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 is: an actinic ray-sensitive or radiation-sensitive resin composition containing a resin, a photoacid generator, and acid diffusion control agents, wherein at least one of the acid diffusion control agents contains a compound having a specific structure, and the content of the compound having the specific structure is 0.5 mass % or more with respect to the total solid content of the actinic ray-sensitive or radiation-sensitive resin composition. Also provided are 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.

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 resist material containing one or more compounds having an amine oxide structure as a basic component.

[0005] Japanese Patent Application Publication No. 2008-102383

[0006] Recently, the performance required of resist compositions has become higher. In particular, there is a demand for improved line width roughness (LWR) performance when forming fine patterns. LWR performance refers to the ability to reduce the LWR of a pattern. In addition, there is a demand for excellent stability of pattern characteristics over time (hereinafter also referred to as "PCD stability") relative to the time from application of the resist composition to exposure (PCD: Post Coating Delay). The more excellent the PCD stability, the smaller the change in pattern characteristics relative to the time from application of the resist composition to exposure, and therefore the better.

[0007] An object of the present invention is to provide an actinic ray-sensitive or radiation-sensitive resin composition that has excellent LWR performance and excellent PCD stability. Another object of the present invention is to provide an actinic ray-sensitive or radiation-sensitive film, a pattern formation method, and a method for manufacturing an electronic device using the actinic ray-sensitive or radiation-sensitive resin composition.

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

[0009] [1] An actinic ray-sensitive or radiation-sensitive resin composition containing a resin, a photoacid generator, and an acid diffusion controller, wherein the acid diffusion controller contains a compound represented by the following formula (1), and the content of the compound represented by formula (1) is 0.5 mass % or more based on the total solid content of the actinic ray-sensitive or radiation-sensitive resin composition:

[0010]

[0011] In formula (1), A １ represents a nitrogen-containing aromatic heterocycle. １may have a substituent. [2] The actinic ray-sensitive or radiation-sensitive resin composition according to [1], wherein the compound represented by formula (1) does not have at least one selected from the group consisting of a sulfonate anion and a carboxylate anion. [3] The actinic ray-sensitive or radiation-sensitive resin composition according to [1] or [2], wherein the resin contains a repeating unit having a group that decomposes under the action of an acid and increases polarity. [4] The actinic ray-sensitive or radiation-sensitive resin composition according to any one of [1] to [3], wherein the resin contains a repeating unit having a phenolic hydroxyl group. [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 Rｐ１ , R ｂ３ and R ｐ２ , and R ｐ１ and R ｐ２ may be bonded to each other to form a ring. ｂ１ Is L ｂ１ [6] The actinic ray-sensitive or radiation-sensitive resin composition according to any one of [1] to [5], wherein the content of the compound represented by formula (1) is 2 mass % or more based on the total solid content of the actinic ray-sensitive or radiation-sensitive resin composition. [7] The actinic ray-sensitive or radiation-sensitive resin composition according to any one of [1] to [6], wherein the compound represented by formula (1) is a compound represented by formula (2):

[0014]

[0015] In formula (2), R ａ１ , R ａ２ , R ａ３ , R ａ４ and R ａ５ R each independently represents a hydrogen atom or a substituent. ａ１ , R ａ２ , R ａ３ , R ａ４ and R ａ５ At least two of the R in the formula (2) may be bonded to form a ring. ａ１ , R ａ２ , R ａ３ , R ａ４ and R ａ５ each independently represent a hydrogen atom, a halogen atom, an alkyl group, a cycloalkyl group, an aryl group, a heteroaryl group, an alkenyl group, an alkynyl group, an alkoxy group, a cycloalkyloxy group, an aryloxy group, a heteroaryloxy group, an alkoxycarbonyl group, a cycloalkyloxycarbonyl group, an aryloxycarbonyl group, a heteroaryloxycarbonyl group, or a group represented by the following formula (3):

[0016]

[0017] In formula (3), L １ is a single bond, —O—, —S— or —NRＣ１ - represents. Ｃ１ represents a hydrogen atom or a substituent. ２ is -C(=O)-, -S(=O)- or -S(=O) ２ - represents. １ represents a group represented by the following formula (T-1), an alkenyl group, or an alkynyl group. * represents a bonding position.

[0018]

[0019] In formula (T-1), k1 and k2 each independently represent 0 or 1. Ｔ１ and R Ｔ２ each independently represents a hydrogen atom or a substituent. Ｔ１ represents an aryl group or a heteroaryl group. # represents a bonding position. [9] The actinic ray-sensitive or radiation-sensitive resin composition according to any one of [1] to [8], wherein the molecular weight of the compound represented by formula (1) is 250 or more.

[10] The actinic ray-sensitive or radiation-sensitive resin composition according to any one of [1] to [9], wherein the pKa of the acid generated by decomposition of the photoacid generator is -2.0 or more and less than 1.5.

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

[10] , wherein the acid generated by decomposition of the photoacid generator is an arylsulfonic acid.

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

[11] , wherein the compound represented by formula (1) is a compound having a group represented by formula (3):

[0020]

[0021] In formula (3), L １ is a single bond, —O—, —S— or —NR Ｃ１ - represents. Ｃ１ represents a hydrogen atom or a substituent. ２ is -C(=O)-, -S(=O)- or -S(=O) ２ - represents. １ represents a group represented by the following formula (T-1), an alkenyl group, or an alkynyl group. * represents a bonding position.

[0022]

[0023] In formula (T-1), k1 and k2 each independently represent 0 or 1. Ｔ１ and R Ｔ２ each independently represents a hydrogen atom or a substituent. Ｔ１ represents an aryl group or a heteroaryl group. # represents a bonding position.

[13] R in the above formula (2) ａ１ , R ａ２ , R ａ３ , R ａ４ and R ａ５ each independently represents a hydrogen atom, a halogen atom, an alkyl group, an aryl group, a heteroaryl group, an alkenyl group, an alkynyl group, an alkoxy group, an aryloxy group, a heteroaryloxy group, or a group represented by the above formula (3), and R ａ１ , R ａ２ , R ａ３ , R ａ４ and R ａ５ wherein at least one of the groups represents a group represented by formula (3).

[14] 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

[13] .

[15] 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

[13] , exposing the actinic ray-sensitive or radiation-sensitive film to light, and developing the exposed actinic ray-sensitive or radiation-sensitive film with a developer.

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

[15] .

[0024] The present invention can provide an actinic ray-sensitive or radiation-sensitive resin composition having excellent LWR performance and excellent PCD stability. The present invention can also provide an actinic ray-sensitive or radiation-sensitive film, a pattern forming method, and a method for manufacturing an electronic device using the actinic ray-sensitive or radiation-sensitive resin composition.

[0025] 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.

[0026] 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.

[0027] 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.

[0028] 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).

[0029] 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:

[0030] (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.).

[0031] 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".

[0032] 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).

[0033] 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.

[0034] 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.

[0035] 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.

[0036] <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, and an acid diffusion controller, wherein the acid diffusion controller contains a compound represented by the following formula (1), and the content of the compound represented by formula (1) is 0.5 mass % or more based on the total solids content of the actinic ray-sensitive or radiation-sensitive resin composition.

[0037]

[0038] In formula (1), A １ represents a nitrogen-containing aromatic heterocycle. １ may have a substituent.

[0039] The mechanism by which the composition of the present invention provides the above-mentioned effects has not been clarified, but the inventors have hypothesized it as follows. However, the present invention is not limited by the hypothetical mechanism below. In the present invention, it is believed that by using a specific amount or more of the compound represented by formula (1) as an acid diffusion controller, the distribution of the materials is made uniform through appropriate interactions, thereby achieving the above-mentioned effects.

[0040] 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.

[0041] The composition of the present invention contains at least a resin, a photoacid generator, and an acid diffusion controller. The resin, photoacid generator, and acid diffusion controller may be different compounds, or one compound may serve as at least two of the resin, photoacid generator, and acid diffusion controller. However, it is preferable that the resin, photoacid generator, and acid diffusion controller are different compounds.

[0042] [Acid Diffusion Controller] The composition of the present invention contains an acid diffusion controller. The acid diffusion controller traps the acid generated from the photoacid generator upon exposure and can act as a quencher that suppresses the reaction of the acid-decomposable resin in unexposed areas due to excess generated acid. The acid diffusion controller contained in the composition of the present invention includes a compound represented by the following formula (1):

[0043]

[0044] In formula (1), A １ represents a nitrogen-containing aromatic heterocycle. １ may have a substituent.

[0045] A in formula (1) １ represents a nitrogen-containing aromatic heterocycle. １ The nitrogen-containing aromatic heterocycle represented by the formula (I) may be a monocycle or a polycycle. １ The number of carbon atoms in the nitrogen-containing aromatic heterocycle represented by the formula (I) is not particularly limited, but is preferably 2 to 20, more preferably 3 to 15, and even more preferably 4 to 14. １ The number of ring atoms of the nitrogen-containing aromatic heterocycle represented by the formula (I) is not particularly limited, but is preferably 3 to 30, more preferably 4 to 20, and even more preferably 5 to 15. １ The nitrogen-containing aromatic heterocycle represented by the formula (1) may further contain a heteroatom (for example, at least one heteroatom selected from the group consisting of a nitrogen atom, an oxygen atom, and a sulfur atom) as a ring member atom in addition to the nitrogen atom described in formula (1). １Examples of the nitrogen-containing aromatic heterocycle represented by the formula (I) include five-membered nitrogen-containing aromatic heterocycles such as imidazole, pyrazole, oxazole, isoxazole, thiazole, isothiazole, triazole, oxadiazole, thiadiazole, dioxazole, dithiazole, and tetrazole, and six-membered nitrogen-containing aromatic heterocycles such as pyridine, pyrazine, pyrimidine, pyridazine, triazine, and oxazine.

[0046] Also, A １ The nitrogen-containing aromatic heterocycle represented by the formula (I) is selected from the group consisting of the five-membered nitrogen-containing aromatic heterocycle and the six-membered nitrogen-containing aromatic heterocycle, the five-membered nitrogen-containing aromatic heterocycle, the six-membered nitrogen-containing aromatic heterocycle, aromatic hydrocarbons (for example, monocyclic or polycyclic aromatic hydrocarbons having 6 to 15 carbon atoms such as benzene and naphthalene), cycloalkanes (for example, monocyclic or polycyclic cycloalkanes having 3 to 12 carbon atoms such as cyclopentane and cyclohexane), cycloalkenes (for example, monocyclic or polycyclic cycloalkene having 3 to 12 carbon atoms such as cyclohexene), non-aromatic heterocycles (for example, pyrrolidine, pyridine), and 6-membered non-aromatic heterocycles such as morpholine, piperidine, piperazine, tetrahydropyran, etc.) (e.g., indole, isoindole, benzimidazole, benzotriazole, benzoxazole, benzothiazole, purine, quinazoline, quinoxaline, cinnoline, pteridine, acridine, quinoline, isoquinoline, etc.).

[0047] A １ (A １ The nitrogen-containing aromatic heterocycle represented by the following formula (A) may have a substituent. １ The substituent that A may have is not particularly limited, and examples thereof include the aforementioned substituent T. １The substituent that may be substituted is preferably at least one selected from the group consisting of a halogen atom, an alkyl group, a cycloalkyl group, an aryl group, a heteroaryl group, an alkenyl group, an alkynyl group, an alkoxy group, a cycloalkyloxy group, an aryloxy group, a heteroaryloxy group, an alkoxycarbonyl group, a cycloalkyloxycarbonyl group, an aryloxycarbonyl group, a heteroaryloxycarbonyl group, and a group represented by the following formula (3):

[0048]

[0049] In formula (3), L １ is a single bond, —O—, —S— or —NR Ｃ１ - represents. Ｃ１ represents a hydrogen atom or a substituent. ２ is -C(=O)-, -S(=O)- or -S(=O) ２ - represents. １ represents a group represented by the following formula (T-1), an alkenyl group, or an alkynyl group. * represents a bonding position.

[0050]

[0051] In formula (T-1), k1 and k2 each independently represent 0 or 1. Ｔ１ and R Ｔ２ each independently represents a hydrogen atom or a substituent. Ｔ１ represents an aryl group or a heteroaryl group. # represents the bonding position.

[0052] A １ The halogen atom as a substituent that may be possessed by is preferably a fluorine atom, a chlorine atom, a bromine atom or an iodine atom.

[0053] A １The alkyl group as a substituent that may be present may be either linear or branched. The number of carbon atoms in the alkyl group is not particularly limited, but is preferably 1 to 20, may be 1 to 10, or may be 1 to 5. The alkyl group may have a substituent. 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, a t-butyl group, and a trifluoromethyl group.

[0054] A １ The explanation, specific examples and preferred ranges of the alkyl groups contained in the alkoxy group and alkoxycarbonyl group as the substituents that may be contained in A are given in the above. １ The alkyl group is the same as the alkyl group which may be a substituent on the group.

[0055] A １ The cycloalkyl group as a substituent that may be present may be monocyclic or polycyclic. The cycloalkyl group preferably has 3 to 20 carbon atoms, and may have 4 to 15 carbon atoms. 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. The cycloalkyl group may have a substituent. One or more methylene groups constituting the cycloalkane ring of the cycloalkyl group may be replaced with a heteroatom such as an oxygen atom, a carbonyl group, a sulfonyl group, or a group containing a heteroatom such as an ester bond, or a vinylidene group. Furthermore, in the cycloalkyl group, one or more ethylene groups constituting the cycloalkane ring may be replaced with a vinylene group.

[0056] A １ The explanation, specific examples and preferred ranges of the cycloalkyloxy group and the cycloalkyl group contained in the cycloalkyloxycarbonyl group as the substituents that may be contained in A are given in the above. １ is the same as the cycloalkyl group which may be substituted by the group represented by the formula (1).

[0057] A １The aryl group as a substituent that may be substituted by is preferably an aryl group having 6 to 20 carbon atoms, more preferably an aryl group having 6 to 15 carbon atoms, further preferably a phenyl group or a naphthyl group, and particularly preferably a phenyl group. The aryl group may have a substituent.

[0058] A １ The explanation, specific examples and preferred ranges of the aryl group contained in the aryloxy group and aryloxycarbonyl group as the substituents that may be contained in A are given in the above. １ The aryl group is the same as the aryl group which may be a substituent on the group.

[0059] A １ The heteroaryl group as a substituent that may be present is preferably a heteroaryl group having 3 to 19 carbon atoms, and may be a heteroaryl group having 4 to 14 carbon atoms. The heteroaryl group preferably contains at least one heteroatom selected from the group consisting of an oxygen atom, a sulfur atom, and a nitrogen atom as a ring member. The heteroaryl group preferably has 4 to 20 ring atoms, and may have 5 to 15 ring atoms. Examples of heteroaryl groups include a pyrrolyl group, a furanyl group, a thiophenyl group, an indolyl group, a benzofuranyl group, and a benzothiophenyl group. The heteroaryl group may have a substituent.

[0060] A １ The heteroaryloxy group and the heteroaryl group contained in the heteroaryloxycarbonyl group as the substituents that may be contained in A are described in detail in the above. １ The heteroaryl group is the same as the heteroaryl group which may be substituted by the group represented by the formula (1).

[0061] A １ The alkenyl group as a substituent that may be present may be linear or branched, and is preferably an alkenyl group having 2 to 20 carbon atoms, and may also be an alkenyl group having 2 to 15 carbon atoms. Examples of the alkenyl group include a vinyl group and an allyl group. The alkenyl group may have a substituent.

[0062] A １The alkynyl group as a substituent that may be substituted may be linear or branched, and is preferably an alkynyl group having 2 to 20 carbon atoms, and may also be an alkynyl group having 2 to 15 carbon atoms. Examples of the alkynyl group include an ethynyl group and a propargyl group. The alkynyl group may have a substituent.

[0063] L in formula (3) １ is a single bond, —O—, —S— or —NR Ｃ１ - represents. Ｃ１ represents a hydrogen atom or a substituent, and preferably represents a hydrogen atom. Ｃ１ The substituent represented by is not particularly limited, and examples thereof include the aforementioned substituent T. １ is -O- or -NR Ｃ１ It is preferred that it represents -.

[0064] L in formula (3) ２ is -C(=O)-, -S(=O)- or -S(=O) ２ -, -C(=O)- or -S(=O) ２ It is preferred that it represents -.

[0065] T in formula (3) １ represents a group represented by formula (T-1), an alkenyl group, or an alkynyl group, and preferably represents a group represented by formula (T-1).

[0066] T １ The alkenyl group represented by the formula (I) may be linear or branched, and is preferably an alkenyl group having 2 to 20 carbon atoms, more preferably an alkenyl group having 2 to 15 carbon atoms, and even more preferably an alkenyl group having 2 to 10 carbon atoms. Examples of the alkenyl group include a vinyl group and an allyl group. The alkenyl group may have a substituent.

[0067] T １ The alkynyl group represented by the formula (I) may be linear or branched, and is preferably an alkynyl group having 2 to 20 carbon atoms, more preferably an alkynyl group having 2 to 15 carbon atoms, and even more preferably an alkynyl group having 2 to 10 carbon atoms. Examples of the alkynyl group include an ethynyl group and a propargyl group. The alkynyl group may have a substituent.

[0068] In formula (T-1), k1 represents 0 or 1.

[0069] In formula (T-1), k2 represents 0 or 1.

[0070] R in formula (T-1) Ｔ１ and R Ｔ２ R each independently represents a hydrogen atom or a substituent. Ｔ１ and R Ｔ２ The substituent represented by the formula (I) is not particularly limited, and examples thereof include an alkyl group, an alkoxy group, an alkylthio group, a cycloalkyl group, a cycloalkyloxy group, a cycloalkylthio group, an aryl group, a heteroaryl group, an aryloxy group, and an arylthio group.

[0071] R Ｔ１ and R Ｔ２ The alkyl group represented by the formula (I) may be either linear or branched. The number of carbon atoms in the alkyl group is not particularly limited, but is preferably 1 to 20, more preferably 1 to 10, and particularly preferably 1 to 5. The alkyl group may have a substituent. 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, a t-butyl group, and a trifluoromethyl group. R Ｔ１ and R Ｔ２ The explanation, specific examples and preferred ranges of the alkyl groups contained in the alkoxy groups and alkylthio groups represented by the formula Ｔ１ and R Ｔ２ It is the same as the alkyl group represented by the following formula:

[0072] R Ｔ１ and R Ｔ２The cycloalkyl group represented by the formula (I) may be monocyclic or polycyclic. The cycloalkyl group preferably has 3 to 20 carbon atoms, more preferably 4 to 15 carbon atoms. 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. The cycloalkyl group may have a substituent. One or more methylene groups constituting the cycloalkane ring of the cycloalkyl group may be replaced with a heteroatom such as an oxygen atom, a carbonyl group, a sulfonyl group, or a group having a heteroatom such as an ester bond, or a vinylidene group. Furthermore, in the cycloalkyl group, one or more ethylene groups constituting the cycloalkane ring may be replaced with a vinylene group. R Ｔ１ and R Ｔ２ The explanation, specific examples and preferred ranges of the cycloalkyl group contained in the cycloalkyloxy group and cycloalkylthio group represented by the formula Ｔ１ and R Ｔ２ It is the same as the cycloalkyl group represented by the following formula:

[0073] R Ｔ１ and R Ｔ２ The aryl group represented by the formula (I) is preferably an aryl group having 6 to 20 carbon atoms, more preferably an aryl group having 6 to 15 carbon atoms, further preferably a phenyl group or a naphthyl group, and particularly preferably a phenyl group. The aryl group may have a substituent. Ｔ１ and R Ｔ２ The explanation, specific examples and preferred ranges of the aryl group contained in the aryloxy group and arylthio group represented by the formula Ｔ１ and R Ｔ２ It is the same as the aryl group represented by the following formula:

[0074] R Ｔ１ and R Ｔ２The heteroaryl group represented by the formula (I) is preferably a heteroaryl group having 3 to 19 carbon atoms, and more preferably a heteroaryl group having 4 to 14 carbon atoms. The heteroaryl group preferably contains at least one heteroatom selected from the group consisting of an oxygen atom, a sulfur atom, and a nitrogen atom as a ring member. The heteroaryl group preferably has 4 to 20 ring atoms, and more preferably 5 to 15 ring atoms. Examples of heteroaryl groups include a pyrrolyl group, a furanyl group, a thiophenyl group, an indolyl group, a benzofuranyl group, and a benzothiophenyl group. The heteroaryl group may have a substituent.

[0075] R Ｔ１ and R Ｔ２ preferably represents a hydrogen atom.

[0076] Ar in formula (T-1) Ｔ１ represents an aryl group or a heteroaryl group. Ｔ１ The aryl group represented by the formula (I) is preferably an aryl group having 6 to 20 carbon atoms, more preferably an aryl group having 6 to 15 carbon atoms, still more preferably a phenyl group or a naphthyl group, and particularly preferably a phenyl group. The aryl group may have a substituent.

[0077] Ar Ｔ１ The heteroaryl group represented by the formula (I) is preferably a heteroaryl group having 3 to 19 carbon atoms, and more preferably a heteroaryl group having 4 to 14 carbon atoms. The heteroaryl group preferably contains at least one heteroatom selected from the group consisting of an oxygen atom, a sulfur atom, and a nitrogen atom as a ring member. The heteroaryl group preferably has 4 to 20 ring atoms, and more preferably 5 to 15 ring atoms. Examples of heteroaryl groups include a pyrrolyl group, a furanyl group, a thiophenyl group, an indolyl group, a benzofuranyl group, and a benzothiophenyl group. The heteroaryl group may have a substituent.

[0078] Ar Ｔ１ preferably represents an aryl group.

[0079] In one preferred embodiment of the composition of the present invention, the compound represented by formula (1) is a compound having a group represented by formula (3).

[0080] The compound represented by formula (1) is preferably a compound represented by the following formula (2):

[0081]

[0082] In formula (2), R ａ１ , R ａ２ , R ａ３ , R ａ４ and R ａ５ R each independently represents a hydrogen atom or a substituent. ａ１ , R ａ２ , R ａ３ , R ａ４ and R ａ５ At least two of these may be bonded to form a ring.

[0083] R in formula (2) ａ１ , R ａ２ , R ａ３ , R ａ４ and R ａ５ The description, specific examples and preferred ranges of the substituents represented by A １ The substituents are the same as those that may be possessed by the group.

[0084] R in formula (2) ａ１ , R ａ２ , R ａ３ , R ａ４ and R ａ５ each independently represents a hydrogen atom, a halogen atom, an alkyl group, a cycloalkyl group, an aryl group, a heteroaryl group, an alkenyl group, an alkynyl group, an alkoxy group, a cycloalkyloxy group, an aryloxy group, a heteroaryloxy group, an alkoxycarbonyl group, a cycloalkyloxycarbonyl group, an aryloxycarbonyl group, a heteroaryloxycarbonyl group, or a group represented by the above formula (3).

[0085] R in formula (2) ａ１ , R ａ２ , R ａ３ , R ａ４ and R ａ５each independently represents a hydrogen atom, a halogen atom, an alkyl group, an aryl group, a heteroaryl group, an alkenyl group, an alkynyl group, an alkoxy group, an aryloxy group, a heteroaryloxy group, or a group represented by the above formula (3), and R ａ１ , R ａ２ , R ａ３ , R ａ４ and R ａ５ It is more preferable that at least one of the groups represented by the formula (3) is a group represented by the formula (3).

[0086] R in formula (2) ａ１ , R ａ２ , R ａ３ , R ａ４ and R ａ５ At least two of R may be bonded to form a ring. ａ１ , R ａ２ , R ａ３ , R ａ４ and R ａ５ The ring formed by bonding at least two of these (also referred to as "ring X") may be an aromatic ring or a non-aromatic ring. Examples of aromatic rings include aromatic carbon rings and aromatic heterocycles. Examples of non-aromatic rings include non-aromatic carbon rings and non-aromatic heterocycles. Ring X may be a monocycle or a polycycle. Ring X may have a substituent. The substituent that ring X may have is not particularly limited, and examples thereof include the aforementioned substituent T.

[0087] The case where ring X is a non-aromatic carbocyclic ring will be described below. The non-aromatic carbocyclic ring may be saturated or unsaturated. The number of carbon atoms in the non-aromatic carbocyclic ring is not particularly limited, but is preferably 3 to 30, more preferably 3 to 20, and even more preferably 3 to 12. The non-aromatic carbocyclic ring is preferably a cycloalkane ring or a cycloalkene ring. The non-aromatic carbocyclic ring may be a monocyclic hydrocarbon or a polycyclic hydrocarbon.

[0088] Examples of monocyclic hydrocarbons include cycloalkanes having 3 to 12 carbon atoms, such as cyclopentane, cyclohexane, cycloheptane, and cyclooctane, and cycloalkenes having 3 to 12 carbon atoms, such as cyclohexene.

[0089] Examples of polycyclic hydrocarbons include cycloalkanes having 6 to 20 carbon atoms, such as norbornane, tetracyclodecane, tetracyclododecane, and adamantane, and cycloalkenes having 6 to 20 carbon atoms, such as norbornene. The non-aromatic carbocyclic ring may have a substituent. One or more methylene groups constituting the ring of the non-aromatic carbocyclic ring may be substituted with at least one bond selected from the group consisting of a carbonyl bond, an ester bond, an amide bond, and a sulfone bond.

[0090] The case where ring X is a non-aromatic heterocycle will be described below. The non-aromatic heterocycle may be saturated or unsaturated. The non-aromatic heterocycle preferably contains at least one heteroatom selected from the group consisting of a nitrogen atom, an oxygen atom, and a sulfur atom. The number of ring atoms in the non-aromatic heterocycle is not particularly limited, but is preferably 3 to 20, more preferably 3 to 15, and even more preferably 3 to 12. The number of carbon atoms in the non-aromatic heterocycle is not particularly limited, but is preferably 1 to 18, more preferably 2 to 15, and even more preferably 2 to 10. The non-aromatic heterocycle may be monocyclic or polycyclic. Examples of non-aromatic heterocycles include 5-membered non-aromatic heterocycles such as pyrrolidine, pyrroline, 2-oxazolidone, tetrahydrofuran, and tetrahydrothiophene, and 6-membered non-aromatic heterocycles such as morpholine, piperidine, piperazine, and tetrahydropyran. The non-aromatic heterocycle may also be a fused ring having a structure in which the 5-membered non-aromatic heterocycle or the 6-membered non-aromatic heterocycle is fused with at least one selected from the group consisting of a cycloalkane (e.g., a monocyclic or polycyclic cycloalkane having 3 to 12 carbon atoms, such as cyclopentane or cyclohexane), a cycloalkene (e.g., a monocyclic or polycyclic cycloalkene having 3 to 12 carbon atoms, such as cyclohexene), the 5-membered non-aromatic heterocycle, and the 6-membered non-aromatic heterocycle. The non-aromatic heterocycle may have a substituent. One or more methylene groups constituting the ring of the non-aromatic heterocycle may be replaced with at least one selected from the group consisting of a carbonyl bond, an ester bond, an amide bond, and a sulfone bond. When the bond between adjacent atoms contained in the non-aromatic heterocycle is a single bond, the single bond may be replaced with a multiple bond (e.g., a double bond).

[0091] The case where ring X is an aromatic carbocyclic ring will be described below. The number of carbon atoms in the aromatic carbocyclic ring is not particularly limited, but is preferably 6 to 30, more preferably 6 to 20, and even more preferably 6 to 15. The aromatic carbocyclic ring may be monocyclic or polycyclic. The aromatic carbocyclic ring is more preferably a benzene ring or a naphthalene ring. The aromatic carbocyclic ring may also be a fused ring having a structure in which an aromatic hydrocarbon (e.g., a monocyclic or polycyclic aromatic hydrocarbon having 6 to 15 carbon atoms, such as benzene or naphthalene) is fused with at least one selected from the group consisting of a cycloalkane (e.g., a monocyclic or polycyclic cycloalkane having 3 to 12 carbon atoms, such as cyclopentane or cyclohexane), a cycloalkene (e.g., a monocyclic or polycyclic cycloalkene having 3 to 12 carbon atoms, such as cyclohexene), or a non-aromatic heterocyclic compound (e.g., the above-mentioned 5-membered non-aromatic heterocyclic ring, the above-mentioned 6-membered non-aromatic heterocyclic ring, etc.). The aromatic carbocyclic ring may have a substituent.

[0092] The case where ring X is an aromatic heterocycle will be described. 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. 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. The number of carbon atoms in the aromatic heterocycle is not particularly limited, but is preferably 2 to 20, more preferably 3 to 15, and even more preferably 4 to 14. The aromatic heterocycle may be monocyclic or polycyclic. Examples of aromatic heterocycles include 5-membered aromatic heterocycles such as pyrrole, imidazole, pyrazole, oxazole, isoxazole, thiazole, isothiazole, triazole, thiophene, furan, oxadiazole, thiadiazole, dioxazole, dithiazole, and tetrazole, and 6-membered aromatic heterocycles such as pyridine, pyrazine, pyrimidine, pyridazine, triazine, thiazine, and oxazine. Furthermore, the aromatic heterocycle may be a fused ring (e.g., indole, isoindole, benzimidazole, benzotriazole, purine, quinazoline, quinoxaline, cinnoline, pteridine, acridine, carbazole, benzofuran, benzothiophene, quinoline, isoquinoline, etc.) having a structure in which the 5-membered aromatic heterocycle or the 6-membered aromatic heterocycle is fused with at least one selected from the group consisting of the 5-membered aromatic heterocycle, the 6-membered aromatic heterocycle, 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 cycloalkene having 3 to 12 carbon atoms, such as cyclohexene), and non-aromatic heterocycles (e.g., the 5-membered non-aromatic heterocycle, the 6-membered non-aromatic heterocycle, etc.). The aromatic heterocycle may have a substituent.

[0093] It is preferable that the compound represented by formula (1) does not have at least one selected from the group consisting of a sulfonate anion and a carboxylate anion. In an embodiment in which the compound represented by formula (1) does not have a sulfonate anion, the compound represented by formula (1) is A １As a substituent of -SO ３ － In an embodiment in which the compound represented by formula (1) does not have a carboxylate anion, the compound represented by formula (1) may be A １ -COO as a substituent － Since sulfonate anions and carboxylate anions have structures that strongly interact with each other, when the compound represented by formula (1) does not have at least one selected from the group consisting of sulfonate anions and carboxylate anions, aggregation of the compound represented by formula (1) and the like is suppressed, and the effects of the present invention are more easily exhibited.

[0094] The molecular weight of the compound represented by formula (1) is preferably 150 or more, more preferably 200 or more, even more preferably 250 or more, and particularly preferably 300 or more. If the molecular weight of the compound represented by formula (1) is large, it is less likely to volatilize, and therefore PCD stability is likely to be reduced. Furthermore, the molecular weight of the compound represented by formula (1) is preferably 3000 or less, more preferably 2000 or less, and even more preferably 1000 or less.

[0095] The content of the compound represented by formula (1) in the composition of the present invention is 0.5% by mass or more, preferably 1% by mass or more, more preferably 2% 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 compound represented by formula (1) in the composition of the present invention is preferably 50% by mass or less, more preferably 40% by mass or less, and even more preferably 30% by mass or less, based on the total solid content of the composition of the present invention. The compound represented by formula (1) may be used alone or in combination with two or more other compounds. When two or more compounds are used, the total content thereof preferably falls within the above-mentioned preferred range. The compound represented by formula (1) can be synthesized by synthesizing a nitrogen-containing aromatic compound and then converting it into an oxide using, for example, the method described in Organic Syntheses, Coll. Vol. 4, p. 828 (1963); Vol. 33, p. 79 (1953).

[0096] Specific examples of the compound represented by formula (1) include compounds Q-1 to Q-13 described in the examples below and the following compounds, but the present invention is not limited to these. Me represents a methyl group.

[0097]

[0098]

[0099] <Acid Diffusion Controller Other Than a Compound Represented by Formula (1)> In addition to the compound represented by Formula (1), the composition of the present invention may contain an acid diffusion controller other than a compound represented by Formula (1) (also referred to as "acid diffusion controller (B)"). The type of acid diffusion controller (B) is not particularly limited, and examples thereof include a basic compound (BA), a low-molecular-weight compound (BB) having a nitrogen atom and a group that is cleaved by the action of an acid, and a compound (BC) whose acid diffusion control ability is reduced or eliminated by irradiation with actinic rays or radiation. Examples of the compound (BC) include an onium salt compound (BD) of an acid that is a weaker acid than the acid generated from a photoacid generator or the like, and a basic compound (BE) whose basicity is reduced or eliminated by irradiation with actinic rays or radiation. Specific examples of the basic compound (BA) include those described in paragraphs

[0132] to

[0136] of WO 2020 / 066824. Specific examples of the basic compound (BE) 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 (BB) having a nitrogen atom and having a group that leaves under the action of an acid include those described in paragraphs

[0156] to

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

[0305] to

[0314] of WO 2020 / 158337.

[0100] 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.

[0101] The molecular weight of the acid diffusion controller (B) 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.

[0102] The acid diffusion controller (B) may be a compound that changes into an acid having a pKa of 1.5 or more and less than 10 when irradiated with actinic rays or radiation.

[0103] When the composition of the present invention contains an acid diffusion controller (B) in addition to the compound represented by Formula (1), the content of the acid diffusion controller (B) is less than 100% by mass, more preferably 50% by mass or less, and even more preferably 30% by mass or less, based on the total amount of acid diffusion controllers in the composition of the present invention (the total amount of the compound represented by Formula (1) and the acid diffusion controller (B)). The content of the acid diffusion controller (B) may be 1% by mass or more, based on the total amount of acid diffusion controllers in the composition of the present invention. Only one type of acid diffusion controller (B) 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. It is also preferred that the composition of the present invention does not contain an acid diffusion controller (B).

[0104] [Resin] The composition of the present invention contains a resin (also referred to as "resin (P)"). The resin (P) preferably contains a repeating unit having a group that decomposes under the action of acid and increases in 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.

[0105] (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.

[0106] 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)

[0107] 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 ３ When all of Rx are alkyl groups (linear or branched), １ ~Rx ３ At least two of Rx are preferably methyl groups. １ ~Rx ３ each independently preferably represents a linear or branched alkyl group, and Rx １ ~Rx ３ More preferably, Rx each independently represents a linear alkyl group. １ ~Rx ３ may be bonded to 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 ~Rx３ The aryl group in Rx is preferably an aryl group having 6 to 10 carbon atoms, and examples thereof include a phenyl group, a naphthyl group, and an anthryl group. １ ~Rx ３ The 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 ~Rx ３ 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.

[0108] In formula (Y3), R ３６ ~R ３８ R each independently represents a hydrogen atom or a monovalent organic group. ３７ and R ３８may be bonded to each other to form a ring. Examples of the monovalent organic group include an alkyl group, a cycloalkyl group, an aryl group, an aralkyl group, and an alkenyl group. ３６ is also preferably a hydrogen atom. The alkyl group, cycloalkyl group, aryl group, and aralkyl group may contain a heteroatom such as an oxygen atom and / or a group 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. ３８ The 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.

[0109] 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.

[0110] 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).

[0111]

[0112] 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. ｂ３represents 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 Is L ｂ１ may be bonded to the aromatic ring to which

[0113] 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.

[0114] In formula (b-1), L ｂ１ represents a single bond or —C(═O)O—, and is preferably a single bond.

[0115] 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.

[0116] 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.

[0117] 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.

[0118] 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.

[0119] In formula (b-1), R ｐ２ 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). ｐ２ is converted to R by the action of an acid. ｐ２ is eliminated to produce a carboxyl group.

[0120] 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—. ｂ３The 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.

[0121] R ｂ３ The 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 ｂ３Examples 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.

[0122] R ｂ３ may be a carboxyl group.

[0123] 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.

[0124] R ｂ３ may 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.

[0125] R ｂ３ can further have one or more substituents, R ｂ３ may have a substituent.

[0126] 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 ｐ２may 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

[0127] Specific examples of the repeating unit having an acid-decomposable group include the repeating units described in

[0148] to

[0152] ,

[0163] to

[0166] ,

[0181] and

[0182] of JP-A-2023-35836, but the present invention is not limited thereto.

[0128] 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).

[0129] 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.

[0130] (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 (Pa3):

[0131]

[0132] In formula (Pa3), R １０１ , R １０２ and R １０３ R each independently represents a hydrogen atom, an alkyl group, a cycloalkyl group, a halogen atom, a cyano group, or an alkoxycarbonyl group. １０２ is Ar Ａ may be bonded to form a ring, in which case R １０２ represents a single bond or an alkylene group. Ａrepresents a single bond or a divalent linking group. Ａ represents an aromatic ring group, and k represents an integer of 1 to 5.

[0133] R in formula (Pa3) １０１ , R １０２ and R １０３ R each independently represents a hydrogen atom, an alkyl group, a cycloalkyl group, a halogen atom, a cyano group, or an alkoxycarbonyl group. １０１ , R １０２ and R １０３ 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, more preferably 1 to 5, and particularly preferably 1 to 3. Examples of the alkyl group include a methyl group, an ethyl group, an n-propyl group, an isopropyl group, an n-butyl group, an isobutyl group, and a t-butyl group. １０１ , R １０２ and R １０３ The number of carbon atoms in the cycloalkyl group is not particularly limited, but is preferably 3 to 20, and more preferably 5 to 15. １０１ , R １０２ and R １０３ The cycloalkyl group of R is preferably a monocyclic cycloalkyl group such as a cyclopentyl group or a cyclohexyl group, or a polycyclic cycloalkyl group such as a norbornyl group, a tetracyclodecanyl group, a tetracyclododecanyl group, or an adamantyl group. １０１ , R １０２ and R １０３ Examples of the halogen atom in R include a fluorine atom, a chlorine atom, a bromine atom, and an iodine atom, and a fluorine atom or an iodine atom is preferred. １０１ , R １０２ and R １０３ The alkyl group contained in the alkoxycarbonyl group may be either linear or branched. The number of carbon atoms in the alkyl group contained in the alkoxycarbonyl group is not particularly limited, but is preferably 1 to 5, and more preferably 1 to 3.

[0134] Ar in formula (Pa3) Ａrepresents an aromatic ring group, more specifically, a (k+1)-valent aromatic ring group. When k is 1, the divalent aromatic ring group is preferably an arylene group having 6 to 18 carbon atoms, such as a phenylene group, a tolylene group, a naphthylene group, or an anthracenylene group, or a divalent aromatic ring group containing a heterocycle, such as a thiophene ring, a furan ring, a pyrrole ring, a benzothiophene ring, a benzofuran ring, a benzopyrrole ring, a triazine ring, an imidazole ring, a benzimidazole ring, a triazole ring, a thiadiazole ring, or a thiazole ring. The aromatic ring group may have a substituent. When k is an integer of 2 or more, specific examples of the (k+1)-valent aromatic ring group include groups obtained by removing any (k-1) hydrogen atoms from the above-mentioned specific examples of the divalent aromatic ring group. The (k+1)-valent aromatic ring group may further have a substituent. The substituent that the (k+1)-valent aromatic ring group may have is not particularly limited, and examples thereof include alkyl groups such as methyl, ethyl, propyl, isopropyl, n-butyl, sec-butyl, hexyl, 2-ethylhexyl, octyl, and dodecyl; alkoxy groups such as methoxy, ethoxy, hydroxyethoxy, propoxy, hydroxypropoxy, and butoxy; and aryl groups such as phenyl. Ａ preferably represents an aromatic ring group having 6 to 18 carbon atoms, and more preferably represents a benzene ring group, a naphthalene ring group or a biphenylene ring group.

[0135] L in formula (Pa3) Ａ represents a single bond or a divalent linking group. Ａ The divalent linking group represented by is not particularly limited, but examples thereof include —COO—, —CONR １０４ -, an alkylene group, or a group formed by combining two or more of these groups. １０４ represents a hydrogen atom or an alkyl group. The alkylene group is not particularly limited, but is preferably an alkylene group having 1 to 8 carbon atoms, such as a methylene group, an ethylene group, a propylene group, a butylene group, a hexylene group, or an octylene group. R １０４When represents an alkyl group, examples of the alkyl group include alkyl groups having 20 or less carbon atoms, such as a methyl group, an ethyl group, a propyl group, an isopropyl group, an n-butyl group, a sec-butyl group, a hexyl group, a 2-ethylhexyl group, an octyl group, and a dodecyl group, and alkyl groups having 8 or less carbon atoms are preferred.

[0136] The repeating unit represented by formula (Pa3) preferably has a hydroxystyrene structure. Ａ preferably represents a benzene ring group. k preferably represents an integer of 1 to 3, and more preferably represents 1 or 2.

[0137] Specific examples of repeating units having a phenolic hydroxyl group include, for example, repeating units described in

[0194] to

[0197] of JP-A No. 2023-35836, but the present invention is not limited thereto.

[0138] 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).

[0139] 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.

[0140] 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.

[0141] When the resin (P) contains a repeating unit having a photoacid generating group, the content of the repeating unit having a photoacid generating group is preferably 1 mol% or more, more preferably 3 mol% or more, and particularly preferably 5 mol% or more, based on the total repeating units in the resin (P). Furthermore, the content of the repeating unit having a photoacid generating group is preferably 40 mol% or less, more preferably 30 mol% or less, and particularly preferably 20 mol% or less, based on the total repeating units in the resin (P). It is also preferable that the resin (P) does not contain a repeating unit having a photoacid generating group.

[0142] 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.

[0143] 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.

[0144] [Photoacid Generator] The composition of the present invention contains a photoacid generator. The photoacid generator is a compound that generates an acid upon irradiation with actinic rays or radiation. The photoacid generator may be a compound different from the compound represented by formula (1) or may be the same compound, but is preferably a different compound. The photoacid generator may be a compound different from the resin (P) or may be the same compound.

[0145] The photoacid generator preferably decomposes upon irradiation with actinic rays or radiation to generate an acid. The pKa of the acid generated by decomposition of the photoacid generator is preferably −3.0 or more and less than 3.0, and more preferably −2.0 or more and less than 1.5. The acid generated by decomposition of the photoacid generator is preferably an arylsulfonic acid.

[0146] The photoacid generator may be in the form of a low molecular weight compound or may be incorporated into a resin. Furthermore, a photoacid generator in the form of a low molecular weight compound and a photoacid generator in the form of a resin may be used in combination. When the photoacid generator is in the form of a low molecular weight compound, the molecular weight of the photoacid generator is not particularly limited, but is preferably 100 to 3,000, more preferably 150 to 2,500, and even more preferably 200 to 2,000. When the photoacid generator is incorporated into a resin, it may be incorporated into resin (P) or into a resin different from resin (P). When resin (P) does not have the repeating unit having a photoacid-generating group described above, the composition of the present invention preferably contains a photoacid generator that is a compound different from resin (P). When resin (P) has a repeating unit having a photoacid-generating group, the composition of the present invention may or may not contain a separate photoacid generator. The photoacid generator is preferably in the form of a low molecular weight compound. The photoacid generator is preferably an onium salt.

[0147] Examples of the photoacid generator include "M ＋ X － ", and it is preferably a compound that generates an organic acid upon exposure. Examples of the organic acid include sulfonic acids (aliphatic sulfonic acids, aromatic sulfonic acids, camphorsulfonic acids, etc.), carboxylic acids (aliphatic carboxylic acids, aromatic carboxylic acids, aralkyl carboxylic acids, etc.), carbonylsulfonylimido acids, bis(alkylsulfonyl)imido acids, and tris(alkylsulfonyl)methido acids.

[0148] "M ＋ X － In the compound represented by the formula ", M ＋represents a cation, preferably an organic cation. The cation is not particularly limited. The cation may have a valence of 1 or 2 or more. The cation is preferably a cation represented by formula (ZaI) (hereinafter also referred to as "cation (ZaI)") or a cation represented by formula (ZaII) (hereinafter also referred to as "cation (ZaII)").

[0149]

[0150] In the above formula (ZaI), R ２０１ , R ２０２ , and R ２０３ R each independently represents an organic group. ２０１ , R ２０２ , and R ２０３ The number of carbon atoms in the organic group represented by R is preferably 1 to 30, and more preferably 1 to 20. ２０１ ~R ２０３ Two of these may be bonded to form a ring structure, and the ring may contain an oxygen atom, a sulfur atom, an ester group, an amide group, or a carbonyl group. ２０１ ~R ２０３ Examples of groups formed by combining two of these include alkylene groups (e.g., butylene and pentylene groups) and —CH ２ -CH ２ -O-CH ２ -CH ２ - are listed.

[0151] 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.

[0152] 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 ２０３A 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.

[0153] 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.

[0154] R２０１ ~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. The acid-decomposable group is intended to be a group that decomposes under the action of acid to generate a polar group, and preferably has a structure in which the polar group is protected by a group that leaves under the action of acid. The above polar groups and leaving groups are as described above.

[0155] 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.

[0156] R ２０１ ~R ２０３Examples of the alkyl group and cycloalkyl group in R include linear alkyl groups having 1 to 10 carbon atoms or branched alkyl groups having 3 to 10 carbon atoms (e.g., methyl, ethyl, propyl, butyl, and pentyl groups), and cycloalkyl groups having 3 to 10 carbon atoms (e.g., cyclopentyl, cyclohexyl, and norbornyl groups). ２０１ ~R ２０３ may be further substituted with a halogen atom, an alkoxy group (e.g., having 1 to 5 carbon atoms), a hydroxyl group, a cyano group, or a nitro group. ２０１ ~R ２０３ It is also preferred that the substituents independently form an acid-decomposable group by any combination of the substituents.

[0157] Next, the cation (ZaI-3b) will be described. The cation (ZaI-3b) is a cation represented by the following formula (ZaI-3b).

[0158]

[0159] In formula (ZaI-3b), R １ｃ ~R ５ｃ R each independently represents a hydrogen atom, an alkyl group, a cycloalkyl group, an aryl group, an alkoxy group, an aryloxy group, an alkoxycarbonyl group, an alkylcarbonyloxy group, a cycloalkylcarbonyloxy group, a halogen atom, a hydroxyl group, a nitro group, an alkylthio group, or an arylthio group. ６ｃ and R ７ｃ R each independently represents a hydrogen atom, an alkyl group (for example, a t-butyl group), a cycloalkyl group, a halogen atom, a cyano group, or an aryl group. ｘ and R ｙ R each independently represents an alkyl group, a cycloalkyl group, a 2-oxoalkyl group, a 2-oxocycloalkyl group, an alkoxycarbonylalkyl group, an allyl group, or a vinyl group. １ｃ ~R ７ｃ , and R ｘ and R ｙ It is also preferred that the substituents independently form an acid-decomposable group by any combination of the substituents.

[0160] 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.

[0161] R １ｃ ~R ５ｃ Two or more of the following, R ６ｃ and R ７ｃ , and R ｘ and R ｙ Examples of the group formed by bonding of R include alkylene groups such as butylene and pentylene. The 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.

[0162] R １ｃ ~R ５ｃ , R ６ｃ , R ７ｃ , R ｘ , R ｙ , and R １ｃ ~R ５ｃ Two or more of the following, R ５ｃ and R ６ｃ , R ６ｃ and R ７ｃ , R ５ｃ and R ｘ , and R ｘ and R ｙThe ring formed by bonding together may have a substituent.

[0163] Next, the cation (ZaI-4b) will be described. The cation (ZaI-4b) is a cation represented by the following formula (ZaI-4b).

[0164]

[0165] In formula (ZaI-4b), l represents an integer of 0 to 2, and r represents an integer of 0 to 8. １３ represents a hydrogen atom, a halogen atom (for example, a fluorine atom or an iodine atom), a hydroxyl group, an alkyl group, a halogenated alkyl group, an alkoxy group, a carboxyl group, an alkoxycarbonyl group, or a group containing a cycloalkyl group (which may be a cycloalkyl group itself or a group containing a cycloalkyl group as a part). These groups may have a substituent. R １４ represents a hydroxyl group, a halogen atom (for example, a fluorine atom or an iodine atom), an alkyl group, a halogenated alkyl group, an alkoxy group, an alkoxycarbonyl group, an alkylcarbonyl group, an alkylsulfonyl group, a cycloalkylsulfonyl group, or a group containing a cycloalkyl group (which may be a cycloalkyl group itself or a group containing a cycloalkyl group as a part). These groups may have a substituent. R １４ When a plurality of R are present, each independently represents the above group such as a hydroxyl group. １５ each independently represents an alkyl group, a cycloalkyl group, or a naphthyl group. １５ may be bonded to each other to form a ring. １５ When two R are bonded to each other to form a ring, the ring skeleton may contain a heteroatom such as an oxygen atom or a nitrogen atom. １５ are preferably alkylene groups and bonded to each other to form a ring structure. １５ The ring formed by bonding together may have a substituent.

[0166] In formula (ZaI-4b), R １３ , R１４ , and R １５ The alkyl group in R may be linear or branched. The number of carbon atoms in the alkyl group is preferably 1 to 10. The alkyl group is preferably a methyl group, an ethyl group, an n-butyl group, a t-butyl group, or the like. １３ ~R １５ , and R ｘ and R ｙ It is also preferred that each of the substituents independently form an acid-decomposable group by any combination of the substituents.

[0167] Next, formula (ZaII) will be described. In formula (ZaII), R ２０４ and R ２０５ R each independently represents an aryl group, an alkyl group, or a cycloalkyl group. ２０４ and R ２０５ The aryl group in R is preferably a phenyl group or a naphthyl group, and more preferably a phenyl group. ２０４ and R ２０５ The aryl group in R may be an aryl group having a heterocycle containing an oxygen atom, a nitrogen atom, a sulfur atom, or the like. Examples of the skeleton of the aryl group having a heterocycle include pyrrole, furan, thiophene, indole, benzofuran, and benzothiophene. ２０４ and R ２０５ The alkyl group and cycloalkyl group are preferably a linear alkyl group having 1 to 10 carbon atoms or a branched alkyl group having 3 to 10 carbon atoms (e.g., methyl, ethyl, propyl, butyl, or pentyl), or a cycloalkyl group having 3 to 10 carbon atoms (e.g., cyclopentyl, cyclohexyl, or norbornyl).

[0168] R ２０４ and R ２０５ The aryl group, alkyl group, and cycloalkyl group in R may each independently have a substituent. ２０４ and R ２０５Examples of the substituents that the aryl group, alkyl group, and cycloalkyl group may have include alkyl groups (e.g., having 1 to 15 carbon atoms), cycloalkyl groups (e.g., having 3 to 15 carbon atoms), aryl groups (e.g., having 6 to 15 carbon atoms), alkoxy groups (e.g., having 1 to 15 carbon atoms), halogen atoms, hydroxyl groups, and phenylthio groups. ２０４ and R ２０５ It is also preferred that the substituents independently form an acid-decomposable group by any combination of the substituents.

[0169] Specific examples of organic cations are shown below, but are not limited to these.

[0170]

[0171]

[0172] "M ＋ X － In the compound represented by the formula "X － represents an anion, preferably an organic anion. The anion is not particularly limited, and examples thereof include monovalent or divalent or higher anions. The anion is preferably an anion having a significantly low ability to cause a nucleophilic reaction, and more preferably a non-nucleophilic anion.

[0173] 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.

[0174] 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).

[0175] 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.

[0176] 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).

[0177] 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.

[0178] An example of the sulfonylimide anion is a saccharin anion.

[0179] 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.

[0180] 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.

[0181] Preferred non-nucleophilic anions include aliphatic sulfonate anions in which at least the α-position of the sulfonic acid is substituted with a fluorine atom, aromatic sulfonate anions substituted with a fluorine atom or a group having a fluorine atom, bis(alkylsulfonyl)imide anions in which an alkyl group is substituted with a fluorine atom, and tris(alkylsulfonyl)methide anions in which an alkyl group is substituted with a fluorine atom. Among these, perfluoroaliphatic sulfonate anions (preferably having 4 to 8 carbon atoms) and benzenesulfonate anions having a fluorine atom are more preferred, and nonafluorobutanesulfonate anions, perfluorooctanesulfonate anions, pentafluorobenzenesulfonate anions, and 3,5-bis(trifluoromethyl)benzenesulfonate anions are even more preferred.

[0182] The non-nucleophilic anion is also preferably an anion represented by the following formula (AN1).

[0183]

[0184] In formula (AN1), R１ and R ２ each independently represents a hydrogen atom or a substituent. The substituent is not particularly limited, but a group that is not an electron-withdrawing group is preferred. Examples of groups that are not electron-withdrawing groups include hydrocarbon groups, hydroxyl groups, oxyhydrocarbon groups, oxycarbonyl hydrocarbon groups, amino groups, hydrocarbon-substituted amino groups, and hydrocarbon-substituted amide groups. Examples of groups that are not electron-withdrawing groups include, each independently, -R', -OH, -OR', -OCOR', -NH ２ , -NR' ２ , —NHR′, or —NHCOR′ is preferred, where R′ is a monovalent hydrocarbon group.

[0185] Examples of the monovalent hydrocarbon group represented by R' include monovalent linear or branched hydrocarbon groups such as alkyl groups such as methyl, ethyl, propyl, and butyl; alkenyl groups such as ethenyl, propenyl, and butenyl; alkynyl groups such as ethynyl, propynyl, and butynyl; cycloalkyl groups such as cyclopropyl, cyclobutyl, cyclopentyl, cyclohexyl, norbornyl, and adamantyl; monovalent alicyclic hydrocarbon groups such as cycloalkenyl groups such as cyclopropenyl, cyclobutenyl, cyclopentenyl, and norbornenyl; aryl groups such as phenyl, tolyl, xylyl, mesityl, naphthyl, methylnaphthyl, anthryl, and methylanthryl; and aralkyl groups such as benzyl, phenethyl, phenylpropyl, naphthylmethyl, and anthrylmethyl. Among these, R １ and R ２ are each independently preferably a hydrocarbon group (preferably a cycloalkyl group) or a hydrogen atom.

[0186] L represents a divalent linking group. When a plurality of L's are present, they may be the same or different. Examples of the divalent linking group include -O-CO-O-, -COO-, -CONH-, -CO-, -O-, -S-, -SO-, and -SO ２Examples of the divalent linking group include -, an alkylene group (preferably having 1 to 6 carbon atoms), a cycloalkylene group (preferably having 3 to 15 carbon atoms), an alkenylene group (preferably having 2 to 6 carbon atoms), and a divalent linking group formed by combining a plurality of these groups. Among these, examples of the divalent linking group include -O-CO-O-, -COO-, -CONH-, -CO-, -O-, and -SO ２ -, -O-CO-O-alkylene group-, -COO-alkylene group-, or -CONH-alkylene group- is preferred, and -O-CO-O-, -O-CO-O-alkylene group-, -COO-, -CONH-, or -SO ２ - or -COO-alkylene group- is more preferred.

[0187] As L, for example, a group represented by the following formula (AN1-1) is preferable: ａ - (CR ２ａ ２ ) Ｘ -Q-(CR ２ｂ ２ ) Ｙ -* ｂ (AN1-1)

[0188] In formula (AN1-1), * ａ is R in formula (AN1). ３ Represents the bonding position with * ｂ represents -C(R １ ) (R ２ X and Y each independently represent an integer of 0 to 10, preferably an integer of 0 to 3. R ２ａ and R ２ｂ R each independently represents a hydrogen atom or a substituent. ２ａ and R ２ｂ When there are multiple R ２ａ and R ２ｂ may be the same or different, provided that when Y is 1 or more, -C(R １ ) (R ２ )- and CR directly bonded ２ｂ ２ R in ２ｂ is other than a fluorine atom. Q is * Ａ -O-CO-O-*Ｂ , * Ａ -CO-* Ｂ , * Ａ -CO-O-* Ｂ , * Ａ -O-CO-* Ｂ , * Ａ -O-* Ｂ , * Ａ -S-* Ｂ , or * Ａ -SO ２ -* Ｂ where X+Y in formula (AN1-1) is 1 or more, and R ２ａ and R ２ｂ are all hydrogen atoms, Q is * Ａ -O-CO-O-* Ｂ , * Ａ -CO-* Ｂ , * Ａ -O-CO-* Ｂ , * Ａ -O-* Ｂ , * Ａ -S-* Ｂ , or * Ａ -SO ２ -* Ｂ Represents. Ａ is R in formula (AN1). ３ represents the bonding position on the side, and * Ｂ represents -SO in formula (AN1). ３ － represents the bonding position on the side.

[0189] In formula (AN1), R ３ represents an organic group. The organic group is not particularly limited as long as it has one or more carbon atoms, and may be a linear group (for example, a linear alkyl group), a branched group (for example, a branched alkyl group such as a t-butyl group), or a cyclic group. The organic group may or may not have a substituent. The organic group may or may not have a heteroatom (such as an oxygen atom, a sulfur atom, and / or a nitrogen atom).

[0190] Among them, R ３is preferably an organic group having a cyclic structure. The cyclic structure may be monocyclic or polycyclic and may have a substituent. The ring in the organic group having a cyclic structure is preferably directly bonded to L in formula (AN1). The organic group having a cyclic structure may or may not have a heteroatom (oxygen atom, sulfur atom, and / or nitrogen atom, etc.). The heteroatom may be substituted for one or more of the carbon atoms forming the cyclic structure. The organic group having a cyclic structure is preferably, for example, a hydrocarbon group having a cyclic structure, a lactone ring group, or a sultone ring group. Among these, the organic group having a cyclic structure is preferably a hydrocarbon group having a cyclic structure. The hydrocarbon group having a cyclic structure is preferably a monocyclic or polycyclic cycloalkyl group. These groups may have a substituent. The cycloalkyl group may be monocyclic (e.g., a cyclohexyl group) or polycyclic (e.g., an adamantyl group), and preferably has 5 to 12 carbon atoms. As the lactone group and sultone group, for example, a group in which one hydrogen atom has been removed from a ring atom constituting the lactone structure or sultone structure in any of the structures represented by the above-mentioned formulae (LC1-1) to (LC1-22) and the structures represented by the above-mentioned formulae (SL1-1) to (SL1-3) is preferred.

[0191] R ３ Preferably, R contains a halogen atom. ３ The halogen atom contained in is preferably a fluorine atom or an iodine atom, and more preferably an iodine atom. When the resist composition is used as an EUV resist, the number of halogen atoms is preferably as large as possible from the viewpoint of the efficiency of absorbing EUV light. When an iodine atom is contained, a structure in which the iodine atom is directly bonded to a carbon atom on an aromatic ring is preferred.

[0192] As the anion represented by formula (AN1), the anions described in

[0040] to

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

[0193] The non-nucleophilic anion may be a benzenesulfonate anion, and is preferably a benzenesulfonate anion substituted with a branched alkyl group or a cycloalkyl group.

[0194] The non-nucleophilic anion is also preferably an anion represented by the following formula (AN2).

[0195]

[0196] In formula (AN2), o represents an integer of 1 to 3. p represents an integer of 0 to 10. q represents an integer of 0 to 10.

[0197] Xf represents a hydrogen atom, a fluorine atom, an alkyl group substituted with at least one fluorine atom, or an organic group having no fluorine atoms. The number of carbon atoms in this alkyl group is preferably 1 to 10, more preferably 1 to 4. The alkyl group substituted with at least one fluorine atom is preferably a perfluoroalkyl group. Xf is preferably a fluorine atom or a perfluoroalkyl group having 1 to 4 carbon atoms, and is preferably a fluorine atom or CF ３ It is more preferable that both Xf's are fluorine atoms.

[0198] R ４ and R ５ R each independently represents a hydrogen atom, a fluorine atom, an alkyl group, or an alkyl group substituted with at least one fluorine atom. ４ and R ５ If there are multiple R ４ and R ５ may be the same or different. ４ and R ５ The alkyl group represented by the formula (I) preferably has 1 to 4 carbon atoms. The alkyl group may have a substituent. ４ and R ５ is preferably a hydrogen atom.

[0199] L represents a divalent linking group, and is defined the same as L in formula (AN1).

[0200] W represents an organic group containing a cyclic structure. Among these, a cyclic organic group is preferred. Examples of the cyclic organic group include an alicyclic group, an aryl group, and a heterocyclic group. The alicyclic group may be monocyclic or polycyclic. Examples of the monocyclic alicyclic group include a monocyclic cycloalkyl group such as a cyclopentyl group, a cyclohexyl group, and a cyclooctyl group. Examples of the polycyclic alicyclic group include a polycyclic cycloalkyl group such as a norbornyl group, a tricyclodecanyl group, a tetracyclodecanyl group, a tetracyclododecanyl group, and an adamantyl group. Among these, alicyclic groups having a bulky structure with 7 or more carbon atoms, such as a norbornyl group, a tricyclodecanyl group, a tetracyclodecanyl group, a tetracyclododecanyl group, and an adamantyl group, are preferred.

[0201] The aryl group may be monocyclic or polycyclic. Examples of the aryl group include a phenyl group, a naphthyl group, a phenanthryl group, and an anthryl group. The heterocyclic group may be monocyclic or polycyclic. In particular, a polycyclic heterocyclic group can further suppress the diffusion of acid. The heterocyclic group may or may not have aromaticity. Examples of heterocyclic rings having aromaticity include a furan ring, a thiophene ring, a benzofuran ring, a benzothiophene ring, a dibenzofuran ring, a dibenzothiophene ring, and a pyridine ring. Examples of heterocyclic rings having no aromaticity include a tetrahydropyran ring, a lactone ring, a sultone ring, and a decahydroisoquinoline ring. The heterocyclic ring in the heterocyclic group is preferably a furan ring, a thiophene ring, a pyridine ring, or a decahydroisoquinoline ring.

[0202] The cyclic organic group may have a substituent. Examples of the substituent include an alkyl group (which may be either linear or branched, and preferably has 1 to 12 carbon atoms), a cycloalkyl group (which may be either monocyclic, polycyclic, or spirocyclic, and preferably has 3 to 20 carbon atoms), an aryl group (which preferably has 6 to 14 carbon atoms), a hydroxyl group, an alkoxy group, an ester group, an amide group, a urethane group, a ureido group, a thioether group, a sulfonamide group, and a sulfonate ester group. The carbon constituting the cyclic organic group (the carbon that contributes to ring formation) may be a carbonyl carbon.

[0203] W preferably contains a halogen atom. The halogen atom contained in W is preferably a fluorine atom or an iodine atom, and more preferably an iodine atom. When the resist composition is used as an EUV resist, the greater the number of halogen atoms, the better from the viewpoint of the absorption efficiency of EUV light. When an iodine atom is contained, a structure in which the iodine atom is directly bonded to a carbon atom on an aromatic ring is preferred.

[0204] As the anion represented by formula (AN2), the anions described in

[0076] of WO 2023 / 157455,

[0071] to

[0089] of JP-A 2021-81708,

[0033] to

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

[0031] to

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

[0205] The anion represented by formula (AN2) is SO ３ － -CF ２ -CH ２ -OCO-(L) ｑ’ -W, SO ３ － -CF ２ -CHF-CH ２ -OCO-(L) ｑ’ -W, SO ３ － -CF ２ -COO-(L) ｑ’ -W, SO ３ － -CF ２ -CF ２ -CH ２ -CH２ - (L) ｑ -W or SO ３ － -CF ２ -CH(CF ３ ) -OCO-(L) ｑ’ -W is preferred. Here, L, q and W are the same as those in formula (AN2). q' represents an integer of 0 to 10.

[0206] As the non-nucleophilic anion, an aromatic sulfonate anion (aryl sulfonate anion) represented by the following formula (AN3) is also preferred.

[0207]

[0208] In formula (AN3), Ar represents an aryl group (such as a phenyl group) and may further have a substituent other than the sulfonate anion and the -(D-B) group. Examples of the substituent that may further be had include a fluorine atom and a hydroxyl group. n represents an integer of 0 or greater. n is preferably 1 to 4, more preferably 2 to 3, and even more preferably 3.

[0209] D represents a single bond or a divalent linking group. Examples of the divalent linking group include an ether group, a thioether group, a carbonyl group, a sulfoxide group, a sulfone group, a sulfonate ester group, an ester group, and a group formed by combining two or more of these groups.

[0210] B represents a hydrocarbon group. B is preferably an aliphatic hydrocarbon group, and more preferably an isopropyl group, a cyclohexyl group, or an aryl group which may further have a substituent (such as a tricyclohexylphenyl group).

[0211] B preferably contains a halogen atom. The halogen atom contained in B is preferably a fluorine atom or an iodine atom, and more preferably an iodine atom. When the resist composition is used as an EUV resist, the greater the number of halogen atoms, the better, from the viewpoint of the absorption efficiency of EUV light. When an iodine atom is contained, a structure in which the iodine atom is directly bonded to a carbon atom on an aromatic ring is preferred.

[0212] As the anion represented by formula (AN3), the anions described in

[0029] to

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

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

[0213] As the non-nucleophilic anion, a disulfonamide anion is also preferred. The disulfonamide anion is, for example, N － (SO ２ -R ｑ ) ２ where R ｑ represents an alkyl group which may have a substituent, preferably a fluoroalkyl group, more preferably a perfluoroalkyl group. ｑ may be bonded to each other to form a ring. ｑ The group formed by bonding together is preferably an alkylene group which may have a substituent, more preferably a fluoroalkylene group, and even more preferably a perfluoroalkylene group. The alkylene group preferably has 2 to 4 carbon atoms.

[0214] Further, examples of the non-nucleophilic anion include anions represented by the following formulas (d1-1) to (d1-4).

[0215]

[0216] 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).

[0217] In formula (d1-2), Z ２ｃ represents a hydrocarbon group having 1 to 30 carbon atoms which may have a substituent (provided that the carbon atom adjacent to S is not substituted with a fluorine atom). ２ｃThe hydrocarbon group in the formula (d1-2) may be linear or branched, or may have a cyclic structure. In addition, a carbon atom in the hydrocarbon group (preferably, a carbon atom that is a ring atom when the hydrocarbon group has a cyclic structure) may be a carbonyl carbon (-CO-). Examples of the hydrocarbon group include a group having a norbornyl group that may have a substituent. The carbon atom forming the norbornyl group may be a carbonyl carbon. ２ｃ -SO ３ － " is preferably different from the anions represented by the above formulae (AN1) to (AN3). For example, Z ２ｃ is preferably other than an aryl group. For example, Z ２ｃ In the -SO ３ － The atoms at the α-position and β-position to Z are preferably atoms other than carbon atoms having a fluorine atom as a substituent. ２ｃ is -SO ３ － The atom at the α-position and / or the atom at the β-position to the aryl group is preferably a ring atom in a cyclic group.

[0218] 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.

[0219] 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.

[0220] The organic anions may be used alone or in combination of two or more.

[0221] The photoacid generator may be a compound in a form other than those described above, for example, a compound described in

[0312] to

[0384] of JP-A No. 2023-35836.

[0222] The content of the photoacid generator in the composition of the present invention is not particularly limited, but is preferably 1% by mass or more, more preferably 5% by mass or more, and even more preferably 10% by mass or more, based on the total solid content of the composition of the present invention. Furthermore, the content of the photoacid generator is preferably 70% by mass or less, more preferably 60% by mass or less, and even more preferably 50% by mass or less, based on the total solid content of the composition of the present invention. Only one photoacid generator may be used, or two or more may be used. When two or more photoacid generators are used, it is preferable that the total content thereof is within the above-mentioned preferred content range.

[0223] [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.

[0224] The hydrophobic resin contains fluorine atoms, silicon atoms, and CH atoms contained in the side chain portion of the resin in order to be unevenly distributed on the surface layer of the film. ３ It is preferable to have one or more of the partial structures, and more preferably two or more. The hydrophobic resin preferably has a hydrocarbon group having 5 or more carbon atoms. These groups may be present in the main chain of the resin or may be substituted on a side chain. Examples of hydrophobic resins include the compounds described in paragraphs

[0275] to

[0279] of WO 2020 / 004306.

[0225] 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.

[0226] [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.

[0227] 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.

[0228] [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).

[0229] 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.

[0230] 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.

[0231] 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.

[0232] [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).

[0233] 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.

[0234] <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.

[0235] (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.

[0236] 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.

[0237] 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.

[0238] 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.

[0239] 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.

[0240] 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.

[0241] (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.

[0242] 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.

[0243] (Step 3: Development Step) Step 3 is a step of developing the exposed resist film using 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).

[0244] 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.

[0245] 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.

[0246] 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.

[0247] 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.

[0248] (Other Steps) The pattern formation method preferably includes, after step 3, a step of cleaning with a rinse liquid.

[0249] 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.

[0250] 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.

[0251] 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).

[0252] 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.

[0253] 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.

[0254] 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.

[0255] 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).

[0256] 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.

[0257] 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.

[0258] <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).

[0259] 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.

[0260] The various components used in the resist compositions of the examples and comparative examples are shown below.

[0261] <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).

[0262]

[0263] The structural formula of the repeating unit is shown below.

[0264]

[0265] <Photoacid Generator> The compounds used as photoacid generators are shown below, where Me represents a methyl group.

[0266]

[0267] The pKa of the acid (generated acid) generated by decomposition of the photoacid generator upon irradiation with actinic rays or radiation is shown in Table 2 below.

[0268]

[0269] <Acid Diffusion Controller> The compounds used as acid diffusion controllers are shown below. Me represents a methyl group. Q-1 to Q-13 are compounds represented by formula (1), and RQ-1 to RQ-4 are not compounds represented by formula (1).

[0270]

[0271]

[0272]

[0273] The molecular weights of Q-1 to Q-13 are shown in Table 3 below.

[0274]

[0275] <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.

[0276]

[0277] <Surfactant> The surfactants used are as follows: W-1: Megafac R08 (manufactured by DIC Corporation)

[0278] <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

[0279] <Preparation of Resist Compositions> The components shown in Tables 4 and 5 below were dissolved in the solvents shown in the tables to prepare solutions with the solid content concentrations shown in the tables. 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 the tables, 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. When multiple photoacid generators and acid diffusion controllers were used, each was listed in multiple columns in the table. For example, resist composition R-32 contained 10.0 mass % of Q-3 and 10.0 mass % of Q-4 as acid diffusion controllers. In resist compositions that used surfactants, the surfactant content was 0.1 mass %. The "mass ratio" of the solvent refers to the content (mass ratio) of each solvent listed in the "Type" column relative to all solvents (the total amount of the solvents listed in the "Type" column). The type and mass ratio of each solvent is shown separated by a " / ". The types and mass ratios correspond from left to right.

[0280]

[0281]

[0282] <Pattern Forming 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 if the Si wafer was replaced with a chromium substrate. The wafer on which the resist film had been formed 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 110°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.

[0283] <Performance Evaluation> [LWR Performance] The exposure dose (electron beam dose) when resolving a 1:1 line and space pattern with a line width of 50 nm using a critical dimension scanning electron microscope (S-9380II manufactured by Hitachi, Ltd.) 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 (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.

[0284] [PCD Stability] After applying a resist composition, the resist composition was immediately exposed and developed by the method described above (pattern formation method (1)) at an exposure dose sufficient to form a 1:1 line and space pattern with a line width of 50 nm and a space width of 50 nm. A pattern was formed by measuring the line width (L0) of the resist composition, and then storing the resist composition at 40°C for one month and then exposing and developing by the method described above (pattern formation method (1)) to form a pattern. The line width (L1) of the resist composition was measured and the line width change rate was calculated using the following formula: Line width change rate (%) = 100 × (L0 - L1) nm / 50 nm A smaller line width change rate indicates better PCD stability and better performance. A rating of B or higher is preferred, and A is more preferred. A: Line width change rate is less than 2% B: Line width change rate is 2% or more but less than 4% C: Line width change rate is 4% or more but less than 6% D: Line width change rate is 6% or more

[0285] [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.

[0286] 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.

[0287]

[0288] <Pattern Forming 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. It should be noted that similar results were obtained even if the Si wafer was replaced with a chrome substrate. The wafer on which the resist film was formed was subjected to pattern exposure using an EUV exposure apparatus (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 exposure, the wafer was heated on a hot plate at 110°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.

[0289] <Performance Evaluation> [LWR Performance] The exposure dose (EUV irradiation dose) when resolving a 1:1 line and space pattern with a line width of 50 nm using a critical dimension scanning electron microscope (S-9380II manufactured by Hitachi, Ltd.) 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 (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.

[0290] [PCD Stability] After applying the resist composition, the resist composition was immediately exposed and developed by the method described above (pattern formation method (2)) at an exposure dose sufficient to form a 1:1 line and space pattern with a line width of 50 nm and a space width of 50 nm. A pattern was formed by measuring the line width (L0) of the resist composition, and then storing the resist composition at 40°C for one month and then exposing and developing by the method described above (pattern formation method (2)) to form a pattern. The line width (L1) of the resist composition was measured and the line width change rate was calculated using the following formula: Line width change rate (%) = 100 × (L0 - L1) nm / 50 nm A smaller line width change rate indicates better PCD stability and better performance. A rating of B or higher is preferred, and A is more preferred. A: Line width change rate is less than 2% B: Line width change rate is 2% or more but less than 4% C: Line width change rate is 4% or more but less than 6% D: Line width change rate is 6% or more

[0291] [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.

[0292] 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.

[0293]

[0294] The above results demonstrate that the resist compositions used in the examples have excellent LWR performance and PCD stability. They also demonstrate excellent resolution.

[0295] The present invention can provide an actinic ray-sensitive or radiation-sensitive resin composition having excellent LWR performance and excellent PCD stability. The present invention can also provide an actinic ray-sensitive or radiation-sensitive film, a pattern forming method, and a method for manufacturing an electronic device using the actinic ray-sensitive or radiation-sensitive resin composition.

[0296] 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. 2024-153909) filed on September 6, 2024, the contents of which are incorporated herein by reference.

Claims

1. An actinic ray-sensitive or radiation-sensitive resin composition containing a resin, a photoacid generator, and an acid diffusion controller, wherein the acid diffusion controller comprises a compound represented by the following formula (1), and the content of the compound represented by formula (1) is 0.5 mass% or more based on the total solid content of the actinic ray-sensitive or radiation-sensitive resin composition: In formula (1), A １ represents a nitrogen-containing aromatic heterocycle. １ may have a substituent.

2. The actinic ray-sensitive or radiation-sensitive resin composition according to claim 1, wherein the compound represented by formula (1) does not have at least one anion selected from the group consisting of a sulfonate anion and a carboxylate anion.

3. The actinic ray- or radiation-sensitive resin composition according to claim 1, wherein the resin contains a repeating unit having a group that decomposes under the action of an acid and exhibits increased polarity.

4. 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.

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 Is L ｂ１ may be bonded to the aromatic ring to which 6. The actinic ray-sensitive or radiation-sensitive resin composition according to claim 1, wherein the content of the compound represented by formula (1) is 2 mass% or more based on the total solid content of the actinic ray-sensitive or radiation-sensitive resin composition.

7. The actinic ray-sensitive or radiation-sensitive resin composition according to claim 1, wherein the compound represented by formula (1) is a compound represented by formula (2): In formula (2), R ａ１ , R ａ２ , R ａ３ , R ａ４ and R ａ５ R each independently represents a hydrogen atom or a substituent. ａ１ , R ａ２ , R ａ３ , R ａ４ and R ａ５ At least two of these may be bonded to form a ring.

8. R in the formula (2) ａ１ , R ａ２ , R ａ３ , R ａ４ and R ａ５ each independently represent a hydrogen atom, a halogen atom, an alkyl group, a cycloalkyl group, an aryl group, a heteroaryl group, an alkenyl group, an alkynyl group, an alkoxy group, a cycloalkyloxy group, an aryloxy group, a heteroaryloxy group, an alkoxycarbonyl group, a cycloalkyloxycarbonyl group, an aryloxycarbonyl group, a heteroaryloxycarbonyl group, or a group represented by the following formula (3): In formula (3), L １ is a single bond, —O—, —S— or —NR Ｃ１ - represents. Ｃ１ represents a hydrogen atom or a substituent. ２ is -C(=O)-, -S(=O)- or -S(=O) ２ - represents. １ represents a group represented by the following formula (T-1), an alkenyl group, or an alkynyl group. * represents a bonding position. In formula (T-1), k1 and k2 each independently represent 0 or 1. Ｔ１ and R Ｔ２ each independently represents a hydrogen atom or a substituent. Ｔ１ represents an aryl group or a heteroaryl group. # represents the bonding position.

9. The actinic ray-sensitive or radiation-sensitive resin composition according to claim 1, wherein the compound represented by formula (1) has a molecular weight of 250 or more.

10. The actinic ray-sensitive or radiation-sensitive resin composition according to claim 1, wherein the photoacid generator decomposes to generate an acid having a pKa of -2.0 or more and less than 1.

5.

11. The actinic ray-sensitive or radiation-sensitive resin composition according to claim 1, wherein the acid generated by decomposition of the photoacid generator is an arylsulfonic acid.

12. The actinic ray-sensitive or radiation-sensitive resin composition according to claim 1, wherein the compound represented by formula (1) is a compound having a group represented by formula (3): In formula (3), L １ is a single bond, —O—, —S— or —NR Ｃ１ - represents. Ｃ１ represents a hydrogen atom or a substituent. ２ is -C(=O)-, -S(=O)- or -S(=O) ２ - represents. １ represents a group represented by the following formula (T-1), an alkenyl group, or an alkynyl group. * represents a bonding position. In formula (T-1), k1 and k2 each independently represent 0 or 1. Ｔ１ and R Ｔ２ each independently represents a hydrogen atom or a substituent. Ｔ１ represents an aryl group or a heteroaryl group. # represents the bonding position.

13. R in the formula (2) ａ１ , R ａ２ , R ａ３ , R ａ４ and R ａ５ each independently represents a hydrogen atom, a halogen atom, an alkyl group, an aryl group, a heteroaryl group, an alkenyl group, an alkynyl group, an alkoxy group, an aryloxy group, a heteroaryloxy group, or a group represented by the formula (3), and R ａ１ , R ａ２ , R ａ３ , R ａ４ and R ａ５ The actinic ray-sensitive or radiation-sensitive resin composition according to claim 8 , wherein at least one of the following is a group represented by formula (3):

14. 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 13.

15. 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 13; exposing the actinic ray-sensitive or radiation-sensitive film; and developing the exposed actinic ray-sensitive or radiation-sensitive film using a developer.

16. A method for manufacturing an electronic device, comprising the pattern formation method according to claim 15.

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