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

Abstract

Provided are an actinic-ray-sensitive or radiation-sensitive resin composition, an actinic-ray-sensitive or radiation-sensitive film using the actinic-ray-sensitive or radiation-sensitive resin composition, a pattern formation method, and a method for manufacturing an electronic device. The actinic-ray-sensitive or radiation-sensitive resin composition contains: a resin; a photoacid generator (C) having, in the molecule thereof, a nonionic acid generating moiety that decomposes upon irradiation with actinic rays or radiation to generate an acid, and a basic moiety; and an acid diffusion control agent (Q), wherein the content of the acid diffusion control agent (Q) is 7 mass% or more relative to the content of the photoacid generator (C).

Description

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

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

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

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

[0004] Patent Document 1 describes a chemically amplified positive-working photosensitive composition containing an acid generator that generates an acid when irradiated with actinic rays or radiation, a resin whose solubility in alkali increases due to the action of the acid, and an acid diffusion inhibitor that contains a compound having a specific structure.

[0005] Japanese Patent Application Publication No. 2021-107850

[0006] Recently, the performance requirements for resist compositions have become increasingly stringent. In particular, further improvements are being sought in resolution and line width roughness (LWR) performance when forming fine patterns. LWR performance refers to the ability to reduce the LWR of a pattern. Further improvements in the process margin of resist compositions are also expected. The process margin refers to the tolerance range (margin) within which a desired result can be obtained even if various conditions (e.g., heating temperature) in the pattern formation process using a resist composition vary. The wider this tolerance range, the better the process margin. In pattern formation using a resist composition, a resist film formed from the resist composition may be baked (heated) after exposure and before development. The process margin with respect to the baking temperature is also referred to as "bake temperature dependency." The smaller the bake temperature dependency, the smaller the change in performance with respect to changes in bake temperature, and the better the result.

[0007] Therefore, an object of the present invention is to provide an actinic ray-sensitive or radiation-sensitive resin composition and an actinic ray-sensitive or radiation-sensitive film that are excellent in resolution and LWR performance and have little bake temperature dependency during pattern formation, a pattern formation method using the actinic ray-sensitive or radiation-sensitive resin composition, and a method for manufacturing an electronic device.

[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 comprising: a resin; a photoacid generator (C) having, in its molecule, a nonionic acid-generating moiety that decomposes upon irradiation with actinic rays or radiation to generate an acid and a basic moiety; and an acid diffusion controller (Q), wherein the content of the acid diffusion controller (Q) is 7 mass% or more relative to the content of the photoacid generator (C). [2] The actinic ray-sensitive or radiation-sensitive resin composition according to [1], wherein the resin contains a repeating unit having a group that decomposes under the action of an acid to increase its polarity. [3] The actinic ray-sensitive or radiation-sensitive resin composition according to [1] or [2], wherein the resin contains a repeating unit having a phenolic hydroxyl group. [4] The actinic ray-sensitive or radiation-sensitive resin composition according to any one of [1] to [3], wherein the acid-generating moiety of the photoacid generator (C) contains a group represented by any of the following formulas (1) to (3):

[0010]

[0011] In formula (1), X １１ represents a hydrogen atom or a substituent. １１ represents an alkyl group, a cycloalkyl group, an aryl group, a heteroaryl group, an alkenyl group, a cycloalkenyl group, or an alkynyl group. １１ and R １１ may be bonded to form a ring. * represents the bonding position. In formula (2), X ２１ and X ２２ R each independently represents a hydrogen atom or a substituent. ２１ represents an alkyl group, a cycloalkyl group, an aryl group, a heteroaryl group, an alkenyl group, a cycloalkenyl group, or an alkynyl group. m represents 0 or 1. n represents 0 or 1. * represents a bonding position. X ２１ and X ２２ , X ２１ and R ２１ and X ２２ and R ２１ may be bonded to form a ring. ３１ and X ３２each independently represents a cyano group, an alkyl group, a cycloalkyl group, an acyl group, an alkoxycarbonyl group, an aryloxycarbonyl group, a heteroaryloxycarbonyl group, an aryl group, a heteroaryl group, an alkenyl group, a cycloalkenyl group, or an alkynyl group. ３１ and X ３２ may be bonded to form a ring. * represents a bonding position. [5] The actinic ray-sensitive or radiation-sensitive resin composition according to any one of [1] to [4], wherein the resin contains a repeating unit represented by the following formula (b-1):

[0012]

[0013] In formula (b-1), R ｂ１ and R ｂ２ each independently represents a hydrogen atom or an alkyl group. ｂ１ represents a single bond or -C(=O)O-. r represents an integer of 0 to 2. ｐ１ and R ｐ２ R each independently represents a group that is eliminated by the action of an acid. ｂ３ represents a halogen atom, an alkyl group, a cycloalkyl group, an alkoxy group, an aryloxy group, an alkylthio group, an arylthio group, an aryl group, a heteroaryl group, an ester group, a carboxyl group, or a group formed by combining two or more of these. s and t each independently represent an integer of 0 to 4, provided that at least one of s and t is an integer of 1 or greater. u represents an integer of 0 to (5+2r-s-t). R ｐ１ If there are multiple R ｐ１ may be the same or different and may be bonded to each other to form a ring. ｐ２ If there are multiple R ｐ２ may be the same or different and may be bonded to each other to form a ring. ｂ３ If there are multiple R ｂ３ may be the same or different and may be bonded to each other to form a ring. ｂ３ and R ｐ１ , R ｂ３ and R ｐ２ , and R ｐ１ and R ｐ２may be bonded to each other to form a ring. ｂ１ The aromatic ring to which R is bonded ｂ１ may be bonded to. [6] The actinic ray-sensitive or radiation-sensitive resin composition according to any one of [1] to [5], wherein the basic moiety of the photoacid generator (C) contains an ionic structure of a sulfonium salt or an iodonium salt. [7] The actinic ray-sensitive or radiation-sensitive resin composition according to any one of [1] to [6], wherein the pKa of the acid generated from the acid generation moiety of the photoacid generator (C) is -2.0 or more and less than 1.5. [8] The actinic ray-sensitive or radiation-sensitive resin composition according to any one of [1] to [7], wherein the acid generated from the acid generation moiety of the photoacid generator (C) is an arylsulfonic acid. [9] The actinic ray-sensitive or radiation-sensitive resin composition according to any one of [1] to [8], wherein the molecular weight of the acid generated from the acid generation moiety of the photoacid generator (C) is 250 or more.

[10] The actinic ray-sensitive or radiation-sensitive resin composition according to any one of [1] to [9], wherein the photoacid generator (C) is a compound represented by the following formula (4):

[0014]

[0015] In formula (4), X ４１ and X ４２ R each independently represents a hydrogen atom, an alkyl group, a cycloalkyl group, an aryl group, a heteroaryl group, an alkenyl group, a cycloalkenyl group, or an alkynyl group. ４１ represents an alkyl group, a cycloalkyl group, an aryl group, a heteroaryl group, an alkenyl group, a cycloalkenyl group, or an alkynyl group. ４２ represents a substituent. k represents an integer of 0 to 5. When k represents an integer of 2 or more, a plurality of R ４２ may be the same or different, and multiple R ４２ may be bonded to form a ring. ４１ , R ４２ , X ４１ and X ４２

[11] The actinic ray-sensitive or radiation-sensitive resin composition according to any one of [1] to

[10] , wherein the molecular weight of the acid generated from the acid-generating moiety of the photoacid generator (C) is 400 or more.

[12] An actinic ray-sensitive or radiation-sensitive film formed from the actinic ray-sensitive or radiation-sensitive resin composition according to any one of [1] to

[11] .

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

[11] ; exposing the actinic ray-sensitive or radiation-sensitive film; and developing the exposed actinic ray-sensitive or radiation-sensitive film with a developer.

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

[13] .

[0016] The present invention can provide an actinic ray-sensitive or radiation-sensitive resin composition and an actinic ray-sensitive or radiation-sensitive film that are excellent in resolution and LWR performance and have little bake temperature dependency during pattern formation, a pattern formation method using the actinic ray-sensitive or radiation-sensitive resin composition, and a method for manufacturing an electronic device.

[0017] 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.

[0018] In this specification, "actinic rays" or "radiation" refers to, for example, the bright line spectrum of a mercury lamp, far ultraviolet rays typified by excimer lasers, extreme ultraviolet rays (EUV), X-rays, soft X-rays, and electron beams (EB). In this specification, "light" refers to actinic rays or radiation. Unless otherwise specified, in this specification, "exposure" includes not only exposure using the bright line spectrum of a mercury lamp, far ultraviolet rays typified by excimer lasers, extreme ultraviolet rays, X-rays, and EUV, but also drawing using particle beams such as electron beams and ion beams. In this specification, the word "to" is used to mean that the numerical values ​​before and after it are included as the lower and upper limits.

[0019] 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.

[0020] 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).

[0021] 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:

[0022] (Substituent T) Examples of the substituent T include halogen atoms such as a fluorine atom, a chlorine atom, a bromine atom, and an iodine atom; alkoxy groups such as a methoxy group, an ethoxy group, and a tert-butoxy group; a cycloalkyloxy group; an aryloxy group such as a phenoxy group and a p-tolyloxy group; an alkoxycarbonyl group such as a methoxycarbonyl group and a butoxycarbonyl group; a cycloalkyloxycarbonyl group; an aryloxycarbonyl group such as a phenoxycarbonyl group; an acyloxy group such as an acetoxy group, a propionyloxy group, and a benzoyloxy group; an acetyl group, a benzoyl group, an isobutyryl group, an acryloyl group, a methacrylate group, a methyl ... Examples of the substituent T include acyl groups such as phenylsulfanyl and methoxalyl groups; sulfanyl groups; alkylsulfanyl groups such as methylsulfanyl and tert-butylsulfanyl groups; arylsulfanyl groups such as phenylsulfanyl and p-tolylsulfanyl groups; 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; sulfonamido groups; silyl groups; amino groups; carbamoyl groups; alkylsulfonyl groups; arylsulfonyl groups; etc. In addition, when these substituents can further have one or more substituents, examples of the substituent T also include groups having one or more substituents selected from the above-mentioned substituents as the further substituents (e.g., monoalkylamino groups, dialkylamino groups, arylamino groups, trifluoromethyl groups, etc.).

[0023] 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".

[0024] 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).

[0025] 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.

[0026] 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.

[0027] In this specification, the term "solid content" refers to components that form an actinic ray-sensitive or radiation-sensitive film, 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.

[0028] <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 resin; a photoacid generator (C) having, in its molecule, a nonionic acid-generating moiety that decomposes upon irradiation with actinic rays or radiation to generate an acid, and a basic moiety; and an acid diffusion controller (Q), wherein the content of the acid diffusion controller (Q) is 7 mass% or more relative to the content of the photoacid generator (C).

[0029] Although the mechanism by which the composition of the present invention achieves the above-mentioned effects is not clear, the inventors have hypothesized it as follows. However, the present invention is not limited in any way by the hypothesized mechanism below. It is believed that using a compound containing a nonionic acid-generating moiety as the photoacid generator increases compatibility with other components in the composition of the present invention. Furthermore, since the photoacid generator has a basic moiety capable of quenching acid, it is easy to suppress acid diffusion, thereby improving resolution, LWR performance, and bake temperature dependency. Furthermore, it is believed that the resolution and LWR performance can be further improved by maintaining a certain mass ratio of the acid diffusion controller content to the photoacid generator content.

[0030] The composition of the present invention is preferably a resist composition, and may be either a positive resist composition or a negative resist composition. The composition of the present invention may be a resist composition for alkali development or a resist composition for organic solvent development. The composition of the present invention may be either a chemically amplified resist composition or a non-chemically amplified resist composition. 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 preferably a resist film.

[0031] [Photoacid Generator (C)] The composition of the present invention contains a photoacid generator (C) (also simply referred to as "photoacid generator (C)") having, in its molecule, a nonionic acid-generating moiety that decomposes upon irradiation with actinic rays or radiation to generate an acid, and a basic moiety.

[0032] The photoacid generator (C) has a nonionic acid-generating moiety that decomposes upon irradiation with actinic rays or radiation to generate an acid. The nonionic acid-generating moiety is a moiety that forms an acid and is covalently bonded to another moiety, and upon irradiation with actinic rays or radiation, the covalent bond is cleaved to generate an acid.

[0033] The acid generating site of the photoacid generator (C) preferably contains a group represented by any one of the following formulas (1) to (3).

[0034]

[0035] In formula (1), X １１ represents a hydrogen atom or a substituent. １１ represents an alkyl group, a cycloalkyl group, an aryl group, a heteroaryl group, an alkenyl group, a cycloalkenyl group, or an alkynyl group. １１ and R １１ may be bonded to form a ring. * represents the bonding position. In formula (2), X ２１ and X ２２ R each independently represents a hydrogen atom or a substituent. ２１ represents an alkyl group, a cycloalkyl group, an aryl group, a heteroaryl group, an alkenyl group, a cycloalkenyl group, or an alkynyl group. m represents 0 or 1. n represents 0 or 1. * represents a bonding position. In formula (3), X ３１ and X ３２ each independently represents a cyano group, an alkyl group, a cycloalkyl group, an acyl group, an alkoxycarbonyl group, an aryloxycarbonyl group, a heteroaryloxycarbonyl group, an aryl group, a heteroaryl group, an alkenyl group, a cycloalkenyl group, or an alkynyl group. ３１ and X ３２ may be bonded to form a ring. * indicates the bonding position.

[0036] X in formula (1) １１ represents a hydrogen atom or a substituent. １１ The substituent represented by is not particularly limited, and examples thereof include the aforementioned substituent T. X is preferably an organic group, and more preferably an organic group having 1 to 30 carbon atoms. １１The substituent represented by is preferably an alkyl group, an alkoxy group, an alkylthio group, a cycloalkyl group, a cycloalkyloxy group, a cycloalkylthio group, an aryl group, an aryloxy group, an arylthio group, an acyl group, an alkoxycarbonyl group, a cycloalkyloxycarbonyl group, an aryloxycarbonyl group, a heteroaryl group, a heteroaryloxy group, a heteroaryloxycarbonyl group, a formyl group, or a group formed by combining two or more of these, and more preferably an acyl group. These groups may further have one or more substituents.

[0037] X １１ The alkyl group represented by may be linear or branched. The number of carbon atoms in the alkyl group is not particularly limited, and is, for example, preferably 1 to 30, more preferably 1 to 20, and even more preferably 1 to 15. The alkyl group may have a substituent. The alkyl group may also contain at least one of an ether bond (-O-) and a thioether bond (-S-) in the chain. Examples of the alkyl group include a methyl group, an ethyl group, a propyl group, an isopropyl group, an n-butyl group, an isobutyl group, a sec-butyl group, a t-butyl group, a pentyl group, a neopentyl group, a hexyl group, a heptyl group, an octyl group, a nonyl group, a decyl group, an undecyl group, a dodecyl group, a tridecyl group, a tetradecyl group, a pentadecyl group, a hexadecyl group, a heptadecyl group, an octadecyl group, a nonadecyl group, and an eicosyl group.

[0038] X １１ The explanation, specific examples and preferred ranges of the alkyl groups contained in the alkoxy group, alkylthio group and alkoxycarbonyl group represented by X are as described above. １１ is the same as that in the alkyl group represented by

[0039] X １１The cycloalkyl group represented by may be monocyclic or polycyclic. The number of carbon atoms in the cycloalkyl group is not particularly limited, and is preferably 3 to 30, more preferably 4 to 20, and even more preferably 5 to 15. The cycloalkyl group may have a substituent. In the cycloalkyl group, for example, one or more methylene groups constituting the cycloalkane ring may be replaced with a heteroatom such as an oxygen atom or a sulfur atom, or a group having a heteroatom such as a carbonyl group. In addition, in the cycloalkyl group, one or more ethylene groups constituting the cycloalkane ring may be replaced with a vinylene group. Examples of the cycloalkyl group include a cyclopentyl group, a cyclohexyl group, a norbornyl group, a tetracyclodecanyl group, a tetracyclododecanyl group, and an adamantyl group.

[0040] X １１ The explanation, specific examples and preferred ranges of the cycloalkyl group contained in the cycloalkyloxy group, cycloalkylthio group and cycloalkyloxycarbonyl group represented by X are as described above. １１ is the same as that in the cycloalkyl group represented by

[0041] X １１The number of carbon atoms in the aryl group represented by is not particularly limited, and for example, is preferably 6 to 30, more preferably 6 to 20, and even more preferably 6 to 15. The aryl group may have a substituent. The aryl group may be a monocyclic group or a polycyclic group. The aryl group is an aromatic hydrocarbon (for example, a monocyclic or polycyclic aromatic hydrocarbon having 6 to 15 carbon atoms, such as benzene or naphthalene), a cycloalkane (for example, a monocyclic or polycyclic cycloalkane having 3 to 12 carbon atoms, such as cyclopentane or cyclohexane, which may have one or more carbonyl groups as a ring-constituting group), a cycloalkene (for example, a monocyclic or polycyclic cycloalkene having 3 to 12 carbon atoms, such as cyclohexene, which may have one or more carbonyl groups as a ring-constituting group), a non-aromatic heterocyclic compound (for example, pyrrolidine, pyrroline, Five-membered non-aromatic heterocyclic compounds such as oxazolidone, tetrahydrofuran, 1,3-dioxolane, and tetrahydrothiophene, and six-membered non-aromatic heterocyclic compounds such as morpholine, piperidine, piperazine, and tetrahydropyran. The ring-constituting group may have at least one selected from the group consisting of a carbonyl group, a sulfonyl group, and an ethylene group. The aryl group may also be a group obtained by removing one hydrogen atom from a fused ring compound (e.g., indane, indene, etc.) having a structure condensed with at least one selected from the group consisting of aryl groups. Examples of the aryl group include a phenyl group, a naphthyl group, an anthryl group, a fluorenyl group, and a phenanthryl group. A phenyl group or a naphthyl group is preferred, and a phenyl group is more preferred.

[0042] X １１ The explanation, specific examples and preferred ranges of the aryl group contained in the aryloxy group, arylthio group and aryloxycarbonyl group represented by X are respectively described above. １１ The same applies to the aryl group represented by the formula (I).

[0043] X １１The heteroaryl group (aromatic heterocyclic group) represented by the formula (I) preferably contains at least one heteroatom selected from the group consisting of a nitrogen atom, an oxygen atom, and a sulfur atom as a ring member. The number of ring members of the heteroaryl group is not particularly limited, but is preferably 3 to 30, more preferably 4 to 20, and even more preferably 5 to 15. The number of carbon atoms of the heteroaryl group is not particularly limited, but is preferably 1 to 28, more preferably 2 to 18, and even more preferably 2 to 13. The heteroaryl group may have a substituent. The heteroaryl group may be a monocyclic group or a polycyclic group. Examples of heteroaryl groups include groups obtained by removing one hydrogen atom from five-membered aromatic heterocyclic compounds such as pyrrole, imidazole, pyrazole, oxazole, isoxazole, thiazole, isothiazole, triazole, thiophene, furan, oxadiazole, thiadiazole, dioxazole, dithiazole, and tetrazole, and six-membered aromatic heterocyclic compounds such as pyridine, pyrazine, pyrimidine, pyridazine, triazine, thiazine, and oxazine. The heteroaryl group may be any of the five-membered aromatic heterocyclic compounds and six-membered aromatic heterocyclic compounds, aromatic hydrocarbons (e.g., monocyclic or polycyclic aromatic hydrocarbons having 6 to 15 carbon atoms, such as benzene and naphthalene), cycloalkanes (e.g., monocyclic or polycyclic cycloalkanes having 3 to 12 carbon atoms, such as cyclopentane and cyclohexane), cycloalkenes (e.g., monocyclic or polycyclic cycloalkenes having 3 to 12 carbon atoms, such as cyclohexene), non-aromatic heterocyclic compounds (e.g., pyrrolidine, pyrroline, 2-oxazolidone, and six-membered ring non-aromatic heterocyclic compounds such as morpholine, piperidine, piperazine, tetrahydropyran, etc.), or a group obtained by removing one hydrogen atom from a fused ring compound (e.g., indole, isoindole, benzimidazole, benzotriazole, purine, quinazoline, quinoxaline, cinnoline, pteridine, acridine, carbazole, benzofuran, benzothiophene, quinoline, isoquinoline, etc.) having a structure fused with at least one selected from the group consisting of: five-membered ring non-aromatic heterocyclic compounds such as benzophenone, tetrahydrofuran, and tetrahydrothiophene; and six-membered ring non-aromatic heterocyclic compounds such as morpholine, piperidine, piperazine, and tetrahydropyran.

[0044] X １１ The acyl group represented by R Ｃ１ -C(=O)-, and R Ｃ１ R preferably represents an organic group. Ｃ１ The organic group represented by R is preferably an alkyl group, a cycloalkyl group, an aryl group, or a heteroaryl group. Ｃ１ The description, specific examples and preferred ranges of the organic group represented by X are as described above. １１ It is the same as in

[0045] X １１ The heteroaryloxy group represented by R Ｃ２ It is a group represented by —O—. Ｃ２ represents a heteroaryl group. Ｃ２ The description, specific examples and preferred ranges of the heteroaryl group represented by are the same as those of the above-mentioned X １１ It is the same as in

[0046] X １１ The explanation, specific examples and preferred ranges of the heteroaryl group contained in the heteroaryloxycarbonyl group represented by the formula (I) are the same as those of the above-mentioned X １１ The heteroaryl group is the same as that represented by the formula (I).

[0047] R in formula (1) １１ represents an alkyl group, a cycloalkyl group, an aryl group, a heteroaryl group, an alkenyl group, a cycloalkenyl group or an alkynyl group, and preferably represents an alkyl group, a cycloalkyl group, an aryl group or a heteroaryl group.

[0048] R １１The alkyl group represented by may be linear or branched. The number of carbon atoms in the alkyl group is not particularly limited, and is, for example, preferably 1 to 30, more preferably 1 to 20, and even more preferably 1 to 15. The alkyl group may have a substituent. The alkyl group may also contain at least one of an ether bond (-O-) and a thioether bond (-S-) in the chain. Examples of the alkyl group include a methyl group, an ethyl group, a propyl group, an isopropyl group, an n-butyl group, an isobutyl group, a sec-butyl group, a t-butyl group, a pentyl group, a neopentyl group, a hexyl group, a heptyl group, an octyl group, a nonyl group, a decyl group, an undecyl group, a dodecyl group, a tridecyl group, a tetradecyl group, a pentadecyl group, a hexadecyl group, a heptadecyl group, an octadecyl group, a nonadecyl group, and an eicosyl group.

[0049] R １１ The cycloalkyl group represented by may be monocyclic or polycyclic. The number of carbon atoms in the cycloalkyl group is not particularly limited, and is preferably 3 to 30, more preferably 4 to 20, and even more preferably 5 to 15. The cycloalkyl group may have a substituent. In the cycloalkyl group, for example, one or more methylene groups constituting the cycloalkane ring may be replaced with a heteroatom such as an oxygen atom or a sulfur atom, or a group having a heteroatom such as a carbonyl group. In addition, in the cycloalkyl group, one or more ethylene groups constituting the cycloalkane ring may be replaced with a vinylene group. Examples of the cycloalkyl group include a cyclopentyl group, a cyclohexyl group, a norbornyl group, a tetracyclodecanyl group, a tetracyclododecanyl group, and an adamantyl group.

[0050] R １１The number of carbon atoms in the aryl group represented by is not particularly limited, and for example, is preferably 6 to 30, more preferably 6 to 20, and even more preferably 6 to 15. The aryl group may have a substituent. The aryl group may be a monocyclic group or a polycyclic group. The aryl group is an aromatic hydrocarbon (for example, a monocyclic or polycyclic aromatic hydrocarbon having 6 to 15 carbon atoms, such as benzene or naphthalene), a cycloalkane (for example, a monocyclic or polycyclic cycloalkane having 3 to 12 carbon atoms, such as cyclopentane or cyclohexane, which may have one or more carbonyl groups as a ring-constituting group), a cycloalkene (for example, a monocyclic or polycyclic cycloalkene having 3 to 12 carbon atoms, such as cyclohexene, which may have one or more carbonyl groups as a ring-constituting group), a non-aromatic heterocyclic compound (for example, pyrrolidine, pyrroline, Five-membered non-aromatic heterocyclic compounds such as oxazolidone, tetrahydrofuran, 1,3-dioxolane, and tetrahydrothiophene, and six-membered non-aromatic heterocyclic compounds such as morpholine, piperidine, piperazine, and tetrahydropyran. The ring-constituting group may have at least one selected from the group consisting of a carbonyl group, a sulfonyl group, and an ethylene group. The aryl group may also be a group obtained by removing one hydrogen atom from a fused ring compound (e.g., indane, indene, etc.) having a structure condensed with at least one selected from the group consisting of aryl groups. Examples of the aryl group include a phenyl group, a naphthyl group, an anthryl group, a fluorenyl group, and a phenanthryl group. A phenyl group or a naphthyl group is preferred, and a phenyl group is more preferred.

[0051] R １１The heteroaryl group (aromatic heterocyclic group) represented by the formula (I) preferably contains at least one heteroatom selected from the group consisting of a nitrogen atom, an oxygen atom, and a sulfur atom as a ring member. The number of ring members of the heteroaryl group is not particularly limited, but is preferably 3 to 30, more preferably 4 to 20, and even more preferably 5 to 15. The number of carbon atoms of the heteroaryl group is not particularly limited, but is preferably 1 to 28, more preferably 2 to 18, and even more preferably 2 to 13. The heteroaryl group may have a substituent. The heteroaryl group may be a monocyclic group or a polycyclic group. Examples of heteroaryl groups include groups obtained by removing one hydrogen atom from five-membered aromatic heterocyclic compounds such as pyrrole, imidazole, pyrazole, oxazole, isoxazole, thiazole, isothiazole, triazole, thiophene, furan, oxadiazole, thiadiazole, dioxazole, dithiazole, and tetrazole, and six-membered aromatic heterocyclic compounds such as pyridine, pyrazine, pyrimidine, pyridazine, triazine, thiazine, and oxazine. The heteroaryl group may be any of the five-membered aromatic heterocyclic compounds and six-membered aromatic heterocyclic compounds, aromatic hydrocarbons (e.g., monocyclic or polycyclic aromatic hydrocarbons having 6 to 15 carbon atoms, such as benzene and naphthalene), cycloalkanes (e.g., monocyclic or polycyclic cycloalkanes having 3 to 12 carbon atoms, such as cyclopentane and cyclohexane), cycloalkenes (e.g., monocyclic or polycyclic cycloalkenes having 3 to 12 carbon atoms, such as cyclohexene), non-aromatic heterocyclic compounds (e.g., pyrrolidine, pyrroline, 2-oxazolidone, and six-membered ring non-aromatic heterocyclic compounds such as morpholine, piperidine, piperazine, tetrahydropyran, etc.), or a group obtained by removing one hydrogen atom from a fused ring compound (e.g., indole, isoindole, benzimidazole, benzotriazole, purine, quinazoline, quinoxaline, cinnoline, pteridine, acridine, carbazole, benzofuran, benzothiophene, quinoline, isoquinoline, etc.) having a structure fused with at least one selected from the group consisting of: five-membered ring non-aromatic heterocyclic compounds such as benzophenone, tetrahydrofuran, and tetrahydrothiophene; and six-membered ring non-aromatic heterocyclic compounds such as morpholine, piperidine, piperazine, and tetrahydropyran.

[0052] R １１ The number of carbon atoms in the alkenyl group represented by is not particularly limited, and is preferably 2 to 20, and more preferably 3 to 10. The alkenyl group may have a substituent, and may have two or more unsaturated bonds within the alkenyl group. Examples of the alkenyl group include an ethenyl group.

[0053] R １１ The number of carbon atoms in the alkynyl group represented by is not particularly limited, and is preferably 2 to 20, and more preferably 3 to 10. The alkynyl group may have a substituent, and may have two or more unsaturated bonds within the alkynyl group. Examples of the alkynyl group include an ethynyl group.

[0054] R １１ The number of carbon atoms in the cycloalkenyl group represented by is not particularly limited, and is, for example, preferably 4 to 30, more preferably 5 to 15. The cycloalkenyl group may have a substituent, and may have two or more unsaturated bonds within the cycloalkenyl group.

[0055] X １１ and R １１ may be bonded to form a ring. For example, X １１ represents a formyl group, and R １１ When represents an aryl group, X １１ The hydrogen atom of the formyl group represented by is eliminated to form R １１ In addition, X may be bonded to an aryl group represented by １１ and R １１ may be bonded by a single bond or via a linking group. Examples of the linking group include -O-, -S-, -CO-, -CO ２ -, -SO-, -SO ２ -, an alkylene group (preferably having 1 to 5 carbon atoms), an alkenylene group (preferably having 2 to 5 carbon atoms), and a group formed by combining two or more of these.

[0056] X in formula (1) １１ and R １１ At least one of the groups may have a basic site, but preferably does not have a basic site. Basic sites will be described later.

[0057] X in formula (2)２１ and X ２２ each independently represents a hydrogen atom or a substituent. ２１ and X ２２ The substituent represented by is not particularly limited, and examples thereof include the aforementioned substituent T. X is preferably an organic group, and more preferably an organic group having 1 to 30 carbon atoms. ２１ and X ２２ The substituent represented by is preferably an alkyl group, a cycloalkyl group, an aryl group, a heteroaryl group, an alkenyl group, a cycloalkenyl group, or an alkynyl group. These groups may further have one or more substituents. The explanation, specific examples, and preferred ranges of each of these groups are described in the above-mentioned R in formula (1). １１ It is the same as in X. ２１ and X ２２ preferably represents a hydrogen atom, an alkyl group or an aryl group.

[0058] R in formula (2) ２１ represents an alkyl group, a cycloalkyl group, an aryl group, a heteroaryl group, an alkenyl group, a cycloalkenyl group, or an alkynyl group. These groups may further have one or more substituents. The explanation, specific examples, and preferred ranges of each of these groups are given in the above-mentioned R １１ It is the same as in R ２１ preferably represents an aryl or heteroaryl group.

[0059] In formula (2), m represents 0 or 1, and preferably represents 1.

[0060] In formula (2), n represents 0 or 1, and preferably represents 1.

[0061] X in formula (2) ２１ , X ２２ and R ２１ At least one of the groups may have a basic site, but preferably does not have a basic site. Basic sites will be described later.

[0062] X in formula (3) ３１ and X ３２each independently represents a cyano group, an alkyl group, a cycloalkyl group, an acyl group, an alkoxycarbonyl group, an aryloxycarbonyl group, a heteroaryloxycarbonyl group, an aryl group, a heteroaryl group, an alkenyl group, a cycloalkenyl group, or an alkynyl group. ３１ and X ３２ The alkyl group, cycloalkyl group, acyl group, alkoxycarbonyl group, aryloxycarbonyl group, heteroaryloxycarbonyl group, aryl group, heteroaryl group, alkenyl group and cycloalkenyl group represented by may further have one or more substituents. The explanation, specific examples and preferred ranges of each of these groups are given in the above-mentioned formula (1) R １１ In or X １１ It is the same as in X. ３１ and X ３２ preferably represents a cyano group, an alkyl group, an aryl group or a heteroaryl group.

[0063] X ３１ and X ３２ may be bonded to form a ring. ３１ and X ３２ may be bonded by a single bond or via a linking group. Examples of the linking group include -O-, -S-, -CO-, -CO ２ -, -SO-, -SO ２ -, an alkylene group (preferably having 1 to 5 carbon atoms), an alkenylene group (preferably having 2 to 5 carbon atoms), and a group formed by combining two or more of these.

[0064] In addition, X in formula (3) ３１ and X ３２ At least one of the groups may have a basic site, but preferably does not have a basic site. Basic sites will be described later.

[0065] The photoacid generator (C) is preferably a compound represented by any one of the following formulas (1-1) to (3-1).

[0066]

[0067] In formula (1-1), X １１ represents a hydrogen atom or a substituent.１１ represents an alkyl group, a cycloalkyl group, an aryl group, a heteroaryl group, an alkenyl group, a cycloalkenyl group, or an alkynyl group. １１ and R １１ may be bonded to form a ring. Ｃ represents a substituent. ２１ and X ２２ R each independently represents a hydrogen atom or a substituent. ２１ represents an alkyl group, a cycloalkyl group, an aryl group, a heteroaryl group, an alkenyl group, a cycloalkenyl group, or an alkynyl group. m represents 0 or 1. n represents 0 or 1. R Ｃ represents a substituent. ３１ and X ３２ each independently represents a cyano group, an alkyl group, a cycloalkyl group, an aryl group, a heteroaryl group, an alkenyl group, a cycloalkenyl group, or an alkynyl group. ３１ and X ３２ may be bonded to form a ring. Ｃ represents a substituent.

[0068] X in formula (1-1) １１ and R １１ The explanation, specific examples and preferred ranges of X in the above formula (1) are as follows: １１ and R １１ The X in formula (1-1) is the same as that in １１ , R １１ and R Ｃ At least one of R Ｃ It is preferable that the basic site is contained in the hydroxyl group. The basic site will be described later.

[0069] X in formula (2-1) ２１ , X ２２ and R ２１ The explanation, specific examples and preferred ranges of X in the above formula (2) are as follows: ２１ , X ２２ and R ２１ It is preferable that m in formula (2-1) represents 1. It is preferable that n in formula (2-1) represents 1. X in formula (2-1) ２１ , X ２２, R ２１ and R Ｃ At least one of R Ｃ It is preferable that the basic site is contained in the hydroxyl group. The basic site will be described later.

[0070] X in formula (3-1) ３１ and X ３２ The explanation, specific examples and preferred ranges of X in the above formula (3) are as follows: ３１ and X ３２ The X in formula (3-1) is the same as that in ３１ , X ３２ and R Ｃ At least one of R Ｃ It is preferable that the basic site is contained in the hydroxyl group. The basic site will be described later.

[0071] R in formula (1-1), formula (2-1) and formula (3-1) Ｃ represents a substituent. Ｃ The explanation, specific examples and preferred ranges of the substituents represented by are respectively described in the above-mentioned formula (1) for X １１ It is the same as in

[0072] The photoacid generator (C) is a compound that has a nonionic acid-generating moiety in its molecule that decomposes to generate an acid upon irradiation with actinic rays or radiation, and therefore generates an acid (also referred to as "acid (CA)") upon irradiation with actinic rays or radiation. When the photoacid generator (C) is a compound represented by any of the above formulas (1-1) to (3-1), the acid (CA) is represented by the following formula (5):

[0073]

[0074] In formula (5), R Ｃ represents a substituent. Ｃ is R in formulas (1-1) to (3-1). Ｃ is the same as

[0075] The molecular weight of the acid (acid (CA)) generated from the acid generation site of the photoacid generator (C) is preferably 250 or more, more preferably 400 or more, and even more preferably 500 or more. The molecular weight of the acid (CA) is preferably 3000 or less, and more preferably 2000 or less.

[0076] The pKa of the acid (acid (CA)) generated from the acid generation site of the photoacid generator (C) is preferably −2.0 or more and less than 1.5, more preferably −1.5 or more and 1.0 or less, and even more preferably −1.0 or more and 0.5 or less.

[0077] The acid (acid (CA)) generated from the acid generation site of the photoacid generator (C) is preferably an arylsulfonic acid.

[0078] The photoacid generator (C) is preferably a compound represented by the following formula (4).

[0079]

[0080] In formula (4), X ４１ and X ４２ R each independently represents a hydrogen atom, an alkyl group, a cycloalkyl group, an aryl group, a heteroaryl group, an alkenyl group, a cycloalkenyl group, or an alkynyl group. ４１ represents an alkyl group, a cycloalkyl group, an aryl group, a heteroaryl group, an alkenyl group, a cycloalkenyl group, or an alkynyl group. ４２ represents a substituent. k represents an integer of 0 to 5. When k represents an integer of 2 or more, a plurality of R ４２ may be the same or different, and multiple R ４２ may be bonded to form a ring. ４１ , R ４２ , X ４１ and X ４２ At least one of the amino acids contains a basic site.

[0081] X in formula (4) ４１ and X ４２ each independently represents a hydrogen atom, an alkyl group, a cycloalkyl group, an aryl group, a heteroaryl group, an alkenyl group, a cycloalkenyl group, or an alkynyl group.４１ and X ４２ The alkyl group, cycloalkyl group, aryl group, heteroaryl group, alkenyl group, cycloalkenyl group and alkynyl group represented by may further have one or more substituents. The explanation, specific examples and preferred ranges of each of these groups are described in the above-mentioned R １１ It is the same as in X. ４１ and X ４２ preferably represents a hydrogen atom, an alkyl group or an aryl group.

[0082] R in formula (4) ４１ represents an alkyl group, a cycloalkyl group, an aryl group, a heteroaryl group, an alkenyl group, a cycloalkenyl group, or an alkynyl group. These groups may further have one or more substituents. The explanation, specific examples, and preferred ranges of each of these groups are given in the above-mentioned R １１ It is the same as in R ４１ preferably represents an aryl group.

[0083] R in formula (4) ４２ represents a substituent. ４２ The substituent represented by is not particularly limited, and examples thereof include the aforementioned substituent T, and it is preferably a halogen atom, an alkyl group, a cycloalkyl group, an alkoxy group, an aryloxy group, a cycloalkyloxy group, an alkylthio group, an arylthio group, an aryl group, a heteroaryl group, an ester group, a carboxyl group, or a group formed by combining two or more of these. The halogen atom is preferably a fluorine atom, a chlorine atom, a bromine atom, or an iodine atom. The ester group is preferably a -COOR Ｅ１ or -OCOR Ｅ１ It is preferable that R Ｅ１ represents an organic group, and preferably represents an alkyl group, a cycloalkyl group, or an aryl group. Ｅ１ The description, specific examples and preferred range of the organic group represented by X in the above formula (1) are as follows: １１ It is the same as in R ４２ preferably represents an alkoxy group, an aryloxy group, an arylthio group, an aryl group or a heteroaryl group.

[0084] In formula (4), k represents an integer of 0 to 5, and preferably represents an integer of 1 to 3. When k represents an integer of 2 or more, a plurality of R ４２ may be the same or different, and multiple R ４２ may be bonded to form a ring. ４２ The ring formed by bonding of R may be an aromatic ring or a non-aromatic ring. ４２ The non-aromatic ring formed by bonding is preferably a cycloalkane ring. The cycloalkane ring may be a monocyclic cycloalkane ring such as a cyclopentane ring or a cyclohexane ring, or a polycyclic cycloalkane ring such as a norbornane ring, a tetracyclodecane ring, a tetracyclododecane ring or an adamantane ring. The cycloalkane ring is preferably a monocyclic cycloalkane ring having 5 to 6 carbon atoms. In the cycloalkane ring, one or more of the methylene groups constituting the ring may be replaced with a heteroatom such as an oxygen atom, a sulfur atom or a nitrogen atom, a group having a heteroatom such as a carbonyl group, or a vinylidene group. Furthermore, one or more of the ethylene groups constituting the ring may be replaced with a vinylene group. ４２ The aromatic ring formed by bonding may be an aromatic hydrocarbon ring having 6 to 15 carbon atoms, such as a benzene ring or a naphthalene ring, or an aromatic heterocycle, such as a pyridine ring, a thiophene ring or a furan ring. The aromatic heterocycle preferably contains at least one heteroatom selected from the group consisting of a nitrogen atom, an oxygen atom and a sulfur atom as a ring member. The number of ring atoms in the aromatic heterocycle is not particularly limited, but is preferably 3 to 30, more preferably 4 to 20, and even more preferably 5 to 15. ４２ The ring formed by bonding may have a substituent.

[0085] However, R ４１ , R ４２ , X ４１ and X ４２ At least one of R ４２ It is preferable that the basic site is contained in the hydroxyl group. The basic site will be described later.

[0086] The photoacid generator (C) has a basic site. The basic site has the function of quenching an acid, and preferably has the function of quenching an acid generated from a nonionic acid-generating site. The basic site may include an ionic structure. The ionic structure is a structure containing an anion and a cation. When the photoacid generator (C) has an ionic structure, the structure of the cation that forms a counter salt with the anion of the basic site is not limited. Specific examples include ammonium cation, sulfonium cation, iodonium cation, etc., and a sulfonium cation or an iodonium cation is preferred (i.e., the ionic structure is preferably a sulfonium salt or an iodonium salt). The ionic structure of the sulfonium salt preferably includes an anion of an acid weaker than the acid generated from the acid-generating site of the photoacid generator (C) (i.e., an acid with a pKa greater than that of the acid generated from the acid-generating site of the photoacid generator (C)) and a sulfonium cation. The ionic structure of the iodonium salt preferably contains an anion of an acid weaker than the acid generated from the acid generating site of the photoacid generator (C) (i.e., an acid having a pKa greater than that of the acid generated from the acid generating site of the photoacid generator (C)) and an iodonium cation. The basic site may also contain a nitrogen atom, such as an amine structure.

[0087] The basic moiety preferably has a group represented by the following formula (BA1): The basic moiety having a group represented by the following formula (BA1) may be decomposed by irradiation with actinic rays or radiation to convert into an acid weaker than the acid generated from the acid generating moiety of the photoacid generator (C).

[0088]

[0089] In formula (BA1), E １ － represents a residue of an acid weaker than the acid generated from the acid generating site of the photoacid generator (C) (i.e., an acid having a pKa greater than that of the acid generated from the acid generating site of the photoacid generator (C)), M ＋ represents a cation. * represents a bonding position. An acid residue is a group formed by dissociating a proton from an acid. E １ －is a carboxylate anion group (COO － ), phenolate anion group (Ar—O － ) Ar represents an aromatic ring group, preferably an arylene group having 6 to 20 carbon atoms, more preferably a phenylene group or a naphthylene group. Ar may have a substituent. ) a sulfonate anion group (SO ３ － ), or a sulfonamide group (N － -SO ２ R Ｎ１ It is expressed as: R Ｎ１ represents an organic group, including an organic group having 1 to 10 carbon atoms, and an alkyl group, a fluoroalkyl group, or an aryl group is preferred. ), more preferably represents a carboxylate anion group or a phenolate anion group, and even more preferably represents a carboxylate anion group.

[0090] M in formula (BA1) ＋ The cation represented by M is preferably an organic cation. The valence of the organic cation may be monovalent or divalent or more. ＋ Preferably, M represents a sulfonium cation or an iodonium cation. ＋ The cation represented by formula (ZaI) (hereinafter also referred to as "cation (ZaI)") or the cation represented by formula (ZaII) (hereinafter also referred to as "cation (ZaII)") is preferred.

[0091]

[0092] In the above formula (ZaI), R ２０１ , R ２０２ , and R ２０３ R each independently represents an organic group. ２０１ , R ２０２ , and R ２０３ The number of carbon atoms in the organic group represented by R is preferably 1 to 30, and more preferably 1 to 20. ２０１ ~R ２０３ Two of these may be bonded to form a ring structure, and the ring may contain an oxygen atom, a sulfur atom, an ester group, an amide group, or a carbonyl group. ２０１ ~R ２０３Examples of groups formed by combining two of these include alkylene groups (e.g., butylene and pentylene groups) and —CH ２ -CH ２ -O-CH ２ -CH ２ - are some examples.

[0093] Suitable embodiments of the organic cation in formula (ZaI) include cation (ZaI-1), cation (ZaI-2), cation (ZaI-3b), and cation (ZaI-4b) described below.

[0094] First, the cation (ZaI-1) will be described. The cation (ZaI-1) is R in the above formula (ZaI). ２０１ ~R ２０３ is an arylsulfonium cation, in which at least one of R is an aryl group. ２０１ ~R ２０３ may all be aryl groups, or R ２０１ ~R ２０３ A part of R may be an aryl group, and the rest may be an alkyl group or a cycloalkyl group. ２０１ ~R ２０３ is an aryl group, and R ２０１ ~R ２０３ The remaining two of R may be bonded to form a ring structure, and the ring may contain an oxygen atom, a sulfur atom, an ester group, an amide group, or a carbonyl group. ２０１ ~R ２０３ Examples of groups formed by combining two of the above include alkylene groups in which one or more methylene groups may be substituted with an oxygen atom, a sulfur atom, an ester group, an amide group, and / or a carbonyl group (e.g., butylene group, pentylene group, and —CH ２ -CH ２ -O-CH ２ -CH ２ The arylsulfonium cations include triarylsulfonium cations, diarylalkylsulfonium cations, aryldialkylsulfonium cations, diarylcycloalkylsulfonium cations, and aryldicycloalkylsulfonium cations.

[0095] 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.

[0096] R ２０１ ~R ２０３ Preferred substituents that the aryl group, alkyl group, and cycloalkyl group may have include alkyl groups (e.g., having 1 to 15 carbon atoms), cycloalkyl groups (e.g., having 3 to 15 carbon atoms), aryl groups (e.g., having 6 to 14 carbon atoms), alkoxy groups (e.g., having 1 to 15 carbon atoms), cycloalkylalkoxy groups (e.g., having 1 to 15 carbon atoms), halogen atoms (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. Note that the acid-decomposable group is intended to be a group that decomposes under the action of acid to generate a polar group, and is preferably a structure in which the polar group is protected with a group that leaves under the action of acid. The above polar groups and leaving groups are as described above.

[0097] Next, the cation (ZaI-2) will be described. The cation (ZaI-2) is a cation represented by the formula (ZaI) R ２０１ ~R ２０３ are each independently a cation representing an organic group that does not have an aromatic ring. The aromatic ring also includes an aromatic ring containing a heteroatom. ２０１ ~R ２０３ The number of carbon atoms of the organic group not having an aromatic ring as R is preferably 1 to 30, and more preferably 1 to 20. ２０１ ~R ２０３ are each independently preferably an alkyl group, a cycloalkyl group, an allyl group, or a vinyl group, more preferably a linear or branched 2-oxoalkyl group, a 2-oxocycloalkyl group, or an alkoxycarbonylmethyl group, and still more preferably a linear or branched 2-oxoalkyl group.

[0098] R ２０１ ~R ２０３ Examples of the alkyl group and cycloalkyl group in R include linear alkyl groups having 1 to 10 carbon atoms or branched alkyl groups having 3 to 10 carbon atoms (e.g., methyl, ethyl, propyl, butyl, and pentyl groups), and cycloalkyl groups having 3 to 10 carbon atoms (e.g., cyclopentyl, cyclohexyl, and norbornyl groups). ２０１ ~R ２０３ may be further substituted with a halogen atom, an alkoxy group (e.g., having 1 to 5 carbon atoms), a 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.

[0099] Next, the cation (ZaI-3b) will be described. The cation (ZaI-3b) is a cation represented by the following formula (ZaI-3b).

[0100]

[0101] In formula (ZaI-3b), R １ｃ ~R ５ｃR 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.

[0102] 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.

[0103] R １ｃ ~R ５ｃ Two or more of the following, R ６ｃ and R ７ｃ , and R ｘ and R ｙExamples 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.

[0104] R １ｃ ~R ５ｃ , R ６ｃ , R ７ｃ , R ｘ , R ｙ , and R １ｃ ~R ５ｃ Two or more of the following, R ５ｃ and R ６ｃ , R ６ｃ and R ７ｃ , R ５ｃ and R ｘ , and R ｘ and R ｙ The ring formed by bonding together may have a substituent.

[0105] Next, the cation (ZaI-4b) will be described. The cation (ZaI-4b) is a cation represented by the following formula (ZaI-4b).

[0106]

[0107] 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 １４represents 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.

[0108] In formula (ZaI-4b), R １３ , R １４ , and R １５ The alkyl group in R may be linear or branched. The number of carbon atoms in the alkyl group is preferably 1 to 10. The alkyl group is preferably a methyl group, an ethyl group, an n-butyl group, a t-butyl group, or the like. １３ ~R １５ , and R ｘ and R ｙ It is also preferred that each of the substituents independently form an acid-decomposable group by any combination of the substituents.

[0109] Next, formula (ZaII) will be described. In formula (ZaII), R ２０４ and R ２０５ R each independently represents an aryl group, an alkyl group, or a cycloalkyl group. ２０４ and R ２０５The aryl group in R is preferably a phenyl group or a naphthyl group, and more preferably a phenyl group. ２０４ and R ２０５ The aryl group in R may be an aryl group having a heterocycle containing an oxygen atom, a nitrogen atom, a sulfur atom, or the like. Examples of the skeleton of the aryl group having a heterocycle include pyrrole, furan, thiophene, indole, benzofuran, and benzothiophene. ２０４ and R ２０５ The alkyl group and cycloalkyl group are preferably a linear alkyl group having 1 to 10 carbon atoms or a branched alkyl group having 3 to 10 carbon atoms (e.g., methyl, ethyl, propyl, butyl, or pentyl), or a cycloalkyl group having 3 to 10 carbon atoms (e.g., cyclopentyl, cyclohexyl, or norbornyl).

[0110] R ２０４ and R ２０５ The aryl group, alkyl group, and cycloalkyl group in R may each independently have a substituent. ２０４ and R ２０５ Examples of the substituents that the aryl group, alkyl group, and cycloalkyl group may have include alkyl groups (e.g., having 1 to 15 carbon atoms), cycloalkyl groups (e.g., having 3 to 15 carbon atoms), aryl groups (e.g., having 6 to 15 carbon atoms), alkoxy groups (e.g., having 1 to 15 carbon atoms), halogen atoms, hydroxyl groups, and phenylthio groups. ２０４ and R ２０５ It is also preferred that the substituents independently form an acid-decomposable group by any combination of the substituents.

[0111] Specific examples of organic cations are shown below, but the present invention is not limited to these.

[0112]

[0113]

[0114] When the basic moiety is converted into an acid (also referred to as "acid (QA)") by irradiation with actinic rays or radiation, the pKa of the acid (QA) is preferably 1.00 or more greater than the pKa of the acid (acid (CA)) generated from the acid-generating moiety. The difference between the pKa of the acid (QA) and the pKa of the acid (CA) (the value obtained by subtracting the pKa of the acid (CA) from the pKa of the acid (QA)) is preferably 1.00 or more, more preferably 1.50 to 10.00, and even more preferably 2.00 to 8.00. The pKa of the acid (QA) is, for example, preferably 0.50 to 10.00, more preferably 1.00 to 8.00, and even more preferably 1.50 to 6.00. Note that when calculating the pKa of the acid (QA), the acid-generating moiety of the photoacid generator (C) is calculated using the compound in a decomposed state. When calculating the pKa of the acid (CA), the basic site of the photoacid generator (C) is calculated using the compound in a decomposed state.

[0115] The basic moiety also preferably has a group represented by any one of the following formulae (NA1) to (NA5).

[0116]

[0117] In formulas (NA1) and (NA5), R Ｄ１ and R Ｄ２ may be the same or different, and each independently represents a hydrogen atom, an alkyl group (preferably having 1 to 20 carbon atoms), a cycloalkyl group (preferably having 3 to 20 carbon atoms), or an aryl group (preferably having 6 to 20 carbon atoms). Ｄ１ and R Ｄ２ may be bonded to form a ring. Ｄ３ , R Ｄ４ , R Ｄ５ and R Ｄ６ may be the same or different, and each independently represents an alkyl group (preferably having 1 to 20 carbon atoms), a cycloalkyl group (preferably having 3 to 20 carbon atoms), or an aryl group (preferably having 6 to 20 carbon atoms). Ｄ３ , R Ｄ４ , R Ｄ５ and R Ｄ６ At least two of R may be bonded to form a ring. Ｄ３ , R Ｄ４ , R Ｄ５ and R Ｄ６Preferably, each independently represents an alkyl group. In formulae (NA1) to (NA5), * represents a bonding position.

[0118] R in formulas (NA1) and (NA5) Ｄ１ , R Ｄ２ , R Ｄ３ , R Ｄ４ , R Ｄ５ and R Ｄ６ The alkyl group, cycloalkyl group and aryl group represented by may have a substituent. As for the alkyl group, an aminoalkyl group having 1 to 20 carbon atoms, a hydroxyalkyl group having 1 to 20 carbon atoms, or a cyanoalkyl group having 1 to 20 carbon atoms is preferred. Ｄ１ , R Ｄ２ , R Ｄ３ , R Ｄ４ , R Ｄ５ and R Ｄ６ The alkyl group, cycloalkyl group and aryl group represented by the formula (I) preferably have no substituent (are unsubstituted).

[0119] R in formula (NA1) Ｄ１ and R Ｄ２ may be bonded to form a ring. Ｄ１ and R Ｄ２ The number of ring atoms in the ring formed by bonding R is not particularly limited, but is preferably 3 to 20, more preferably 3 to 10, and even more preferably 3 to 8. Ｄ１ and R Ｄ２ The number of carbon atoms in the ring formed by bonding R is not particularly limited, but is preferably 1 to 18, more preferably 2 to 9, and even more preferably 2 to 7. Ｄ１ and R Ｄ２ The ring formed by bonding of R may be a non-aromatic nitrogen-containing heterocycle or an aromatic nitrogen-containing heterocycle, but is preferably a non-aromatic nitrogen-containing heterocycle. Ｄ１ and R Ｄ２ The ring formed by bonding R may contain at least one of an oxygen atom, a sulfur atom, an ester bond, an amide bond, a carbonyl group, and a sulfonyl group within the ring. Ｄ１ and R Ｄ２ The ring formed by bonding R may have a substituent. Ｄ１ and R Ｄ２When the bond between adjacent atoms contained in the ring formed by bonding is a single bond, the single bond may be replaced with a multiple bond (for example, a double bond).

[0120] The basic moiety may be a group obtained by removing one or more hydrogen atoms from a nitrogen-containing compound such as guanidine, aminopyrrolidine, pyrazole, pyrazoline, piperazine, aminomorpholine, aminoalkylmorpholine, or piperidine. The basic moiety may be a group having at least one structure selected from the group consisting of an imidazole structure, a diazabicyclo structure, an onium hydroxide structure, an onium carboxylate structure, a trialkylamine structure, an aniline structure, and a pyridine structure. The basic moiety may be a group obtained by removing one or more hydrogen atoms from an alkylamine derivative having at least one structure selected from the group consisting of a hydroxyl group and an ether bond, or an aniline derivative having at least one structure selected from the group consisting of a hydroxyl group and an ether bond.

[0121] When the basic moiety contains an amine structure or an ammonium structure, the difference between the pKa of the conjugate acid of the basic moiety (a compound formed by bonding a proton to the nitrogen atom of the basic moiety) and the pKa of the acid (CA) (the value obtained by subtracting the pKa of the acid (CA) from the pKa of the conjugate acid of the basic moiety) is preferably 1.00 or more, more preferably 1.00 to 14.00, and even more preferably 2.00 to 13.00. The pKa of the conjugate acid of the basic moiety is, for example, preferably 1.00 to 14.00, more preferably 3.00 to 13.00, and even more preferably 3.50 to 12.50. When calculating the pKa of the conjugate acid of the basic moiety, the calculation is performed using the acid-generating moiety of the photoacid generator (C) as a compound in an undecomposed state.

[0122] The photoacid generator (C) is preferably a compound represented by the following formula (1-1-1), (1-1-2), (1-1-3), (2-1-1), (2-1-2), (2-1-3), (3-1-1), (3-1-2) or (3-1-3).

[0123]

[0124]

[0125]

[0126] In the formulas (1-1-1), (1-1-2) and (1-1-3), X １１ represents a hydrogen atom or a substituent. １１ represents an alkyl group, a cycloalkyl group, an aryl group, a heteroaryl group, an alkenyl group, a cycloalkenyl group, or an alkynyl group. １１ and R １１ may be bonded to form a ring. Ｃ１ , L Ｃ２ and L Ｃ３ each independently represents a single bond or a divalent linking group; Ar represents an aromatic ring group; M ＋ represents a cation. Ｄ１ and R Ｄ２ R each independently represents a hydrogen atom, an alkyl group, a cycloalkyl group, or an aryl group. Ｄ１ and R Ｄ２ may be bonded to form a ring. ２１ and X ２２ R each independently represents a hydrogen atom or a substituent. ２１ represents an alkyl group, a cycloalkyl group, an aryl group, a heteroaryl group, an alkenyl group, a cycloalkenyl group, or an alkynyl group. m represents 0 or 1. n represents 0 or 1. L Ｃ１ , L Ｃ２ and L Ｃ３ each independently represents a single bond or a divalent linking group; Ar represents an aromatic ring group; M ＋ represents a cation. Ｄ１ and R Ｄ２ R each independently represents a hydrogen atom, an alkyl group, a cycloalkyl group, or an aryl group. Ｄ１ and R Ｄ２ may be bonded to form a ring. ３１ and X ３２ each independently represents a cyano group, an alkyl group, a cycloalkyl group, an aryl group, a heteroaryl group, an alkenyl group, a cycloalkenyl group, or an alkynyl group. ３１ and X ３２ may be bonded to form a ring. Ｃ１, L Ｃ２ and L Ｃ３ each independently represents a single bond or a divalent linking group; Ar represents an aromatic ring group; M ＋ represents a cation. Ｄ１ and R Ｄ２ R each independently represents a hydrogen atom, an alkyl group, a cycloalkyl group, or an aryl group. Ｄ１ and R Ｄ２ may be bonded to form a ring.

[0127] X in formulas (1-1-1), (1-1-2) and (1-1-3) １１ and R １１ The explanation, specific examples and preferred ranges of X in the above formula (1) are as follows: １１ and R １１ It is the same as in

[0128] X in formulas (2-1-1), (2-1-2) and (2-1-3) ２１ , X ２２ and R ２１ The explanation, specific examples and preferred ranges of X in the above formula (2) are as follows: ２１ , X ２２ and R ２１ It is the same as in Formula (2-1-1), (2-1-2) and (2-1-3). It is preferable that m represents 1 in Formula (2-1-1), (2-1-2) and (2-1-3). It is preferable that n represents 1 in Formula (2-1-1), (2-1-2) and (2-1-3).

[0129] X in formulas (3-1-1), (3-1-2) and (3-1-3) ３１ and X ３２ The explanation, specific examples and preferred ranges of X in the above formula (3) are as follows: ３１ and X ３２ It is the same as in

[0130] L in formulas (1-1-1), (1-1-2), (1-1-3), (2-1-1), (2-1-2), (2-1-3), (3-1-1), (3-1-2) and (3-1-3) Ｃ１ , L Ｃ２ and L Ｃ３ each independently represents a single bond or a divalent linking group. Ｃ１ , L Ｃ２ and LＣ３ The divalent linking group represented by is not particularly limited, and examples thereof include an alkylene group (preferably having 1 to 20 carbon atoms), a cycloalkylene group (preferably having 3 to 20 carbon atoms), an alkenylene group (preferably having 2 to 20 carbon atoms), an arylene group (preferably having 6 to 20 carbon atoms), and a group formed by combining two or more of these. These divalent linking groups may have a substituent. The alkylene group and the alkenylene group may have -O-, -S-, -CO-, -CO ２ -, -SO- and -SO ２ - may have at least one selected from the group consisting of Ｃ１ and L Ｃ３ Preferably, contains an arylene group.

[0131] Ar in formulas (1-1-2), (2-1-2), and (3-1-2) represents an aromatic ring group. The aromatic ring group represented by Ar may be an arylene group or a heteroarylene group (aromatic heterocyclic group). As the arylene group, for example, an arylene group having 6 to 18 carbon atoms such as a phenylene group, a tolylene group, a naphthylene group, or an anthracenylene group is preferred. As the aromatic heterocyclic group, a group containing at least one atom selected from the group consisting of a nitrogen atom, an oxygen atom, and a sulfur atom as a ring member is preferred. The number of ring atoms of the aromatic heterocyclic group is preferably 4 to 20. The number of carbon atoms of the aromatic heterocyclic group is preferably 1 to 18. The aromatic heterocyclic group is preferably 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 represented by Ar may have a substituent.

[0132] M in formulas (1-1-1), (1-1-2), (2-1-1), (2-1-2), (3-1-1) and (3-1-2) ＋ represents a cation. ＋ The cation represented by M is not particularly limited. The valence of the cation may be monovalent or divalent or higher. ＋ The explanation, specific examples and preferred ranges of M in the above formula (BA1) are ＋It is the same as in

[0133] R in formulas (1-1-3), (2-1-3) and (3-1-3) Ｄ１ and R Ｄ２ R each independently represents a hydrogen atom, an alkyl group, a cycloalkyl group, or an aryl group. Ｄ１ and R Ｄ２ may be bonded to form a ring. Ｄ１ and R Ｄ２ The explanation, specific examples and preferred ranges of R in the above formula (NA1) are Ｄ１ and R Ｄ２ It is the same as in

[0134] The photoacid generator (C) can be synthesized by referring to a known method.

[0135] Specific examples of the photoacid generator (C) are shown below, but the present invention is not limited to these. Me represents a methyl group.

[0136]

[0137]

[0138]

[0139]

[0140] The content of the photoacid generator (C) in the composition of the present invention is preferably 1% by mass or more, more preferably 3% by mass or more, and even more preferably 5% by mass or more, based on the total solid content of the composition of the present invention. Furthermore, the content of the photoacid generator (C) in the composition of the present invention is preferably 40% by mass or less, more preferably 30% by mass or less, based on the total solid content of the composition of the present invention. Only one type of photoacid generator (C) may be used, or two or more types may be used. When two or more types are used, it is preferable that the total content thereof is within the above-mentioned preferred content range.

[0141] In addition to the photoacid generator (C), the composition of the present invention may further contain a photoacid generator other than the photoacid generator (C) (also referred to as an "other photoacid generator"). When the composition of the present invention contains the other photoacid generator, the content of the photoacid generator (C) is preferably 30% by mass or more, more preferably 40% by mass or more, and even more preferably 50% by mass or more, based on the total amount of the photoacid generators in the composition of the present invention.

[0142] [Resin] The composition of the present invention contains a resin (also referred to as "resin (P)"). The resin (P) is preferably a component separate from the photoacid generator (C) and the acid diffusion controller (Q). The resin (P) preferably contains a repeating unit having a group that decomposes under the action of acid to increase polarity (acid-decomposable group). The resin (P) preferably contains a repeating unit having a phenolic hydroxyl group. The resin (P) more preferably contains a repeating unit having a phenolic hydroxyl group and a repeating unit having an acid-decomposable group. When the resin (P) contains a repeating unit having an acid-decomposable group, the resin (P) is an acid-decomposable resin. In a pattern formation method using the composition of the present invention, when an alkaline developer is used as the developer, a positive pattern is suitably formed, and when an organic developer is used as the developer, a negative pattern is suitably formed.

[0143] (Repeating unit having acid-decomposable group) The acid-decomposable group is a group that decomposes under the action of an acid to increase its polarity. The acid-decomposable group is preferably a group that decomposes under the action of an acid to generate a polar group. The acid-decomposable group preferably has a structure in which a polar group is protected by a group that leaves under the action of an acid (leaving group). Typically, the polarity of the resin (P) increases under the action of an acid, increasing its solubility in an alkaline developer and decreasing its solubility in an organic solvent. The polar group is preferably an alkali-soluble group, and examples thereof include acidic groups such as a carboxy group, a phenolic hydroxyl group, a fluorinated alcohol group, a sulfonic acid group, a phosphate group, a sulfonamide group, a sulfonylimide group, an (alkylsulfonyl)(alkylcarbonyl)methylene group, an (alkylsulfonyl)(alkylcarbonyl)imide group, a bis(alkylcarbonyl)methylene group, a bis(alkylcarbonyl)imide group, a bis(alkylsulfonyl)methylene group, a bis(alkylsulfonyl)imide group, a tris(alkylcarbonyl)methylene group, and a tris(alkylsulfonyl)methylene group, as well as alcoholic hydroxyl groups.

[0144] Examples of the leaving 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)

[0145] 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 aryl group (monocyclic or polycyclic), an aralkyl group (linear or branched), or an alkenyl group (linear or branched). １ ~Rx ３When 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 each other to form a ring (which may be either 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 preferably has 3 to 20 carbon atoms, more preferably 4 to 15 carbon atoms. 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 aralkyl group of Rx １ ~Rx ３ A group in which one hydrogen atom in the alkyl group is substituted with an aryl group (preferably a phenyl group) having 6 to 10 carbon atoms is preferred, and examples thereof include a benzyl 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 ~Rx３ The cycloalkyl group formed by combining the two is preferably a monocyclic cycloalkyl group such as a cyclopentyl group or a cyclohexyl group, or a polycyclic cycloalkyl group such as a norbornyl group, a tetracyclodecanyl group, a tetracyclododecanyl group, or an adamantyl group, and more preferably a monocyclic cycloalkyl group having 5 to 6 carbon atoms. １ ~Rx ３ In the cycloalkyl group formed by bonding these two, for example, one of the methylene groups constituting the ring may be replaced with a heteroatom such as an oxygen atom, a group having a heteroatom such as a carbonyl group, or a vinylidene group. Furthermore, in these cycloalkyl groups, one or more of the ethylene groups constituting the cycloalkane ring may be replaced with a vinylene group. The group represented by formula (Y1) or formula (Y2) can be, for example, Rx １ is a methyl group or an ethyl group, and Rx ２ and Rx ３ and are preferably bonded to form the above-mentioned cycloalkyl group.

[0146] 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 having a heteroatom such as a carbonyl group. For example, the alkyl group, cycloalkyl group, aryl group, and aralkyl group may have one or more methylene groups replaced with a heteroatom such as an oxygen atom and / or a group having a heteroatom such as a carbonyl group. In addition, 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 the repeating unit and another substituent carried by the main chain of the repeating unit is preferably an alkylene group such as a methylene group.

[0147] 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 more preferably an aryl group.

[0148] The repeating unit having an acid-decomposable group is preferably a repeating unit represented by the following formula (b-1): The resin (P) preferably contains a repeating unit represented by the following formula (b-1).

[0149]

[0150] In formula (b-1), R ｂ１ and R ｂ２ each independently represents a hydrogen atom or an alkyl group. ｂ１ represents a single bond or -C(=O)O-. r represents an integer of 0 to 2. ｐ１ and R ｐ２ R each independently represents a group that is eliminated by the action of an acid. ｂ３ represents a halogen atom, an alkyl group, a cycloalkyl group, an alkoxy group, an aryloxy group, an alkylthio group, an arylthio group, an aryl group, a heteroaryl group, an ester group, a carboxyl group, or a group formed by combining two or more of these. s and t each independently represent an integer of 0 to 4, provided that at least one of s and t is an integer of 1 or greater. u represents an integer of 0 to (5+2r-s-t). R ｐ１ If there are multiple R ｐ１ may be the same or different and may be bonded to each other to form a ring. ｐ２ If there are multiple R ｐ２ may be the same or different and may be bonded to each other to form a ring. ｂ３ If there are multiple R ｂ３ may be the same or different and may be bonded to each other to form a ring. ｂ３ and R ｐ１ , R ｂ３ and Rｐ２ , and R ｐ１ and R ｐ２ may be bonded to each other to form a ring. ｂ１ Is L ｂ１ may be bonded to the aromatic ring to which

[0151] In formula (b-1), R ｂ１ and R ｂ２ The 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 5, and more preferably 1 to 3. The alkyl group may further have a substituent. ｂ１ and R ｂ２ is preferably a hydrogen atom.

[0152] In formula (b-1), L ｂ１ represents a single bond or —C(═O)O—, and is preferably a single bond.

[0153] In formula (b-1), r represents an integer of 0 to 2, preferably 0 or 1, and more preferably 0. The aromatic ring in formula (b-1) is benzene when r represents 0, naphthalene when r represents 1, and anthracene when r represents 2.

[0154] In formula (b-1), s represents an integer of 0 to 4, preferably an integer of 0 to 2, and more preferably 0 or 1.

[0155] In formula (b-1), R ｐ１ represents a group which is eliminated by the action of an acid. The group which is eliminated by the action of an acid is not particularly limited, but examples thereof include the groups represented by the above formulae (Y1) to (Y4). ｐ１ is converted to R by the action of an acid. ｐ１ is eliminated to produce a hydroxyl group.

[0156] In formula (b-1), t represents an integer of 0 to 4, preferably an integer of 0 to 2, and more preferably 0 or 1. At least one of s and t is an integer of 1 or greater.

[0157] In formula (b-1), R ｐ２represents a group which is eliminated by the action of an acid. The group which is eliminated by the action of an acid is not particularly limited, but examples thereof include the groups represented by the above formulae (Y1) to (Y4). ｐ２ is converted to R by the action of an acid. ｐ２ is eliminated to produce a carboxyl group.

[0158] In formula (b-1), R ｂ３ represents a halogen atom, an alkyl group, a cycloalkyl group, an alkoxy group, an aryloxy group, an alkylthio group, an arylthio group, an aryl group, a heteroaryl group, an ester group, a carboxyl group, or a group formed by combining two or more of these. ｂ３ 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. ｂ３ The 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, and more preferably 1 to 6. ｂ３ The methylene group contained in the alkyl group may be substituted with at least one of —CO— and —O—. ｂ３ 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. ｂ３ 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. ｂ３ The alkyl group contained in the alkoxy group may be either linear or branched. The number of carbon atoms in the alkyl group contained in the alkoxy group is not particularly limited, but is preferably 1 to 10, and more preferably 1 to 6. ｂ３ The number of carbon atoms in the aryl group contained in the aryloxy group is not particularly limited, but is preferably 6 to 20, and more preferably 6 to 10. ｂ３ The aryl group contained in the aryloxy group is most preferably a phenyl group.

[0159] R ｂ３The alkyl group contained in the alkylthio group may be either linear or branched. ｂ３ The number of carbon atoms in the alkyl group contained in the alkylthio group is not particularly limited, but is preferably 1 to 10, and more preferably 1 to 6. ｂ３ The number of carbon atoms in the aryl group contained in the arylthio group is not particularly limited, but is preferably 6 to 20, and more preferably 6 to 10. ｂ３ The aryl group contained in the arylthio group of R is most preferably a phenyl group. ｂ３ The number of carbon atoms in the aryl group is not particularly limited, but is preferably 6 to 20, and more preferably 6 to 10. ｂ３ The aryl group in R is most preferably a phenyl group. ｂ３ The heteroaryl group preferably contains at least one heteroatom selected from the group consisting of a sulfur atom, a nitrogen atom, and an oxygen atom. The number of heteroatoms contained in the heteroaryl group is preferably 1 to 5, more preferably 1 to 3. The number of carbon atoms in the heteroaryl group is not particularly limited, but is preferably 2 to 20, more preferably 3 to 15. The heteroaryl group may be monocyclic or polycyclic. R ｂ３ Examples of the heteroaryl group include a thienyl group, a furanyl group, a benzothienyl group, a dibenzothienyl group, a benzofuranyl group, a pyrrolyl group, an oxazolyl group, a thiazolyl group, a pyridyl group, an isothiazolyl group, and a thiadiazolyl group.

[0160] R ｂ３ may be a carboxyl group.

[0161] R ｂ３ The ester group is a group containing —COO—, and is preferably an alkoxycarbonyl group or an alkylcarbonyloxy group. The alkyl group contained in the alkoxycarbonyl group or alkylcarbonyloxy group may be either linear or branched. The number of carbon atoms in the alkyl group contained in the alkoxycarbonyl group or alkylcarbonyloxy group is not particularly limited, but is preferably 1 to 10, and more preferably 1 to 6.

[0162] R ｂ３may be a group formed by combining two or more of the above groups. The group formed by combining two or more of the above groups is not particularly limited, but examples thereof include a group formed by combining an ester group with at least one group selected from the group consisting of a halogen atom, an alkyl group, a cycloalkyl group, an alkoxy group, an aryloxy group, an alkylthio group, an arylthio group, an aryl group, a heteroaryl group, and a carboxyl group.

[0163] R ｂ３ can further have one or more substituents, R ｂ３ may have a substituent.

[0164] In formula (b-1), u represents an integer of 0 to (5+2r-s-t). u is preferably an integer of 0 to 4, more preferably an integer of 0 to 2. When u is 2 or more, a plurality of R ｂ３ may be the same or different, and may be bonded to each other to form a ring (which may be a monocyclic or polycyclic ring). ｂ３ and R ｐ１ , R ｂ３ and R ｐ２ , R ｐ１ and R ｐ２ may be bonded to each other to form a ring (which may be a monocyclic or polycyclic ring). ｂ１ Is L ｂ１ may be bonded to the aromatic ring to which

[0165] Specific examples of repeating units having an acid-decomposable group are shown below, but the present invention is not limited to these. In the following structural formula, Me represents a methyl group, and Rx represents H, CH ３ , C.F. ３ or CH ２ Rxa and Rxb each independently represent a linear or branched alkyl group having 1 to 5 carbon atoms; p represents an integer of 0 or more; １ is H, CH ３ , C.F. ３ or CH ２ Z represents a substituent, and when there are a plurality of Z's, they may be the same or different.

[0166]

[0167]

[0168]

[0169]

[0170]

[0171] The content of the repeating units having an acid-decomposable group is preferably 5 mol% or more, more preferably 10 mol% or more, and even more preferably 15 mol% or more, based on the total repeating units in the resin (P), and the content of the repeating units having an acid-decomposable group is preferably 70 mol% or less, more preferably 60 mol% or less, and even more preferably 50 mol% or less, based on the total repeating units in the resin (P).

[0172] The repeating unit having an acid-decomposable group contained in the resin (P) may be one type or two or more types. When the resin (P) contains two or more types of repeating units having an acid-decomposable group, it is preferable that the total content thereof is within the above-mentioned suitable content range.

[0173] (Repeating unit having a phenolic hydroxyl group) The resin (P) preferably contains 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 (Pa1). The resin (P) preferably contains a repeating unit represented by the following formula (Pa1).

[0174]

[0175] In formula (Pa1), R Ａ１ ~R Ａ３ each independently represents a hydrogen atom, an alkyl group, a cycloalkyl group, a halogen atom, a cyano group, or an alkoxycarbonyl group. Ａ represents a single bond or a divalent linking group. Ａ represents an aromatic ring group. Ａ２ and Ar Ａ may be bonded to form a ring. nA represents an integer of 1 to 5.

[0176] The repeating unit represented by formula (Pa1) is preferably a repeating unit different from the repeating unit having an acid-decomposable group described above.

[0177] R in formula (Pa1) 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 Ａ３ The alkyl group represented by may be either linear or branched. The number of carbon atoms in the alkyl group is not particularly limited, but 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. R Ａ１ , R Ａ２ and R Ａ３ The number of carbon atoms in the cycloalkyl group represented by is not particularly limited, but is preferably 3 to 20, and more preferably 5 to 15. Ａ１ , R Ａ２ and R Ａ３ The cycloalkyl group represented by 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. Ａ１ , R Ａ２ and R Ａ３ Examples of the halogen atom represented by R include a fluorine atom, a chlorine atom, a bromine atom, and an iodine atom, and a fluorine atom or an iodine atom is preferred. Ａ１ , R Ａ２ and R Ａ３ The alkyl group contained in the alkoxycarbonyl group represented by the formula (I) may be either linear or branched. The number of carbon atoms in the alkyl group contained in the alkoxycarbonyl group is not particularly limited, but is preferably 1 to 5, and more preferably 1 to 3.

[0178] Ar in formula (Pa1) Ａ represents an aromatic ring group, more specifically, an aromatic ring group having a valence of (nA+1).Ａ The aromatic ring group represented by may be an aromatic hydrocarbon group such as a benzene ring group or a naphthalene ring group, or may be an aromatic heterocyclic group. The aromatic heterocyclic group is preferably a group containing at least one atom selected from the group consisting of a nitrogen atom, an oxygen atom, and a sulfur atom as a ring member. The aromatic heterocyclic group preferably has 4 to 20 ring atoms. The aromatic heterocyclic group preferably has 1 to 18 carbon atoms. When nA 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. Specific examples of the (nA+1)-valent aromatic ring group when nA is an integer of 2 or more include groups obtained by removing any (nA-1) hydrogen atoms from the above-mentioned specific examples of the divalent aromatic ring group. The (nA+1)-valent aromatic ring group may further have a substituent. The substituent that the (nA+1)-valent aromatic ring group may have is not particularly limited, but 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. Ar Ａ preferably represents an aromatic ring group having 6 to 18 carbon atoms, more preferably represents an aromatic hydrocarbon group, and further preferably represents a benzene ring group, a naphthalene ring group or a biphenylene ring group.

[0179] L in formula (Pa1) 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 Ａ４ -, an alkylene group, or a group formed by combining two or more of these groups. Ａ４represents 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 Ａ４ When represents an alkyl group, examples of the alkyl group include alkyl groups having 20 or less carbon atoms, such as a methyl group, an ethyl group, a propyl group, an isopropyl group, an n-butyl group, a sec-butyl group, a hexyl group, a 2-ethylhexyl group, an octyl group, and a dodecyl group, and alkyl groups having 8 or less carbon atoms are preferred.

[0180] R Ａ２ and Ar Ａ may be bonded to form a ring. Ａ２ and Ar Ａ When R Ａ２ and Ar Ａ may be bonded by a single bond or via a linking group. Examples of the linking group include -O-, -S-, -CO-, -CO ２ -, -SO-, -SO ２ -, an alkylene group (preferably having 1 to 5 carbon atoms), an alkenylene group (preferably having 2 to 5 carbon atoms), and a group formed by combining two or more of these.

[0181] The repeating unit represented by formula (Pa1) preferably has a hydroxystyrene structure. Ａ preferably represents a benzene ring group. nA preferably represents an integer of 1 to 3, and more preferably represents 1 or 2.

[0182] Specific examples of the repeating unit represented by formula (Pa1) are shown below, but the present invention is not limited thereto. 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.

[0183]

[0184] The content of repeating units having a phenolic hydroxyl group in the resin (P) is not particularly limited, but is preferably 20 mol% or more, more preferably 30 mol% or more, and even more preferably 40 mol% or more, based on the total repeating units in the resin (P). The content of repeating units having a phenolic hydroxyl group is preferably 90 mol% or less, more preferably 85 mol% or less, and even more preferably 80 mol% or less, based on the total repeating units in the resin (P).

[0185] The repeating unit having a phenolic hydroxyl group contained in the resin (P) may be one type or two or more types. When the resin (P) contains two or more types of repeating units having a phenolic hydroxyl group, it is preferable that the total content thereof is within the above-mentioned suitable content range.

[0186] Resin (P) may contain other repeating units in addition to the repeating unit having a phenolic hydroxyl group and the repeating unit having an acid-decomposable group. Regarding the other repeating units, the contents of paragraphs

[0112] to

[0172] of WO 2022 / 024928 are incorporated by reference.

[0187] Resin (P) can be synthesized according to a conventional method (e.g., radical polymerization). The weight average molecular weight (Mw) of resin (P), as a polystyrene equivalent value measured by GPC, 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 resin (P) 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. 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.

[0188] In the composition of the present invention, the content of resin (P) is preferably 40.0 to 99.9 mass% and more preferably 60.0 to 90.0 mass% based on the total solid content of the composition of the present invention. Resin (P) may be used alone or in combination of two or more. When two or more resins (P) are used, the total content thereof is preferably within the above-mentioned preferred content range.

[0189] [Acid Diffusion Controller (Q)] The composition of the present invention contains an acid diffusion controller (Q). The acid diffusion controller (Q) traps the acid generated from the photoacid generator (C) during exposure and acts as a quencher to suppress the reaction of the acid-decomposable resin in unexposed areas due to excess generated acid. The type of acid diffusion controller (Q) is not particularly limited, and examples include a basic compound (QA), a low-molecular-weight compound (QB) having a nitrogen atom and a group that is cleaved by the action of an acid, and a compound (QC) whose acid diffusion control ability is reduced or eliminated upon irradiation with actinic rays or radiation. Examples of the compound (QC) include an onium salt compound (QD) of an acid that is weaker than the acid (acid (CA)) generated from the photoacid generator (C), and a basic compound (QE) whose basicity is reduced or eliminated upon irradiation with actinic rays or radiation.

[0190] (Basic Compound (QA)) As the basic compound (QA), compounds having structures represented by the following formulae (A) to (E) are preferred.

[0191]

[0192] In formulas (A) and (E), R Ｄ０ , R Ｄ１ and R Ｄ２ may be the same or different, and each independently represents a hydrogen atom, an alkyl group (preferably having 1 to 20 carbon atoms), a cycloalkyl group (preferably having 3 to 20 carbon atoms), or an aryl group (preferably having 6 to 20 carbon atoms). Ｄ１ and R Ｄ２ may be bonded to each other to form a ring. Ｄ０ , R Ｄ１ and R Ｄ２At 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 bond, an amide bond, a carbonyl group, and a sulfonyl group. Ｄ３ , R Ｄ４ , R Ｄ５ and R Ｄ６ may be the same or different, and each independently represents an alkyl group (preferably having 1 to 20 carbon atoms), a cycloalkyl group (preferably having 3 to 20 carbon atoms), or an aryl group (preferably having 6 to 20 carbon atoms). Ｄ３ , R Ｄ４ , R Ｄ５ and R Ｄ６ At least two of R may be bonded to form a ring. Ｄ３ , R Ｄ４ , R Ｄ５ and R Ｄ６ Preferably, each independently represents an alkyl group. In formulas (B), (C), (D) and (E), * represents a bonding position.

[0193] R in formulas (A) and (E) Ｄ０ , R Ｄ１ , R Ｄ２ , R Ｄ３ , R Ｄ４ , R Ｄ５ and R Ｄ６ The alkyl group, cycloalkyl group and aryl group represented by may have a substituent. As for the alkyl group, an aminoalkyl group having 1 to 20 carbon atoms, a hydroxyalkyl group having 1 to 20 carbon atoms, or a cyanoalkyl group having 1 to 20 carbon atoms is preferred as the alkyl group having a substituent. Ｄ０ , R Ｄ１ , R Ｄ２ , R Ｄ３ , R Ｄ４ , R Ｄ５ and R Ｄ６ The alkyl group, cycloalkyl group and aryl group represented by the formula (I) preferably have no substituent (are unsubstituted).

[0194] Examples of the basic compound (QA) include guanidine, aminopyrrolidine, pyrazole, pyrazoline, piperazine, aminomorpholine, aminoalkylmorpholine, and piperidine. The basic compound (QA) may be a compound having at least one structure selected from the group consisting of an imidazole structure, a diazabicyclo structure, an onium hydroxide structure, an onium carboxylate structure, a trialkylamine structure, an aniline structure, and a pyridine structure. The basic compound (QA) may be an alkylamine derivative having at least one structure selected from the group consisting of a hydroxyl group and an ether bond, or an aniline derivative having at least one structure selected from the group consisting of a hydroxyl group and an ether bond.

[0195] The difference between the pKa of the conjugate acid of the basic compound (QA) and the pKa of the acid (CA) (the value obtained by subtracting the pKa of the acid (CA) from the pKa of the conjugate acid of the basic compound (QA)) is preferably 1.00 or more, more preferably 1.00 to 14.00, and even more preferably 2.00 to 13.00. The pKa of the conjugate acid of the basic compound (QA) is, for example, preferably 1.00 to 14.00, and more preferably 1.50 to 13.00.

[0196] (Onium Salt Compound (QD) of an Acid that is Relatively Weaker than the Acid (CA)) The compound (QD) may be a compound that changes into an acid upon irradiation with actinic rays or radiation. The compound (QD) is preferably a compound that changes into an acid having a pKa that is 1.00 or more higher than that of the acid (CA). The difference between the pKa of the acid converted from the compound (QD) and the pKa of the acid (CA) (the value obtained by subtracting the pKa of the acid (CA) from the pKa of the acid converted from the compound (QD)) is preferably 1.00 or more, more preferably 1.00 to 10.00, even more preferably 1.00 to 8.00, and particularly preferably 1.00 to 6.00. The pKa of the acid converted from the compound (QD) is, for example, preferably 0.50 to 10.00, more preferably 1.00 to 8.00, and even more preferably 1.50 to 6.00.

[0197] The compound (QD) is preferably an onium salt compound consisting of an anion and a cation. Examples of the compound (QD) include "M ＋ X － Examples of compounds include compounds (onium salts) represented by the formula "M ＋ represents a cation, and X － represents an anion. ＋ The cation represented by M is not particularly limited. The valence of the cation may be monovalent or divalent or higher. ＋ The explanation, specific examples and preferred ranges of M in the above formula (BA1) are ＋ is the same as

[0198] "M ＋ X － In the compound represented by the formula "X － represents an anion. － The anion represented by is 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.

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

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

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

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

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

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

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

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

[0207] Examples of the non-nucleophilic anion include anions represented by the following formulas (d1-1) to (d1-4), and an anion represented by formula (d1-1) or an anion represented by formula (d1-2) is preferred.

[0208]

[0209] In formula (d1-1), R ５１ represents a hydrocarbon group (for example, an aryl group such as a phenyl group) which may have a substituent (for example, a hydroxyl group).

[0210] In formula (d1-2), Z ２ｃ represents a hydrocarbon group having 1 to 30 carbon atoms which may have a substituent (provided that the carbon atom adjacent to S is not substituted with a fluorine atom). ２ｃThe hydrocarbon group in formula (d1-2) may be linear or branched, or may have a cyclic structure. In addition, a carbon atom in the hydrocarbon group (preferably, a carbon atom that is a ring atom when the hydrocarbon group has a cyclic structure) may be a carbonyl carbon (-CO-). Examples of the hydrocarbon group include a group having a norbornyl group that may have a substituent. The carbon atom forming the norbornyl group may be a carbonyl carbon. Z in formula (d1-2) ２ｃ preferably represents an alkyl group or a cycloalkyl group. ２ｃ In the -SO ３ － It is preferred that the atoms at the α- and β-positions relative to the aryl group do not have fluorine atoms as substituents.

[0211] In formula (d1-3), R ５２ represents an organic group (preferably a hydrocarbon group having a fluorine atom), Y ３ represents a linear, branched, or cyclic alkylene group, an arylene group, or a carbonyl group, and Rf represents a hydrocarbon group.

[0212] In formula (d1-4), R ５３ and R ５４ R each independently represents an organic group (preferably a hydrocarbon group having a fluorine atom). ５３ and R ５４ may be bonded to each other to form a ring.

[0213] The organic anions may be used alone or in combination of two or more.

[0214] Specific examples of the basic compound (QA) include those described in paragraphs

[0132] to

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

[0137] to

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

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

[0156] to

[0163] of WO 2020 / 066824. Specific examples of onium salt compounds (QD) that are weaker acids than the acid generated from a photoacid generator or the like include those described in paragraphs

[0305] to

[0314] of WO 2020 / 158337.

[0215] 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.

[0216] The molecular weight of the acid diffusion controller (Q) is not particularly limited, but is preferably from 100 to 3,000, more preferably from 150 to 2,500, and even more preferably from 200 to 2,000.

[0217] The acid diffusion controller (Q) is also preferably a compound that changes into an acid having a pKa of 0 or more upon irradiation with actinic rays or radiation.

[0218] The content of the acid diffusion controller (Q) in the composition of the present invention is preferably 0.1% by mass or more, more preferably 0.5% by mass or more, and even more preferably 1.0% by mass or more, based on the total solid content of the composition of the present invention. Furthermore, the content of the acid diffusion controller (Q) is preferably 50.0% by mass or less, more preferably 40.0% by mass or less, and even more preferably 30.0% by mass or less, based on the total solid content of the composition of the present invention. Only one type of acid diffusion controller (Q) may be used, or two or more types may be used. When two or more types are used, the total content is preferably within the above-mentioned preferred content range.

[0219] The content of the acid diffusion controller (Q) in the composition of the present invention is 7% by mass or more relative to the content of the photoacid generator (C). The mass ratio of the content of the acid diffusion controller (Q) to the content of the photoacid generator (C) is also referred to as "(Q) / (C)". (Q) / (C) is calculated by (content of the acid diffusion controller (Q) / content of the photoacid generator (C)) x 100(%). When (Q) / (C) is 7% by mass or more, acid diffusion can be suppressed and excellent resist properties can be obtained. (Q) / (C) is more preferably 20% by mass or more, and even more preferably 50% by mass or more. Furthermore, (Q) / (C) is preferably 500% by mass or less, and more preferably 300% by mass or less.

[0220] [Hydrophobic Resin (Resin (T))] The composition of the present invention may further contain a hydrophobic resin (also referred to as "Resin (T)") different from Resin (P). Resin (T) may be a resin that does not contain a repeating unit having an acid-decomposable group. Resin (T) may be a resin that does not contain a repeating unit having a phenolic hydroxyl group. The hydrophobic resin is preferably designed to be unevenly distributed on the surface of the resist film, but unlike surfactants, it does not necessarily need to have a hydrophilic group in the molecule and does not necessarily need to contribute to uniform mixing of polar and non-polar substances.

[0221] The hydrophobic resin contains fluorine atoms, silicon atoms, and CH atoms contained in the side chain portion of the resin in order to be unevenly distributed on the surface layer of the film. ３It is preferable to have one or more of the partial structures, and more preferably two or more. The hydrophobic resin preferably has a hydrocarbon group having 5 or more carbon atoms. These groups may be present in the main chain of the resin or may be substituted on a side chain. Examples of hydrophobic resins include the compounds described in paragraphs

[0275] to

[0279] of WO 2020 / 004306.

[0222] When the composition of the present invention contains a hydrophobic resin, the content of the hydrophobic resin is preferably 0.01 to 20.0 mass% and more preferably 0.1 to 15.0 mass% based on the total solid content of the composition of the present invention. One type of hydrophobic resin may be used, or two or more types may be used. When two or more types are used, the total content thereof is preferably within the above-mentioned preferred content range.

[0223] [Surfactant] The composition of the present invention may contain a surfactant. When a surfactant is contained, a pattern with better adhesion and fewer development defects can be formed. The surfactant is preferably a fluorine-based and / or silicon-based surfactant. Examples of the fluorine-based and / or silicon-based surfactant include the surfactants disclosed in paragraphs

[0218] and

[0219] of WO 2018 / 193954.

[0224] When the composition of the present invention contains a surfactant, the content of the surfactant is preferably 0.0001 to 2.0 mass%, more preferably 0.0005 to 1.0 mass%, and even more preferably 0.1 to 1.0 mass%, based on the total solid content of the composition of the present invention. One type of surfactant may be used, or two or more types may be used. When two or more types are used, the total content thereof preferably falls within the above-mentioned preferred content range.

[0225] [Solvent] The composition of the present invention preferably contains a solvent. The solvent preferably contains (M1) propylene glycol monoalkyl ether carboxylate and (M2) at least one selected from the group consisting of propylene glycol monoalkyl ether, lactate ester, acetate ester, alkoxypropionate ester, linear ketone, cyclic ketone, lactone, and alkylene carbonate. The solvent may further contain components other than components (M1) and (M2).

[0226] 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.

[0227] 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.

[0228] 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.

[0229] [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).

[0230] 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.

[0231] <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 present invention also relates to a pattern forming method. The pattern forming method of the present invention is preferably a pattern forming method comprising the steps of forming an actinic ray- or radiation-sensitive film (typically a resist film) on a substrate using the composition of the present invention, exposing the actinic ray- or radiation-sensitive film, and developing the exposed actinic ray- or radiation-sensitive film using a developer. The procedure of the pattern forming method using the composition of the present invention is not particularly limited, but preferably comprises 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.

[0232] (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.

[0233] 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.

[0234] The composition of the present invention can be applied onto a substrate (e.g., silicon, silicon coated with silicon dioxide) such as those used in the manufacture of integrated circuit elements by an appropriate application method such as a spinner or coater. Spin application using a spinner is preferred. The rotation speed during spin application using a spinner is preferably 1,000 to 3,000 rpm (rotations per minute). After application of the composition of the present invention, the substrate may be dried to form a resist film. If necessary, various undercoating films (inorganic film, organic film, anti-reflective film) may be formed below the resist film.

[0235] 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.

[0236] 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.

[0237] 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.

[0238] (Step 2: Exposure Step) Step 2 is a step of exposing the resist film. Examples of exposure methods include a method in which the formed resist film is irradiated with actinic rays or radiation through a predetermined mask. Examples of actinic rays or radiation include infrared light, visible light, ultraviolet light, far ultraviolet light, extreme ultraviolet light, X-rays, and electron beams, and preferably have a wavelength of 250 nm or less, more preferably 220 nm or less, and far ultraviolet light having a wavelength of 1 to 200 nm, specifically, KrF excimer laser (248 nm), ArF excimer laser (193 nm), F ２ Excimer laser (157 nm), EUV (13.5 nm), X-ray, and electron beam are particularly preferred.

[0239] 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.

[0240] (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).

[0241] 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.

[0242] 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.

[0243] 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.

[0244] 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.

[0245] (Other Steps) The pattern formation method preferably includes, after step 3, a step of cleaning with a rinse liquid.

[0246] 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.

[0247] 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.

[0248] 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).

[0249] 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.

[0250] 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 (parts per trillion) 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.

[0251] 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.

[0252] 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).

[0253] In addition to filter filtration, impurities may be removed using an adsorbent, or a combination of filter filtration and an adsorbent may be used. Known adsorbents can be used as the adsorbent, including inorganic adsorbents such as silica gel and zeolite, and organic adsorbents such as activated carbon. In order to reduce impurities such as metals contained in the various materials, it is necessary to prevent the incorporation of metal impurities during the manufacturing process. Whether metal impurities have been sufficiently removed from the manufacturing equipment can be confirmed by measuring the content of metal components contained in the cleaning solution used to clean the manufacturing equipment. The content of metal components contained in the used cleaning solution is preferably 100 ppt by mass or less, more preferably 10 ppt by mass or less, and even more preferably 1 ppt by mass or less. There is no particular lower limit, and a content of 0 ppt by mass or more is preferred.

[0254] 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.

[0255] <Method for manufacturing an electronic device> This specification also relates to a method for manufacturing an electronic device, including the above-mentioned pattern formation method, and an electronic device manufactured by this manufacturing method. Preferred embodiments of the electronic device of this specification include those installed in electrical and electronic devices (such as home appliances, office automation (OA), media-related devices, optical devices, and communication devices).

[0256] 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.

[0257] The various components used in the resist compositions of the examples and comparative examples are shown below.

[0258] <Resin (P)> MP-1 to MP-8 were used as resin (P). MP-1 to MP-8 contain the repeating units shown in Table 1 below in the amounts shown in Table 1. Table 1 also lists the weight average molecular weight (Mw) and dispersity (Mw / Mn) of each resin. The content of each repeating unit is the content ratio (molar ratio) of each repeating unit to all repeating units contained in each resin. The weight average molecular weight (Mw) and dispersity (Mw / Mn) of the resin were measured by GPC (carrier: tetrahydrofuran (THF)) (amounts converted into polystyrene). The content of the repeating units is １３ Measurement was performed by C-NMR (nuclear magnetic resonance).

[0259]

[0260] The structural formula of the repeating unit is shown below.

[0261]

[0262] <Photoacid Generator (C)> C-1 to C-16 were used as the photoacid generator (C). The structural formulae of C-1 to C-16 are shown below, where Me represents a methyl group.

[0263]

[0264]

[0265] The pKa of the acid (generated acid) generated from the photoacid generator (C) and the molecular weight of the generated acid are shown in Table 2 below. For C-1 to C-6, C-9, and C-12 to C-16, the basic moiety has an amine structure. For C-7, C-8, C-10, and C-11, the basic moiety contains an ionic structure of a sulfonium salt. For C-7, C-8, C-10, and C-11, the basic moiety changes to an acid (acid (QA)) upon irradiation with actinic rays or radiation. The pKa of the conjugate acid of the basic moiety for C-1 to C-6, C-9, and C-12 to C-16, and the pKa of the acid (QA) for C-7, C-8, C-10, and C-11, are shown in Table 2 below. The structural formulas of the generated acids are shown below.

[0266]

[0267]

[0268]

[0269] <Other Photoacid Generators and Acid Diffusion Controllers (Q)> Compounds containing a cation and anion in a molar ratio of 1:1, as shown in Tables 4 and 5 below, were used as photoacid generators other than the photoacid generator (C). Furthermore, compounds containing a cation and anion in a molar ratio of 1:1, as shown in Tables 4 and 5 below, were used as the acid diffusion controller (Q). The structural formulas of the cations and anions are shown below. Me represents a methyl group.

[0270]

[0271] The photoacid generators containing a cation and an anion are compounds that generate an acid upon irradiation with actinic rays or radiation. The acid diffusion controllers (Q) containing a cation and an anion are compounds that change into an acid upon irradiation with actinic rays or radiation. The acids generated from the photoacid generators and the acids converted from the acid diffusion controllers (Q) are the conjugate acids of the anions contained in each compound. The pKa of the conjugate acids of each anion is shown in Table 3 below.

[0272]

[0273] <Hydrophobic Resin> The structural formula, the content (mol %) of each repeating unit, and the weight average molecular weight (Mw) of the hydrophobic resin used are shown below. The content of each repeating unit is the content ratio (molar ratio) of each repeating unit to all repeating units.

[0274]

[0275] <Surfactant> The surfactants used are as follows: W-1: Megafac R08 (manufactured by DIC Corporation)

[0276] <Solvents> The solvents used are as follows: S-1: Propylene glycol monomethyl ether acetate (PGMEA: 1-methoxy-2-acetoxypropane) S-2: Propylene glycol monomethyl ether (PGME: 1-methoxy-2-propanol) S-3: Ethyl lactate S-4: γ-butyrolactone

[0277] <Preparation of Resist Compositions> The components shown in Tables 4 and 5 below were dissolved in the solvents shown in Tables 4 and 5 to prepare solutions with the solid content concentrations shown in Tables 4 and 5. These solutions were then filtered through a polyethylene filter with a pore size of 0.02 μm to prepare resist compositions. The resulting resist compositions were used in the Examples and Comparative Examples. In Tables 4 and 5, the "mass %" column indicates the content (mass ratio) of each component relative to the total solid content in the resist composition. The solid content refers to all components other than the solvent. For resist compositions that used a surfactant, the surfactant content was 0.1 mass %. The "mass ratio" of the solvent refers to the content of each solvent listed in the "Type" column relative to the total solvent (the total amount of the solvents listed in the "Type" column). When two or more solvents were used, the type and mass ratio of each solvent are separated by a " / ". The types and mass ratios correspond from left to right.

[0278]

[0279]

[0280] Examples 1-1 to 1-36, Comparative Examples 1-1 to 1-4 Pattern Formation Method (1): EB Exposure, Alkali Development (EB-Positive) The resist composition was applied to a 6-inch Si wafer that had been previously treated with hexamethyldisilazane (HMDS) using a spin coater Mark 8 manufactured by Tokyo Electron, and then dried on a hot plate at 100°C for 60 seconds to obtain a resist film with a thickness of 100 nm. Note that similar results were obtained even when the Si wafer was replaced with a chromium substrate. The wafer coated with the resist film obtained above was subjected to pattern irradiation using an electron beam lithography system (HL750 manufactured by Hitachi, Ltd., accelerating voltage 50 keV). Writing was performed so as to form a 1:1 line and space. After electron beam lithography, the wafer was heated on a hot plate at 100°C for 60 seconds, developed with a 2.38 mass% aqueous solution of tetramethylammonium hydroxide for 30 seconds, rinsed with pure water, rotated at 4000 rpm for 30 seconds, and then heated at 95°C for 60 seconds to obtain a 1:1 line and space resist pattern with a line width of 50 nm.

[0281] <Performance Evaluation> [Resolution] The cross-sectional shape of the obtained pattern was observed using a scanning electron microscope (S-9380II manufactured by Hitachi, Ltd.). The exposure dose (electron beam irradiation dose) required to resolve a 1:1 line and space resist pattern with a line width of 50 nm was taken as sensitivity (Eop). The limiting resolving power (the minimum line width at which lines and spaces (line:space = 1:1) are separately resolved) at the exposure dose that exhibited the above sensitivity (Eop) was taken as resolution (nm). The smaller this value, the higher the resolution.

[0282] [LWR Performance] The cross-sectional shape of the obtained pattern was observed using a scanning electron microscope (S-9380II manufactured by Hitachi, Ltd.). The exposure dose (electron beam exposure dose) when resolving a 1:1 line and space resist pattern with a line width of 50 nm was taken as the sensitivity (Eop). A line and space pattern with a line width of 50 nm (1:1) resolved at the exposure dose showing the above sensitivity (Eop) was observed from above the pattern using a critical dimension scanning electron microscope (SEM (S-9380II manufactured by Hitachi, Ltd.)). The line width of the pattern was observed at an arbitrary point, and its standard deviation (σ) was calculated. The measurement variation in line width was evaluated using 3σ, and the value of 3σ was taken as the LWR (nm). The smaller the LWR value, the better the LWR performance.

[0283] [Bake Temperature Dependence] The optimal exposure dose was the dose required to reproduce a 1:1 line-and-space pattern with a width of 50 nm after post-exposure baking at 110°C for 90 seconds. Next, after irradiation at the optimal exposure dose for 90 seconds of post-exposure baking at temperatures of 105°C and 115°C, post-baking was performed at two temperatures, +5°C and -5°C relative to the post-baking temperature (i.e., 115°C and 105°C), the resulting line-and-space patterns were measured to determine their line widths L1 and L2. Bake temperature dependence was defined as the change in line width per 1°C of temperature change during baking and calculated using the following formula: Bake temperature dependence (nm / °C) = |L1 - L2| / 10. Evaluation was performed with the following criteria: A indicates a bake temperature dependence of less than 0.1 (nm / °C), B indicates a bake temperature dependence of 0.1 (nm / °C) or greater but less than 0.3 nm, and C indicates a bake temperature dependence of 0.3 (nm / °C) or greater. In practice, it is preferable that the grade be B or higher.

[0284] Table 6 below shows the resist compositions used in each of the Examples and Comparative Examples, as well as the evaluation results of each of the Examples and Comparative Examples.

[0285]

[0286] Examples 2-1 to 2-36, Comparative Examples 2-1 to 2-4 Pattern Formation Method (2): EUV Exposure, Alkali Development (EUV-Positive) The resist composition was applied to a 6-inch Si wafer that had been previously treated with hexamethyldisilazane (HMDS) using a Tokyo Electron Mark 8 spin coater, and then dried on a hot plate at 100°C for 60 seconds to obtain a resist film with a thickness of 100 nm. Note that similar results were obtained even when the Si wafer was replaced with a chrome substrate. The wafer coated with the resist film obtained above was subjected to pattern exposure using an EUV exposure system (Micro Exposure Tool, Exitech, NA (numerical aperture) 0.3, Quadruple, outer sigma 0.68, inner sigma 0.36) and an exposure mask (line / space = 1 / 1). After the exposure, the wafer was heated on a hot plate at 100°C for 90 seconds, immersed in a 2.38% by mass aqueous solution of tetramethylammonium hydroxide (TMAH) for 60 seconds, and then rinsed with water for 30 seconds. Thereafter, the wafer was rotated at 4000 rpm for 30 seconds and heated at 95°C for 60 seconds to obtain a 1:1 line and space resist pattern with a line width of 50 nm.

[0287] <Performance Evaluation> [Resolution] The cross-sectional shape of the obtained pattern was observed using a scanning electron microscope (S-9380II manufactured by Hitachi, Ltd.). The exposure dose (EUV irradiation dose) required to resolve a 1:1 line and space resist pattern with a line width of 50 nm was taken as sensitivity (Eop). The limiting resolving power (the minimum line width at which lines and spaces (line:space = 1:1) are separately resolved) at the exposure dose that exhibited the above sensitivity (Eop) was taken as resolution (nm). The smaller this value, the higher the resolution.

[0288] [LWR Performance] The cross-sectional shape of the obtained pattern was observed using a scanning electron microscope (S-9380II manufactured by Hitachi, Ltd.). The exposure dose (EUV irradiation dose) when resolving a 1:1 line and space resist pattern with a line width of 50 nm was taken as the sensitivity (Eop). A line and space pattern with a line width of 50 nm (1:1) resolved at the exposure dose showing the above sensitivity (Eop) was observed from above the pattern using a critical dimension scanning electron microscope (SEM (S-9380II manufactured by Hitachi, Ltd.)). The line width of the pattern was observed at an arbitrary point, and its standard deviation (σ) was calculated. The measurement variation in line width was evaluated using 3σ, and the value of 3σ was taken as the LWR (nm). The smaller the LWR value, the better the LWR performance.

[0289] [Bake Temperature Dependence] The optimal exposure dose was the dose required to reproduce a 1:1 line and space pattern with a width of 50 nm after post-exposure baking at 110°C for 90 seconds. Next, after irradiation at the optimal exposure dose, post-baking was performed at two temperatures, +5°C and -5°C relative to the post-baking temperature (i.e., 115°C and 105°C), and the resulting line and space patterns were measured to determine their line widths L1 and L2. Bake temperature dependence was defined as the change in line width per 1°C of temperature change during baking and calculated using the following formula: Bake temperature dependence (nm / °C) = |L1 - L2| / 10. The bake temperature dependence was evaluated as follows: A = less than 0.1 (nm / °C); B = 0.1 (nm / °C) or more but less than 0.3 nm; and C = 0.3 (nm / °C). Note that a grade of B or higher is preferable for practical use.

[0290] Table 7 below shows the resist compositions used in each of the Examples and Comparative Examples, as well as the evaluation results of each of the Examples and Comparative Examples.

[0291]

[0292] From the above results, it was found that the resist compositions used in the examples were excellent in resolution and LWR performance, and had little dependency on the bake temperature.

[0293] The present invention can provide an actinic ray-sensitive or radiation-sensitive resin composition and an actinic ray-sensitive or radiation-sensitive film that are excellent in resolution and LWR performance and have little bake temperature dependency during pattern formation, a pattern formation method using the actinic ray-sensitive or radiation-sensitive resin composition, and a method for manufacturing an electronic device.

[0294] 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. 2024-054204) filed on March 28, 2024, the contents of which are incorporated herein by reference.

Claims

1. An actinic ray-sensitive or radiation-sensitive resin composition comprising: a resin; a photoacid generator (C) having, in its molecule, a nonionic acid-generating moiety that decomposes upon irradiation with actinic rays or radiation to generate an acid, and a basic moiety; and an acid diffusion controller (Q), wherein the content of the acid diffusion controller (Q) is 7 mass% or more relative to the content of the photoacid generator (C).

2. The actinic ray- or radiation-sensitive resin composition according to claim 1, wherein the resin contains a repeating unit having a group that is decomposed by the action of an acid to increase polarity.

3. The actinic ray-sensitive or radiation-sensitive resin composition according to claim 1, wherein the resin contains a repeating unit having a phenolic hydroxyl group.

4. The actinic ray-sensitive or radiation-sensitive resin composition according to claim 1, wherein the acid-generating moiety of the photoacid generator (C) contains a group represented by any one of the following formulas (1) to (3): In formula (1), X １１ represents a hydrogen atom or a substituent. １１ represents an alkyl group, a cycloalkyl group, an aryl group, a heteroaryl group, an alkenyl group, a cycloalkenyl group, or an alkynyl group. １１ and R １１ may be bonded to form a ring. * represents the bonding position. In formula (2), X ２１ and X ２２ R each independently represents a hydrogen atom or a substituent. ２１ represents an alkyl group, a cycloalkyl group, an aryl group, a heteroaryl group, an alkenyl group, a cycloalkenyl group, or an alkynyl group. m represents 0 or 1. n represents 0 or 1. * represents a bonding position. X ２１ and X ２２ , X ２１ and R ２１ and X ２２ and R ２１ may be bonded to form a ring. ３１ and X ３２ each independently represents a cyano group, an alkyl group, a cycloalkyl group, an acyl group, an alkoxycarbonyl group, an aryloxycarbonyl group, a heteroaryloxycarbonyl group, an aryl group, a heteroaryl group, an alkenyl group, a cycloalkenyl group, or an alkynyl group. ３１ and X ３２ may be bonded to form a ring. * indicates the bonding position.

5. The actinic ray-sensitive or radiation-sensitive resin composition according to claim 1, wherein the resin contains a repeating unit represented by the following formula (b-1): In formula (b-1), R ｂ１ and R ｂ２ each independently represents a hydrogen atom or an alkyl group. ｂ１ represents a single bond or -C(=O)O-. r represents an integer of 0 to 2. ｐ１ and R ｐ２ R each independently represents a group that is eliminated by the action of an acid. ｂ３ represents a halogen atom, an alkyl group, a cycloalkyl group, an alkoxy group, an aryloxy group, an alkylthio group, an arylthio group, an aryl group, a heteroaryl group, an ester group, a carboxyl group, or a group formed by combining two or more of these. s and t each independently represent an integer of 0 to 4, provided that at least one of s and t is an integer of 1 or greater. u represents an integer of 0 to (5+2r-s-t). R ｐ１ If there are multiple R ｐ１ may be the same or different and may be bonded to each other to form a ring. ｐ２ If there are multiple R ｐ２ may be the same or different and may be bonded to each other to form a ring. ｂ３ If there are multiple R ｂ３ may be the same or different and may be bonded to each other to form a ring. ｂ３ and R ｐ１ , R ｂ３ and R ｐ２ , and R ｐ１ and R ｐ２ may be bonded to each other to form a ring. ｂ１ The aromatic ring to which R is bonded ｂ１ may be combined with 6. The actinic ray-sensitive or radiation-sensitive resin composition according to claim 1, wherein the basic moiety of the photoacid generator (C) contains an ionic structure of a sulfonium salt or an iodonium salt.

7. The actinic ray-sensitive or radiation-sensitive resin composition according to claim 1, wherein the pKa of the acid generated from the acid generation site of the photoacid generator (C) is -2.0 or more and less than 1.

5.

8. The actinic ray-sensitive or radiation-sensitive resin composition according to claim 1, wherein the acid generated from the acid generation site of the photoacid generator (C) is an arylsulfonic acid.

9. The actinic ray-sensitive or radiation-sensitive resin composition according to claim 1, wherein the molecular weight of the acid generated from the acid-generating moiety of the photoacid generator (C) is 250 or more.

10. The actinic ray-sensitive or radiation-sensitive resin composition according to claim 1, wherein the photoacid generator (C) is a compound represented by the following formula (4): In formula (4), X ４１ and X ４２ R each independently represents a hydrogen atom, an alkyl group, a cycloalkyl group, an aryl group, a heteroaryl group, an alkenyl group, a cycloalkenyl group, or an alkynyl group. ４１ represents an alkyl group, a cycloalkyl group, an aryl group, a heteroaryl group, an alkenyl group, a cycloalkenyl group, or an alkynyl group. ４２ represents a substituent. k represents an integer of 0 to 5. When k represents an integer of 2 or more, a plurality of R ４２ may be the same or different, and multiple R ４２ may be bonded to form a ring. ４１ , R ４２ , X ４１ and X ４２ At least one of the amino acids contains a basic site.

11. The actinic ray-sensitive or radiation-sensitive resin composition according to claim 1, wherein the molecular weight of the acid generated from the acid-generating moiety of the photoacid generator (C) is 400 or more.

12. An actinic ray-sensitive or radiation-sensitive film formed from the actinic ray-sensitive or radiation-sensitive resin composition according to any one of claims 1 to 11.

13. A pattern forming method comprising the steps of: forming an actinic ray-sensitive or radiation-sensitive film on a substrate using the actinic ray-sensitive or radiation-sensitive resin composition according to any one of claims 1 to 11; exposing the actinic ray-sensitive or radiation-sensitive film; and developing the exposed actinic ray-sensitive or radiation-sensitive film using a developer.

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

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