetonitrile (330 g) and stirred at room temperature (23°C) for 1 hour. Ethyl acetate (400 mL) was added to the resulting mixture, and the mixture was washed three times with water (300 mL). The organic solvent was then distilled off to obtain X-1-3. X-1-3 and sodium iodide (20.3 g) were dissolved in acetonitrile (470 g) and stirred at 60°C for 1 hour. The resulting mixture was cooled to room temperature and filtered to obtain X-1-4. X-1-4 and X-1-5 (54.6 g) were dissolved in methylene chloride (200 mL), and water (200 mL) was added. After stirring for 1 hour, the aqueous layer was removed, and the organic layer was washed with 0.1 mol / L hydrochloric acid (200 mL) and water (200 mL). The solvent was distilled off to obtain X-1-A (70.2 g) (yield 92%).

[0324] <Synthesis of X-1> Cyclohexanone (8 g) was heated to 80°C under a nitrogen stream. While stirring this liquid, a mixed solution of X-1-A (10 g), cyclohexanone (32 g), and dimethyl 2,2'-azobisisobutyrate [V-601, manufactured by Fujifilm Wako Pure Chemical Industries, Ltd.] (0.5 g) was added dropwise over 6 hours to obtain a reaction liquid. After completion of the dropwise addition, the reaction liquid was stirred at 80°C for an additional 2 hours. The obtained reaction liquid was allowed to cool and then reprecipitated with a large amount of ethyl acetate / heptane (mass ratio 6 / 4), followed by filtration. The obtained solid was dried in vacuo to obtain 6.2 g of X-1.

[0325] Other resins (X) were synthesized in the same manner as above.

[0326] <Resin (A)> Resins A-1 to A-5 were used as resins (A) (resins whose polarity increases under the action of an acid and which are not resins (X)). The structural formula of each resin (structural formula of the repeating unit contained in each resin) is shown below.

[0327]

[0328] For each resin, the content (mol %; corresponding from left to right) of each repeating unit relative to the total repeating units contained, the weight average molecular weight (Mw), and the dispersity (Mw / Mn) are shown in Table 2 below. The weight average molecular weight (Mw) and the dispersity (Mw / Mn) were measured by the above-mentioned method. The content of each repeating unit is １３ Measurement was performed by C-NMR.

[0329]

[0330] <Compound (B)> As the compound (B) (a compound which is a photoacid generator and is not a resin (X)), B-1 to B-6 were used.

[0331]

[0332] <Acid Diffusion Controller> As the acid diffusion controller, C-1 to C-12 were used.

[0333]

[0334] <Hydrophobic Resin> D-1 to D-6 were used as hydrophobic resins. Table 3 below shows the type and content (mol %) of each repeating unit contained in each resin, as well as the weight average molecular weight (Mw) and dispersity (Mw / Mn). The content of a repeating unit is the ratio (molar ratio) of each repeating unit to all repeating units contained in each resin. The type of each repeating unit is shown by the structure of the corresponding monomer. The weight average molecular weight (Mw) and dispersity (Mw / Mn) were measured by the method described above. The content of each repeating unit is １３ Measurement was performed by C-NMR.

[0335]

[0336] The structural formulae of the monomers ME-1 to ME-13 corresponding to the repeating units constituting the hydrophobic resins shown in Table 3 are shown below.

[0337]

[0338] <Surfactant> E-1 to E-3 were used as surfactants. E-1: Megafac F176 (manufactured by DIC Corporation, fluorochemical surfactant) E-2: Megafac R08 (manufactured by DIC Corporation, fluorine and silicon surfactant) E-3: PF656 (manufactured by OMNOVA, fluorochemical surfactant)

[0339] <Solvents> The solvents used are as follows: F-1: Propylene glycol monomethyl ether acetate (PGMEA) F-2: Propylene glycol monomethyl ether (PGME) F-3: Propylene glycol monoethyl ether (PGEE) F-4: Cyclohexanone F-5: Cyclopentanone F-6: 2-heptanone F-7: Ethyl lactate F-8: γ-butyrolactone F-9: Propylene carbonate

[0340] <Preparation of Resist Composition> The components shown in Tables 4 and 5 were mixed to a solids concentration of 2% by mass. The resulting mixture was then filtered, in this order, first through a polyethylene filter with a pore size of 50 nm, then through a nylon filter with a pore size of 10 nm, and finally through a polyethylene filter with a pore size of 5 nm, to prepare a resist composition. In the resist composition, the solids refer to all components other than the solvent. The resulting resist composition was used in the examples and comparative examples. In Tables 4 and 5, the content (mass %) of each component other than the solvent indicates the content (mass %) of each component relative to the total solids in the resist composition. Tables 4 and 5 also show the mixing ratios (mass ratios) of the solvents used. Tables 4 and 5 also show the content (mass %) of the repeating unit (u1) relative to the total amount of resin contained in each resist composition. In Tables 4 and 5, "C ｕ１ " is the content (% by mass) of the repeating unit (u1) relative to the total amount of resin contained in each resist composition. The "resins" contained in the resist compositions of the Examples and Comparative Examples are resin (X), resin (A), a hydrophobic resin, and a surfactant.

[0341]

[0342]

[0343] Examples 1-1 to 1-48, Comparative Examples 1-1 to 1-2: EUV Exposure, Alkali Development An underlayer film-forming composition AL412 (manufactured by Brewer Science) was applied to a silicon wafer and baked at 205°C for 60 seconds to form an underlayer film with a thickness of 20 nm. A resist composition shown in Table 6 was applied to the underlayer film and baked at 100°C for 60 seconds to form a resist film with a thickness of 30 nm. Using an EUV exposure system (manufactured by Exitech, Micro Exposure Tool, NA 0.3, Quadrupol, outer sigma 0.68, inner sigma 0.36), the silicon wafer having the resulting resist film was subjected to pattern exposure. A mask with a line size (line width) of 16 nm and a line:space ratio of 1:1 was used as the reticle. The exposed resist film was baked at 90° C. for 60 seconds, developed with an aqueous solution of tetramethylammonium hydroxide (2.38% by mass) for 30 seconds, rinsed with pure water for 30 seconds, and then spin-dried to obtain a positive pattern.

[0344] Examples 2-1 to 2-48, Comparative Examples 2-1 to 2-2: EUV Exposure, Organic Solvent Development An underlayer film-forming composition AL412 (manufactured by Brewer Science) was applied to a silicon wafer and baked at 205°C for 60 seconds to form an underlayer film with a thickness of 20 nm. A resist composition shown in Table 7 was applied to the underlayer film and baked at 100°C for 60 seconds to form a resist film with a thickness of 30 nm. Using an EUV exposure system (manufactured by Exitech, Micro Exposure Tool, NA 0.3, Quadrupol, outer sigma 0.68, inner sigma 0.36), the silicon wafer having the resulting resist film was subjected to pattern exposure. A mask with a line size of 16 nm and a line:space ratio of 1:1 was used as the reticle. The exposed resist film was baked at 90° C. for 60 seconds, developed with n-butyl acetate for 30 seconds, and then spin-dried to obtain a negative pattern.

[0345] <Evaluation of Defects> The patterns obtained by the above method were counted for the number of defects per silicon wafer using UVision 5 (manufactured by AMAT Corporation) and SEMVision G4 (manufactured by AMAT Corporation), and evaluated according to the following evaluation criteria. The fewer the number of defects, the better. A: Number of defects 50 or less B: Number of defects over 50 and 100 or less C: Number of defects over 100 and 200 or less D: Number of defects over 200 and 300 or less E: Number of defects over 300 and 400 or less F: Number of defects over 400

[0346] <Evaluation of Resolution> Using the above-described resist pattern formation method, the optimum exposure dose Eop (mJ / cm) at which a line and space pattern (L / S pattern) with a target size of line:space=1:1 is formed is determined. ２ ) was determined. The limiting resolution at this Eop, specifically, the minimum dimension of the pattern that could be resolved without collapsing when an L / S pattern was formed by gradually increasing the exposure dose from the optimum exposure dose Eop, was determined using a critical dimension scanning electron microscope (SEM (S-9380II, manufactured by Hitachi, Ltd.)). This was defined as the "limiting resolution (nm)." The smaller the value of the limiting resolution, the better the resolution. The limiting resolution (nm) is preferably 15.0 nm or less, more preferably 14.0 nm or less, even more preferably 13.0 nm or less, and particularly preferably 12.0 nm or less.

[0347] The results are shown in Tables 6 and 7.

[0348]

[0349]

[0350] The results in Tables 6 and 7 show that the resist compositions used in the examples are excellent in resolution and can reduce defects.

[0351] The present invention provides an actinic ray-sensitive or radiation-sensitive resin composition that is excellent in resolution and can reduce defects. The present invention also provides a resist film, a pattern forming method, and a method for manufacturing an electronic device that use the actinic ray-sensitive or radiation-sensitive resin composition.

[0352] Although the present invention has been described in detail and with reference to specific embodiments, it will be apparent to those skilled in the art that various changes and modifications can be made without departing from the spirit and scope of the present invention. This application is based on a Japanese patent application (Patent Application No. 2023-170254) filed on September 29, 2023, the contents of which are incorporated herein by reference.

Claims

1. An actinic ray-sensitive or radiation-sensitive resin composition comprising a solvent and a resin (X) having a repeating unit (u1) that generates an acid upon exposure to actinic rays or radiation, wherein the repeating unit (u1) contains a cation and an anion bonded to a molecular chain of the resin (X), and the content of the repeating unit (u1) is 80 mass% or more relative to the total amount of resin contained in the actinic ray-sensitive or radiation-sensitive resin composition.

2. The actinic ray-sensitive or radiation-sensitive resin composition according to claim 1, wherein the content of the repeating unit (u1) is 90 mass% or more based on the total amount of resin contained in the actinic ray-sensitive or radiation-sensitive resin composition.

3. The actinic ray-sensitive or radiation-sensitive resin composition according to claim 1, wherein the content of the repeating unit (u1) is 95 mass% or more based on the total amount of resin contained in the actinic ray-sensitive or radiation-sensitive resin composition.

4. The actinic ray-sensitive or radiation-sensitive resin composition according to claim 1, wherein the repeating unit (u1) generates an acid having a pKa of 2.0 or less.

5. The actinic ray-sensitive or radiation-sensitive resin composition according to claim 1, wherein the acid generated from the repeating unit (u1) is a sulfonic acid.

6. The actinic ray-sensitive or radiation-sensitive resin composition according to claim 1, wherein the repeating unit (u1) is represented by the following formula (UA1): In formula (UA1), R ａ１ , R ａ２ and R ａ３ each independently represents a hydrogen atom, an alkyl group, a cycloalkyl group, a halogen atom, a cyano group, or an alkoxycarbonyl group. ａ１ represents a single bond or a divalent linking group. １ － represents an anion. ＋ represents a cation.

7. The actinic ray-sensitive or radiation-sensitive resin composition according to claim 1, wherein the repeating unit (u1) is represented by the following formula (UA2): In formula (UA2), R ａ１ , R ａ２ and R ａ３ each independently represents a hydrogen atom, an alkyl group, a cycloalkyl group, a halogen atom, a cyano group, or an alkoxycarbonyl group. ａ２ represents a single bond or a divalent linking group. １ represents an aromatic group. ａ４ represents a substituent other than a fluorine atom. k1 represents an integer of 1 or more. k2 represents an integer of 0 or more. E １ － represents an anion. ＋ represents a cation.

8. The actinic ray-sensitive or radiation-sensitive resin composition according to claim 1, wherein the repeating unit (u1) is represented by the following formula (UA3): In formula (UA3), R ａ１ , R ａ２ and R ａ３ each independently represents a hydrogen atom, an alkyl group, a cycloalkyl group, a halogen atom, a cyano group, or an alkoxycarbonyl group. ａ２ represents a single bond or a divalent linking group. ＋ represents a cation.

9. The actinic ray-sensitive or radiation-sensitive resin composition according to claim 1, wherein the cation is at least one selected from the group consisting of a cation represented by the following formula (ZaI) and a cation represented by the following formula (ZaII): In the formula (ZaI), R ２０１ , R ２０２ and R ２０３ R each independently represents an organic group. ２０１ , R ２０２ and R ２０３ In formula (ZaII), at least two of R may be bonded to form a ring. ２０４ and R ２０５ R each independently represents an organic group. ２０４ and R ２０５ may be bonded to form a ring.

10. The actinic ray-sensitive or radiation-sensitive resin composition according to claim 1, wherein the content of the resin (X) is 60 to 100 mass % based on the total solid content in the actinic ray-sensitive or radiation-sensitive resin composition.

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

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

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

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