Active ray-sensitive or radiation-sensitive resin composition, resist film, pattern forming method, method for producing electronic device, and compound

Abstract

The present invention provides: an active ray-sensitive or radiation-sensitive resin composition, containing (A) a resin and (Q1) an active ray-sensitive or radiation-sensitive acid generator which is an onium salt compound having a structure in which three or more iodine atoms and at least two or more atoms selected from oxygen atoms and sulfur atoms are bonded to the same aromatic ring; an active ray-sensitive or radiation-sensitive film formed from the active ray-sensitive or radiation-sensitive resin composition; a pattern forming method using the active ray-sensitive or radiation-sensitive resin composition; and a method for producing an electronic device.

Description

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

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

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

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

[0004] Various additives are used in actinic ray-sensitive or radiation-sensitive resin compositions to improve their performance. For example, Patent Document 1 discloses an acid generator having a specific structure in which three or more iodine atoms and one oxygen atom are bonded to the same aromatic ring. Patent Document 2 discloses an acid generator having a specific structure in which two iodine atoms and two oxygen atoms are bonded to the same aromatic ring. Patent Document 3 discloses a radiation-sensitive acid generator having a structure in which four or more iodine atoms are bonded to the same aromatic ring.

[0005] Japanese Patent Application Publication No. 2018-025789 Japanese Patent Application Publication No. 2022-075556 International Publication No. 2023 / 157455

[0006] In recent years, resist patterns have become increasingly finer, and attempts have been made to form, for example, line and space (LS) patterns with line widths of 16 nm or less, contact hole patterns with hole diameters of 16 nm or less, and dot patterns with dots of 16 nm or less. To form such fine resist patterns, further improvements in various performances are required. In particular, there is room for improvement in roughness performance and defect suppression. In the case of LS patterns, roughness performance includes, for example, line width roughness (LWR) performance.

[0007] An object of the present invention is to provide an actinic ray-sensitive or radiation-sensitive resin composition that exhibits excellent roughness performance and is capable of suppressing the occurrence of defects in the formation of ultrafine patterns (e.g., line space patterns with line widths of 16 nm or less, contact hole patterns with hole diameters of 16 nm or less, and dot patterns with dot systems of 16 nm or less), an actinic ray-sensitive or radiation-sensitive film formed from the actinic ray-sensitive or radiation-sensitive resin composition, a pattern formation method using the actinic ray-sensitive or radiation-sensitive resin composition, and a method for manufacturing an electronic device. Another object of the present invention is to provide a compound that can be suitably used in 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 comprising: (A) a resin; and (Q1) an actinic ray-sensitive or radiation-sensitive acid generator that is an onium salt compound having a structure in which three or more iodine atoms and at least two or more atoms selected from oxygen atoms and sulfur atoms are bonded to the same aromatic ring.

[0010] [2] The actinic ray-sensitive or radiation-sensitive resin composition according to [1], wherein the actinic ray-sensitive or radiation-sensitive acid generator (Q1) contains an organic anion having a structure in which three or more iodine atoms and at least two or more atoms selected from oxygen atoms and sulfur atoms are bonded to the same aromatic ring.

[0011] [3] The actinic ray-sensitive or radiation-sensitive resin composition according to [1] or [2], wherein the actinic ray-sensitive or radiation-sensitive acid generator (Q1) is a compound that generates, upon exposure, an acid having at least one group selected from a sulfo group, a carboxy group, a methide acid group, a sulfonamide group, a sulfonimide group, and a carbonylsulfonylimide group.

[0012] [4] The actinic ray-sensitive or radiation-sensitive resin composition according to any one of [1] to [3], wherein the actinic ray-sensitive or radiation-sensitive acid generator (Q1) has a sulfonium cation or an iodonium cation.

[0013] [5] The actinic ray-sensitive or radiation-sensitive resin composition according to any one of [1] to [4], wherein the resin (A) contains a repeating unit having an acid-decomposable group. [6] The actinic ray-sensitive or radiation-sensitive resin composition according to any one of [1] to [5], wherein the resin (A) contains a repeating unit having a hydroxyl group bonded to an aromatic ring.

[0014] [7] The actinic ray-sensitive or radiation-sensitive resin composition according to any one of [1] to [7], wherein the aromatic ring in the actinic ray-sensitive or radiation-sensitive acid generator (Q1) is a benzene ring. [8] The actinic ray-sensitive or radiation-sensitive resin composition according to any one of [1] to [7], wherein the actinic ray-sensitive or radiation-sensitive acid generator (Q1) is an onium salt compound having a structure in which four or more iodine atoms and at least two or more atoms selected from oxygen atoms and sulfur atoms are bonded to the same aromatic ring.

[0015] [9] The actinic ray-sensitive or radiation-sensitive resin composition according to [8], wherein the onium salt compound contains an organic anion having a structure in which four or more iodine atoms and at least two or more atoms selected from oxygen atoms and sulfur atoms are bonded to the same aromatic ring.

[0016]

[10] The actinic ray-sensitive or radiation-sensitive resin composition according to any one of [1] to [7], wherein the actinic ray-sensitive or radiation-sensitive acid generator (Q1) is an onium salt compound having a structure in which three or more iodine atoms and two or more oxygen atoms are bonded to the same aromatic ring.

[0017]

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

[10] , wherein the actinic ray-sensitive or radiation-sensitive acid generator (Q1) contains an organic anion represented by the following general formula (1D):

[0018]

[0019] In general formula (1D), R １ Each of R independently represents a hydrogen atom or an organic group. １ may be bonded to each other to form a ring structure together with other atoms in general formula (1D). １ At least one of them has an anionic moiety.

[0020]

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

[11] , wherein the actinic ray-sensitive or radiation-sensitive acid generator (Q1) has a halogen atom in the cation moiety (excluding cases where the halogen atom is a monovalent iodine cation).

[0021]

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

[12] , wherein the actinic ray-sensitive or radiation-sensitive acid generator (Q1) contains an organic cation selected from a sulfonium cation and an iodonium cation, which has a structure in which three or more iodine atoms and at least two or more atoms selected from oxygen atoms and sulfur atoms are bonded to the same aromatic ring.

[0022]

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

[13] , wherein the actinic ray-sensitive or radiation-sensitive acid generator (Q1) contains an actinic ray-sensitive or radiation-sensitive acid generator (Q2) that generates, upon exposure, an acid weaker than that generated upon exposure.

[0023]

[15] 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

[14] .

[0024]

[16] 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 [1] to

[14] ; exposing the actinic ray-sensitive or radiation-sensitive film; and developing the exposed actinic ray-sensitive or radiation-sensitive film using a developer to form a pattern.

[0025]

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

[16] .

[0026]

[18] An onium salt compound comprising: an anion moiety consisting of an organic anion having a structure in which three or more iodine atoms and at least two or more atoms selected from oxygen atoms and sulfur atoms are bonded to the same aromatic ring; and a cation moiety having a sulfonium cation or an iodonium cation.

[0027]

[19] An onium salt compound comprising: a cation moiety containing a sulfonium cation or an iodonium cation, the cation having a structure in which three or more iodine atoms and at least two or more atoms selected from oxygen atoms and sulfur atoms are bonded to the same aromatic ring; and an organic anion moiety.

[0028] According to the present invention, it is possible to provide an actinic ray-sensitive or radiation-sensitive resin composition that is excellent in roughness performance and can suppress the occurrence of defects in the formation of ultrafine patterns (for example, LS patterns with line widths of 16 nm or less), an actinic ray-sensitive or radiation-sensitive resin film formed from the actinic ray-sensitive or radiation-sensitive resin composition, a pattern formation method using the actinic ray-sensitive or radiation-sensitive resin composition, and a method for manufacturing an electronic device. Furthermore, according to the present invention, it is possible to provide a compound that can be suitably used in the actinic ray-sensitive or radiation-sensitive resin composition.

[0029] 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.

[0030] 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.

[0031] 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.

[0032] 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).

[0033] 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:

[0034] (Substituent T) Examples of the substituent T include halogen atoms such as a fluorine atom, a chlorine atom, a bromine atom, and an iodine atom; alkoxy groups such as a methoxy group, an ethoxy group, and a tert-butoxy group; a cycloalkyloxy group; an aryloxy group such as a phenoxy group and a p-tolyloxy group; an alkoxycarbonyl group such as a methoxycarbonyl group and a butoxycarbonyl group; a cycloalkyloxycarbonyl group; an aryloxycarbonyl group such as a phenoxycarbonyl group; an acyloxy group such as an acetoxy group, a propionyloxy group, and a benzoyloxy group; an acetyl group, a benzoyl group, an isobutyryl group, Examples of the substituent T include acyl groups such as acryloyl, methacryloyl, and methoxalyl; sulfanyl groups; alkylsulfanyl groups such as methylsulfanyl and tert-butylsulfanyl; arylsulfanyl groups such as phenylsulfanyl and p-tolylsulfanyl; alkyl groups; alkenyl groups; cycloalkyl groups; aryl groups; aromatic heterocyclic groups; hydroxy groups; carboxyl groups; formyl groups; sulfo groups; cyano groups; alkylaminocarbonyl groups; arylaminocarbonyl groups; sulfonamide groups; silyl groups; amino groups; carbamoyl groups; 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 (for example, monoalkylamino groups, dialkylamino groups, arylamino groups, trifluoromethyl groups, etc.).

[0035] 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".

[0036] 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).

[0037] 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.

[0038] 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.

[0039] 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.

[0040] [Actinic Ray- or Radiation-Sensitive Resin Composition] The actinic ray- or radiation-sensitive resin composition of the present invention (also referred to as "the composition of the present invention") is an actinic ray- or radiation-sensitive resin composition containing (A) a resin and (Q1) an actinic ray- or radiation-sensitive acid generator that is an onium salt compound having a structure in which three or more iodine atoms and at least two or more atoms selected from oxygen atoms and sulfur atoms are bonded to the same aromatic ring (also referred to as "actinic ray- or radiation-sensitive acid generator (Q1)" or simply "acid generator (Q1)").

[0041] Although the reason why the composition of the present invention can achieve excellent roughness performance and suppress the occurrence of defects in the formation of ultrafine patterns (e.g., LS patterns with linewidths of 16 nm or less) is not entirely clear, the present inventors speculate as follows. Because iodine atoms have a high absorption efficiency for EUV light, an acid generator having an aromatic ring to which three or more iodine atoms are bonded can efficiently increase the absorption efficiency of EUV light. Meanwhile, the bond between a carbon atom and an iodine atom (hereinafter referred to as a "C-I bond") is partially cleaved upon irradiation with high-energy EUV light. Furthermore, the present inventors' investigations have revealed that in aromatic rings having three or more iodine atoms, not only the C-I bond but also other bonds around the aromatic ring are partially cleaved upon irradiation with EUV light. When bond cleavage occurs during exposure, the amount of acid generated by exposure decreases or acids with different diffusivities are generated, resulting in deterioration of roughness performance and defect suppression performance. The acid generator (Q1) contained in the composition of the present invention has a structure in which, in addition to three or more iodine atoms, at least two or more atoms selected from oxygen atoms and sulfur atoms are bonded to the same aromatic ring. The presence of at least two or more atoms selected from oxygen atoms and sulfur atoms is believed to suppress cleavage of the C-I bond and other bonds around the aromatic ring. Therefore, it is believed that the absorption efficiency of EUV light can be increased without deteriorating roughness performance or defect suppression performance.

[0042] The composition of the present invention is typically a resist composition, and may be either a positive resist composition or a negative resist composition. The composition of the present invention may be a resist composition for alkali development or a resist composition for organic solvent development. The composition of the present invention may be either a chemically amplified resist composition or a non-chemically amplified resist composition. The composition of the present invention is typically a chemically amplified resist composition. An actinic ray-sensitive or radiation-sensitive film can be formed using the composition of the present invention. The actinic ray-sensitive or radiation-sensitive film formed using the composition of the present invention is typically a resist film. First, the various components of the composition of the present invention will be described in detail below.

[0043] [Resin (A)] The composition of the present invention contains a resin (A). The resin (A) is a resin whose polarity increases under the action of an acid. The resin (A) usually contains a group that decomposes under the action of an acid and whose polarity increases (also referred to as an "acid-decomposable group"), and preferably contains a repeating unit having an acid-decomposable group. When the resin (A) has an acid-decomposable group, in the pattern forming method herein, typically, 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. As the repeating unit having an acid-decomposable group, in addition to the repeating unit having an acid-decomposable group, a repeating unit having an acid-decomposable group containing an unsaturated bond is preferred.

[0044] (Repeating unit having an acid-decomposable group) The acid-decomposable group refers to a group that decomposes under the action of an acid to generate a polar group. The acid-decomposable group preferably has a structure in which a polar group is protected with a group (leaving group) that is released under the action of an acid. In other words, the resin (A) has a repeating unit that decomposes under the action of an acid to generate a polar group. The polarity of a resin having this repeating unit increases under the action of an acid, increasing its solubility in an alkaline developer and decreasing its solubility in an organic solvent. The polar group is preferably an alkali-soluble group, such as a carboxyl group, a phenolic hydroxyl group, a fluorinated alcohol group, a sulfonic acid group, a phosphate group, a sulfonamide group, a sulfonylimide group, a (alkylsulfonyl) (alkylcarbonyl) methylene group, a (alkylsulfonyl) (alkylcarbonyl) imide group, a bis(alkylcarbonyl) methylene group, a bis(alkylcarbonyl) imide group, a bis(alkylsulfonyl) methylene group, a bis(alkylsulfonyl) imide group, a tris(alkylcarbonyl) methylene group, and an acidic group such as a tris(alkylsulfonyl) methylene group, and an alcoholic hydroxyl group. Among these, the polar group is preferably a carboxyl group, a phenolic hydroxyl group, a fluorinated alcohol group (preferably a hexafluoroisopropanol group), or a sulfonic acid group.

[0045] Examples of the group that is eliminated by the action of an acid include groups represented by formulae (Y1) to (Y4). Formula (Y1): —C(Rx １ ) (Rx ２ ) (Rx ３ ) Formula (Y2): -C(=O)OC(Rx １ ) (Rx ２ ) (Rx ３ ) Formula (Y3): -C(R ３６ ) (R ３７ ) (OR ３８ ) Formula (Y4): -C(Rn)(H)(Ar)

[0046] In formula (Y1) and formula (Y2), Rx １ ~Rx ３Rx each independently represents an alkyl group (linear or branched), a cycloalkyl group (monocyclic or polycyclic), an alkenyl group (linear or branched), or an aryl group (monocyclic or polycyclic). １ ~Rx ３ When all of Rx are alkyl groups (linear or branched), １ ~Rx ３ At least two of Rx are preferably methyl groups. １ ~Rx ３ each independently preferably represents a linear or branched alkyl group, and Rx １ ~Rx ３ More preferably, Rx each independently represents a linear alkyl group. １ ~Rx ３ may be bonded to form a monocyclic or polycyclic ring. １ ~Rx ３ The alkyl group of Rx is preferably an alkyl group having 1 to 5 carbon atoms, such as a methyl group, an ethyl group, an n-propyl group, an isopropyl group, an n-butyl group, an isobutyl group, or a t-butyl group. １ ~Rx ３ The cycloalkyl group of Rx is preferably a monocyclic cycloalkyl group such as a cyclopentyl group or a cyclohexyl group, or a polycyclic cycloalkyl group such as a norbornyl group, a tetracyclodecanyl group, a tetracyclododecanyl group, or an adamantyl group. １ ~Rx ３ The aryl group in Rx is preferably an aryl group having 6 to 10 carbon atoms, and examples thereof include a phenyl group, a naphthyl group, and an anthryl group. １ ~Rx ３ The alkenyl group of Rx is preferably a vinyl group. １ ~Rx ３ The ring formed by combining the two is preferably a cycloalkyl group. １ ~Rx ３The cycloalkyl group formed by bonding the two is preferably a monocyclic cycloalkyl group such as a cyclopentyl group or a cyclohexyl group, or a polycyclic cycloalkyl group such as a norbornyl group, a tetracyclodecanyl group, a tetracyclododecanyl group, or an adamantyl group, and more preferably a monocyclic cycloalkyl group having 5 to 6 carbon atoms. １ ~Rx ３ In the cycloalkyl group formed by bonding these two, one of the methylene groups constituting the ring may be replaced with a heteroatom such as an oxygen atom, a group containing a heteroatom such as a carbonyl group, or a vinylidene group. In these cycloalkyl groups, one or more of the ethylene groups constituting the cycloalkane ring may be replaced with a vinylene group. The group represented by formula (Y1) or formula (Y2) can be, for example, Rx １ is a methyl group or an ethyl group, and Rx ２ and Rx ３ and Rx are preferably bonded to form the above-mentioned cycloalkyl group. When the actinic ray-sensitive or radiation-sensitive resin composition is, for example, a resist composition for EUV exposure, １ ~Rx ３ an alkyl group, a cycloalkyl group, an alkenyl group, an aryl group, and Rx １ ~Rx ３ The ring formed by bonding these two groups preferably further has a fluorine atom or an iodine atom as a substituent.

[0047] In formula (Y3), R ３６ ~R ３８ R each independently represents a hydrogen atom or a monovalent organic group. ３７ and R ３８ may be bonded to each other to form a ring. Examples of the monovalent organic group include an alkyl group, a cycloalkyl group, an aryl group, an aralkyl group, and an alkenyl group. ３６is also preferably a hydrogen atom. The alkyl group, cycloalkyl group, aryl group, and aralkyl group may contain a heteroatom such as an oxygen atom and / or a group containing a heteroatom such as a carbonyl group. For example, in the alkyl group, cycloalkyl group, aryl group, and aralkyl group, one or more methylene groups may be replaced with a heteroatom such as an oxygen atom and / or a group containing a heteroatom such as a carbonyl group. R ３８ may bond with another substituent on the main chain of the repeating unit to form a ring. ３８ The group formed by bonding together R and another substituent on the main chain of the repeating unit is preferably an alkylene group such as a methylene group. ３６ ~R ３８ and a monovalent organic group represented by R ３７ and R ３８ It is also preferable that the ring formed by bonding these groups together further has a fluorine atom or an iodine atom as a substituent.

[0048] Formula (Y3) is preferably a group represented by the following formula (Y3-1).

[0049]

[0050] Here, L １ and L ２ Each independently represents a hydrogen atom, an alkyl group, a cycloalkyl group, an aryl group, or a group combining these (for example, a group combining an alkyl group and an aryl group). M represents a single bond or a divalent linking group. Q represents an alkyl group that may contain a heteroatom, a cycloalkyl group that may contain a heteroatom, an aryl group that may contain a heteroatom, an amino group, an ammonium group, a mercapto group, a cyano group, an aldehyde group, or a group combining these (for example, a group combining an alkyl group and a cycloalkyl group). In the alkyl group and the cycloalkyl group, for example, one of the methylene groups may be replaced with a heteroatom such as an oxygen atom, or a group containing a heteroatom such as a carbonyl group. In addition, L １ and L２ It is preferred that one of Q, M, and L is a hydrogen atom, and the other is an alkyl group, a cycloalkyl group, an aryl group, or a group in which an alkylene group and an aryl group are combined. １ At least two of the groups may be bonded to form a ring (preferably a 5- or 6-membered ring). ２ is preferably a secondary or tertiary alkyl group, and more preferably a tertiary alkyl group. Examples of secondary alkyl groups include an isopropyl group, a cyclohexyl group, and a norbornyl group, and examples of tertiary alkyl groups include a tert-butyl group and an adamantane group. In these embodiments, the Tg (glass transition temperature) and activation energy are increased, thereby ensuring film strength and suppressing fogging.

[0051] When the actinic ray-sensitive or radiation-sensitive resin composition is, for example, a resist composition for EUV exposure, L １ and L ２ It is also preferable that the alkyl group, cycloalkyl group, aryl group, and combinations thereof represented by the formula (I) further have a fluorine atom or an iodine atom as a substituent. The alkyl group, cycloalkyl group, aryl group, and aralkyl group preferably contain a heteroatom such as an oxygen atom in addition to the fluorine atom and iodine atom. Specifically, in the alkyl group, cycloalkyl group, aryl group, and aralkyl group, for example, one of the methylene groups may be replaced with a heteroatom such as an oxygen atom, or a group containing a heteroatom such as a carbonyl group. When the actinic ray-sensitive or radiation-sensitive resin composition is, for example, a resist composition for EUV exposure, in the alkyl group which may contain a heteroatom, cycloalkyl group which may contain a heteroatom, aryl group which may contain a heteroatom, amino group, ammonium group, mercapto group, cyano group, aldehyde group, and combinations thereof represented by Q, the heteroatom is preferably selected from the group consisting of a fluorine atom, an iodine atom, and an oxygen atom.

[0052] In formula (Y4), Ar represents an aromatic ring group. Rn represents an alkyl group, a cycloalkyl group, or an aryl group. Rn and Ar may be bonded to each other to form a non-aromatic ring. Ar is preferably an aryl group. When the actinic ray-sensitive or radiation-sensitive resin composition is, for example, a resist composition for EUV exposure, it is also preferable that the aromatic ring group represented by Ar and the alkyl group, cycloalkyl group, and aryl group represented by Rn have a fluorine atom or an iodine atom as a substituent.

[0053] In terms of excellent acid decomposition properties of the repeating unit, when a non-aromatic ring is directly bonded to the polar group (or a residue thereof) in the leaving group protecting the polar group, it is also preferable that the ring atom in the non-aromatic ring adjacent to the ring atom directly bonded to the polar group (or a residue thereof) does not have a halogen atom such as a fluorine atom as a substituent.

[0054] The group that is eliminated by the action of an acid may also be a 2-cyclopentenyl group having a substituent (such as an alkyl group), such as a 3-methyl-2-cyclopentenyl group, or a cyclohexyl group having a substituent (such as an alkyl group), such as a 1,1,4,4-tetramethylcyclohexyl group.

[0055] The repeating unit having an acid-decomposable group is also preferably a repeating unit represented by formula (A).

[0056]

[0057] L １ represents a divalent linking group which may have a fluorine atom or an iodine atom, R １ represents a hydrogen atom, a fluorine atom, an iodine atom, an alkyl group which may have a fluorine atom or an iodine atom, or an aryl group which may have a fluorine atom or an iodine atom; R ２ represents a leaving group which is eliminated by the action of an acid and which may have a fluorine atom or an iodine atom. １ , R １ , and R ２ At least one of L has a fluorine atom or an iodine atom. １Examples of the divalent linking group which may have a fluorine atom or an iodine atom and is represented by the formula: ２ -, hydrocarbon groups which may have a fluorine atom or an iodine atom (for example, alkylene groups, cycloalkylene groups, alkenylene groups, arylene groups, etc.), and linking groups in which a plurality of these groups are linked together. １ As the alkylene group, -CO-, an arylene group, or -arylene group-alkylene group having a fluorine atom or an iodine atom- is preferred, and -CO- or -arylene group-alkylene group having a fluorine atom or an iodine atom- is more preferred. As the arylene group, a phenylene group is preferred. The alkylene group may be linear or branched. The number of carbon atoms in the alkylene group is not particularly limited, but is preferably 1 to 10, and more preferably 1 to 3. The total number of fluorine atoms and iodine atoms contained in the alkylene group having a fluorine atom or an iodine atom is not particularly limited, but is preferably 2 or more, more preferably 2 to 10, and even more preferably 3 to 6.

[0058] R １ The alkyl group represented by R may be linear or branched. The number of carbon atoms in the alkyl group is not particularly limited, but is preferably 1 to 10, and more preferably 1 to 3. １ The total number of fluorine atoms and iodine atoms contained in the alkyl group having a fluorine atom or an iodine atom, represented by the formula (I), is not particularly limited, but is preferably 1 or more, more preferably 1 to 5, and even more preferably 1 to 3. １ The alkyl group represented by the formula (I) may contain a heteroatom other than a halogen atom, such as an oxygen atom.

[0059] R ２ Examples of the leaving group represented by the formulae (Y1) to (Y4) above and which may have a fluorine atom or an iodine atom include leaving groups represented by the formulae (Y1) to (Y4) above and which have a fluorine atom or an iodine atom.

[0060] The repeating unit having an acid-decomposable group is also preferably a repeating unit represented by formula (AI).

[0061]

[0062] In formula (AI), Xa １ represents a hydrogen atom or an alkyl group which may have a substituent. T represents a single bond or a divalent linking group. Rx １ ~Rx ３ each independently represents an alkyl group (linear or branched), a cycloalkyl group (monocyclic or polycyclic), an alkenyl group (linear or branched), or an aryl group (monocyclic or polycyclic). １ ~Rx ３ When all of Rx are alkyl groups (linear or branched), １ ~Rx ３ Preferably, at least two of Rx are methyl groups. １ ~Rx ３ may be bonded to form a monocyclic or polycyclic ring (such as a monocyclic or polycyclic cycloalkyl group).

[0063] Xa １ Examples of the alkyl group represented by the formula (I) which may have a substituent include a methyl group or a —CH ２ -R １１ Examples of the group include a group represented by the following formula: １１ represents a halogen atom (such as a fluorine atom), a hydroxyl group, or a monovalent organic group. １１ Examples of the monovalent organic group represented by the formula (I) include an alkyl group having 5 or less carbon atoms which may be substituted with a halogen atom, an acyl group having 5 or less carbon atoms which may be substituted with a halogen atom, and an alkoxy group having 5 or less carbon atoms which may be substituted with a halogen atom, and an alkyl group having 3 or less carbon atoms is preferred, and a methyl group is more preferred. １ is preferably a hydrogen atom, a methyl group, a trifluoromethyl group, or a hydroxymethyl group.

[0064] Examples of the divalent linking group for T include an alkylene group, an aromatic ring group, a -COO-Rt- group, and a -O-Rt- group. In the formula, Rt represents an alkylene group or a cycloalkylene group. T is preferably a single bond or a -COO-Rt- group. When T represents a -COO-Rt- group, Rt is preferably an alkylene group having 1 to 5 carbon atoms, and is preferably a -CH ２- group, -(CH ２ ) ２ - group or -(CH ２ ) ３ The - group is more preferred.

[0065] Rx １ ~Rx ３ The alkyl group of Rx is preferably an alkyl group having 1 to 4 carbon atoms, such as a methyl group, an ethyl group, an n-propyl group, an isopropyl group, an n-butyl group, an isobutyl group, or a t-butyl group. １ ~Rx ３ The cycloalkyl group of Rx is preferably a monocyclic cycloalkyl group such as a cyclopentyl group or a cyclohexyl group, or a polycyclic cycloalkyl group such as a norbornyl group, a tetracyclodecanyl group, a tetracyclododecanyl group, or an adamantyl group. １ ~Rx ３ The aryl group in Rx is preferably an aryl group having 6 to 10 carbon atoms, and examples thereof include a phenyl group, a naphthyl group, and an anthryl group. １ ~Rx ３ The alkenyl group of Rx is preferably a vinyl group. １ ~Rx ３ As the cycloalkyl group formed by combining the above two, a monocyclic cycloalkyl group such as a cyclopentyl group or a cyclohexyl group is preferred. Polycyclic cycloalkyl groups such as a norbornyl group, a tetracyclodecanyl group, a tetracyclododecanyl group, and an adamantyl group are also preferred. Among these, a monocyclic cycloalkyl group having 5 to 6 carbon atoms is preferred. Rx １ ~Rx ３ The cycloalkyl group formed by bonding these two may have, for example, one of the methylene groups constituting the ring replaced with a heteroatom such as an oxygen atom, a group containing a heteroatom such as a carbonyl group, or a vinylidene group. Furthermore, in these cycloalkyl groups, one or more of the ethylene groups constituting the cycloalkane ring may be replaced with a vinylene group. The repeating unit represented by formula (AI) can be, for example, Rx １ is a methyl group or an ethyl group, and Rx ２ and Rx ３and are preferably bonded to form the above-mentioned cycloalkyl group.

[0066] When each of the above groups has a substituent, examples of the substituent include an alkyl group (having 1 to 4 carbon atoms), a halogen atom, a hydroxyl group, an alkoxy group (having 1 to 4 carbon atoms), a carboxyl group, and an alkoxycarbonyl group (having 2 to 6 carbon atoms). The number of carbon atoms in the substituent is preferably 8 or less.

[0067] The repeating unit represented by formula (AI) may be an acid-decomposable (meth)acrylic acid tertiary alkyl ester repeating unit (Xa １ represents a hydrogen atom or a methyl group, and T represents a single bond).

[0068] The resin (A) may have a repeating unit having an acid-decomposable group containing an unsaturated bond as a repeating unit having an acid-decomposable group. As the repeating unit having an acid-decomposable group containing an unsaturated bond, a repeating unit represented by formula (B) is preferred.

[0069]

[0070] In formula (B), Xb represents a hydrogen atom, a halogen atom, or an alkyl group which may have a substituent. L represents a single bond or a divalent linking group which may have a substituent. Ry １ ~Ry ３ each independently represents a linear or branched alkyl group, a monocyclic or polycyclic cycloalkyl group, an alkenyl group, an alkynyl group, or a monocyclic or polycyclic aryl group, provided that Ry １ ~Ry ３ At least one of R represents an alkenyl group, an alkynyl group, a monocyclic or polycyclic cycloalkenyl group, or a monocyclic or polycyclic aryl group. １ ~Ry ３ may be bonded to form a monocyclic or polycyclic ring (such as a monocyclic or polycyclic cycloalkyl group or cycloalkenyl group).

[0071] The alkyl group represented by Xb, which may have a substituent, is, for example, a methyl group or —CH ２ -R １１Examples of the group include a group represented by the following formula: １１ represents a halogen atom (such as a fluorine atom), a hydroxyl group, or a monovalent organic group, and examples thereof include an alkyl group having 5 or less carbon atoms which may be substituted with a halogen atom, an acyl group having 5 or less carbon atoms which may be substituted with a halogen atom, and an alkoxy group having 5 or less carbon atoms which may be substituted with a halogen atom, preferably an alkyl group having 3 or less carbon atoms, and more preferably a methyl group. Xb is preferably a hydrogen atom, a fluorine atom, a methyl group, a trifluoromethyl group, or a hydroxymethyl group.

[0072] Examples of the divalent linking group for L include a -Rt- group, a -CO- group, a -COO-Rt- group, a -COO-Rt-CO- group, a -Rt-CO- group, and a -O-Rt- group. In the formula, Rt represents an alkylene group, a cycloalkylene group, or an aromatic ring group, and an aromatic ring group is preferable. L is preferably a -Rt- group, a -CO- group, a -COO-Rt-CO- group, or a -Rt-CO- group. Rt may have a substituent such as a halogen atom, a hydroxyl group, or an alkoxy group.

[0073] Ry １ ~Ry ３ The alkyl group of Ry is preferably an alkyl group having 1 to 4 carbon atoms, such as a methyl group, an ethyl group, an n-propyl group, an isopropyl group, an n-butyl group, an isobutyl group, or a t-butyl group. １ ~Ry ３ The cycloalkyl group of Ry is preferably a monocyclic cycloalkyl group such as a cyclopentyl group or a cyclohexyl group, or a polycyclic cycloalkyl group such as a norbornyl group, a tetracyclodecanyl group, a tetracyclododecanyl group, or an adamantyl group. １ ~Ry ３ The aryl group in Ry is preferably an aryl group having 6 to 10 carbon atoms, and examples thereof include a phenyl group, a naphthyl group, and an anthryl group. １ ~Ry ３ The alkenyl group in Ry is preferably a vinyl group. １ ~Ry ３ The alkynyl group in Ry is preferably an ethynyl group. １ ~Ry ３The cycloalkenyl group of Ry is preferably a monocyclic cycloalkyl group having a structure containing a double bond in a part thereof, such as a cyclopentyl group or a cyclohexyl group. １ ~Ry ３ The cycloalkyl group formed by combining the above two groups is preferably a monocyclic cycloalkyl group such as a cyclopentyl group or a cyclohexyl group, or a polycyclic cycloalkyl group such as a norbornyl group, a tetracyclodecanyl group, a tetracyclododecanyl group, or an adamantyl group. Among these, a monocyclic cycloalkyl group having 5 to 6 carbon atoms is more preferred. １ ~Ry ３ The cycloalkyl group or cycloalkenyl group formed by bonding two of the above is, for example, a group in which one of the methylene groups constituting the ring is substituted with a heteroatom such as an oxygen atom, a carbonyl group, or —SO ２ - group and -SO ３ The repeating unit represented by formula (B) may be substituted with a group containing a hetero atom such as a - group, a vinylidene group, or a combination thereof. In addition, in these cycloalkyl groups or cycloalkenyl groups, one or more ethylene groups constituting the cycloalkane ring or cycloalkene ring may be substituted with a vinylene group. １ is a methyl group, an ethyl group, a vinyl group, an allyl group, or an aryl group, and Ry ２ and Ry ３ and are bonded to form the above-mentioned cycloalkyl group or cycloalkenyl group.

[0074] When each of the above groups has a substituent, examples of the substituent include an alkyl group (having 1 to 4 carbon atoms), a halogen atom, a hydroxyl group, an alkoxy group (having 1 to 4 carbon atoms), a carboxyl group, and an alkoxycarbonyl group (having 2 to 6 carbon atoms). The number of carbon atoms in the substituent is preferably 8 or less.

[0075] The repeating unit represented by formula (B) is preferably an acid-decomposable (meth)acrylic acid tertiary ester repeating unit (a repeating unit in which Xb represents a hydrogen atom or a methyl group and L represents a —CO— group), an acid-decomposable hydroxystyrene tertiary alkyl ether repeating unit (a repeating unit in which Xb represents a hydrogen atom or a methyl group and L represents a phenyl group), or an acid-decomposable styrene carboxylic acid tertiary ester repeating unit (a repeating unit in which Xb represents a hydrogen atom or a methyl group and L represents a —Rt—CO— group (Rt is an aromatic group)).

[0076] The content of the repeating units having an acid-decomposable group containing an unsaturated bond is preferably 15 mol% or more, more preferably 20 mol% or more, and even more preferably 30 mol% or more, based on the total repeating units in the resin (A), and the upper limit thereof is preferably 80 mol% or less, more preferably 70 mol% or less, and even more preferably 60 mol% or less, based on the total repeating units in the resin (A).

[0077] The content of the repeating units having an acid-decomposable group is preferably 15 mol% or more, more preferably 20 mol% or more, and even more preferably 30 mol% or more, based on the total repeating units in the resin (A), and the upper limit thereof is preferably 90 mol% or less, more preferably 80 mol% or less, even more preferably 70 mol% or less, and particularly preferably 60 mol% or less, based on the total repeating units in the resin (A).

[0078] Resin (A) may contain at least one repeating unit selected from the group consisting of Group A below, and / or at least one repeating unit selected from the group consisting of Group B below. Group A: A group consisting of the following repeating units (20) to (25). (20) A repeating unit having an acid group, as described below. (21) A repeating unit having neither an acid-decomposable group nor an acid group, and having a fluorine atom, a bromine atom, or an iodine atom, as described below. (22) A repeating unit having a lactone group, a sultone group, or a carbonate group, as described below. (23) A repeating unit having a photoacid-generating group, as described below. (24) A repeating unit represented by Formula (V-1) or Formula (V-2) as described below. (25) A repeating unit for reducing main chain mobility. The repeating units represented by Formulas (A) to (E) as described below correspond to (25) A repeating unit for reducing main chain mobility. Group B: A group consisting of the following repeating units (30) to (32). (30) A repeating unit having at least one group selected from a lactone group, a sultone group, a carbonate group, a hydroxyl group, a cyano group, and an alkali-soluble group, as described below. (31) A repeating unit having an alicyclic hydrocarbon structure and not exhibiting acid decomposability, as described below. (32) A repeating unit represented by formula (III), as described below, having neither a hydroxyl group nor a cyano group.

[0079] The resin (A) preferably has an acid group, and as described below, preferably contains a repeating unit having an acid group. The definition of the acid group will be explained later together with preferred embodiments of the repeating unit having an acid group. When the resin (A) has an acid group, the interaction between the resin (A) and the acid generated from the photoacid generator is more excellent. As a result, the diffusion of the acid is further suppressed, and the cross-sectional shape of the formed pattern can be more rectangular.

[0080] Resin (A) may have at least one repeating unit selected from the group consisting of Group A. When the actinic ray-sensitive or radiation-sensitive resin composition is used as an actinic ray-sensitive or radiation-sensitive resin composition for EUV exposure, resin (A) preferably has at least one repeating unit selected from the group consisting of Group A. Resin (A) may contain at least one of a fluorine atom and an iodine atom. When the actinic ray-sensitive or radiation-sensitive resin composition is used as an actinic ray-sensitive or radiation-sensitive resin composition for EUV exposure, resin (A) preferably contains at least one of a fluorine atom and an iodine atom. When resin (A) contains both fluorine atoms and iodine atoms, resin (A) may have one repeating unit containing both fluorine atoms and iodine atoms, or resin (A) may contain two repeating units: a repeating unit containing a fluorine atom and a repeating unit containing an iodine atom. Resin (A) may have a repeating unit having an aromatic group. When the actinic ray-sensitive or radiation-sensitive resin composition is used as an actinic ray-sensitive or radiation-sensitive resin composition for EUV exposure, it is also preferable that the resin (A) has a repeating unit having an aromatic group. The resin (A) may have at least one repeating unit selected from the group consisting of Group B above. When the actinic ray-sensitive or radiation-sensitive resin composition is used as an actinic ray-sensitive or radiation-sensitive resin composition for ArF, it is preferable that the resin (A) has at least one repeating unit selected from the group consisting of Group B above. Note that when the actinic ray-sensitive or radiation-sensitive resin composition is used as an actinic ray-sensitive or radiation-sensitive resin composition for ArF, it is preferable that the resin (A) does not contain either a fluorine atom or a silicon atom. When the actinic ray-sensitive or radiation-sensitive resin composition is used as an actinic ray-sensitive or radiation-sensitive resin composition for ArF, it is preferable that the resin (A) does not have an aromatic group.

[0081] (Repeating Unit Having an Acid Group) The resin (A) may have a repeating unit having an acid group. The acid group is preferably an acid group having a pKa of 13 or less. The acid dissociation constant of the acid group is preferably 13 or less, more preferably 3 to 13, and even more preferably 5 to 10. When the resin (A) has an acid group having a pKa of 13 or less, the content of the acid group in the resin (A) is not particularly limited, but is often 0.2 to 6.0 mmol / g. Of these, 0.8 to 6.0 mmol / g is preferred, 1.2 to 5.0 mmol / g is more preferred, and 1.6 to 4.0 mmol / g is even more preferred. When the content of the acid group is within the above range, development proceeds well, and the formed pattern shape is excellent, and resolution is also excellent. The acid group is preferably, for example, a carboxyl group, a phenolic hydroxyl group, a fluorinated alcohol group (preferably a hexafluoroisopropanol group), a sulfonic acid group, a sulfonamide group, or an isopropanol group, and among these, a phenolic hydroxyl group is more preferable. In the hexafluoroisopropanol group, one or more (preferably one to two) fluorine atoms may be substituted with a group other than a fluorine atom (such as an alkoxycarbonyl group). The acid group may be, for example, a -C(CF ３ )(OH)—CF ２ In addition, one or more fluorine atoms are substituted with a group other than a fluorine atom to form -C(CF ３ )(OH)—CF ２ The repeating unit having an acid group is preferably a repeating unit different from the repeating unit having a structure in which a polar group is protected with a group that is cleaved by the action of an acid, and a repeating unit having a lactone group, a sultone group, or a carbonate group, which will be described later. The repeating unit having an acid group may have a fluorine atom or an iodine atom.

[0082] The repeating unit having an acid group is preferably a repeating unit having a hydroxyl group bonded to an aromatic ring, and is preferably a repeating unit represented by the following formula (b1-1).

[0083]

[0084] In general formula (b1-1), A ａ１represents a hydrogen atom, an alkyl group, a cycloalkyl group, a halogen atom, or a cyano group. ２１ represents a halogen atom, an alkyl group, a cycloalkyl group, an aryl group, an alkenyl group, an aralkyl group, an alkoxy group, an alkylcarbonyloxy group, an alkylsulfonyloxy group, an alkyloxycarbonyl group, or an aryloxycarbonyl group, and when there are a plurality of R groups, they may be the same or different. ２１ When R ２１ is preferably a hydrogen atom. a represents an integer of 1 to 3. b represents an integer of 0 to (5-a).

[0085] When the resin (A) contains a repeating unit having an acid group, the content of the repeating unit having an acid group is preferably 10 mol% or more, more preferably 15 mol% or more, based on the total repeating units in the resin (A), and the upper limit thereof is preferably 70 mol% or less, more preferably 65 mol% or less, and even more preferably 60 mol% or less, based on the total repeating units in the resin (A).

[0086] (Repeating units having neither an acid-decomposable group nor an acid group, and having a fluorine atom, a bromine atom, or an iodine atom) In addition to the above-mentioned <repeating units having an acid-decomposable group> and <repeating units having an acid group>, the resin (A) may have a repeating unit having neither an acid-decomposable group nor an acid group, and having a fluorine atom, a bromine atom, or an iodine atom (hereinafter also referred to as unit X). The <repeating units having neither an acid-decomposable group nor an acid group, and having a fluorine atom, a bromine atom, or an iodine atom> referred to here is preferably different from other types of repeating units belonging to Group A, such as the <repeating units having a lactone group, a sultone group, or a carbonate group> and the <repeating units having a photoacid-generating group> described below.

[0087] The unit X is preferably a repeating unit represented by formula (C).

[0088]

[0089] L ５ represents a single bond or an ester group. ９represents a hydrogen atom or an alkyl group which may have a fluorine atom or an iodine atom. １０ represents a hydrogen atom, an alkyl group which may have a fluorine atom or an iodine atom, a cycloalkyl group which may have a fluorine atom or an iodine atom, an aryl group which may have a fluorine atom or an iodine atom, or a group which is a combination of these.

[0090] Examples of repeating units having a fluorine atom or an iodine atom are shown below.

[0091] The content of the units X is preferably 0 mol% or more, more preferably 5 mol% or more, and even more preferably 10 mol% or more, based on all repeating units in the resin (A), and the upper limit thereof is preferably 50 mol% or less, more preferably 45 mol% or less, and even more preferably 40 mol% or less, based on all repeating units in the resin (A).

[0092] Among the repeating units of the resin (A), the total content of repeating units containing at least one of a fluorine atom, a bromine atom, and an iodine atom is preferably 10 mol% or more, more preferably 20 mol% or more, even more preferably 30 mol% or more, and particularly preferably 40 mol% or more, based on the total repeating units of the resin (A). The upper limit is not particularly limited, but is, for example, 100 mol% or less, based on the total repeating units of the resin (A). Examples of repeating units containing at least one of a fluorine atom, a bromine atom, and an iodine atom include repeating units having a fluorine atom, a bromine atom, or an iodine atom and an acid-decomposable group, repeating units having a fluorine atom, a bromine atom, or an iodine atom and an acid group, and repeating units having a fluorine atom, a bromine atom, or an iodine atom.

[0093] (Repeating unit having a lactone group, a sultone group, or a carbonate group) The resin (A) may have a repeating unit (hereinafter also referred to as "unit Y") having at least one selected from the group consisting of a lactone group, a sultone group, and a carbonate group. It is also preferable that unit Y does not have a hydroxyl group or an acid group such as a hexafluoropropanol group.

[0094] The lactone group or sultone group may have a lactone structure or a sultone structure. The lactone structure or sultone structure is preferably a 5- to 7-membered lactone structure or a 5- to 7-membered sultone structure. Among these, a 5- to 7-membered lactone structure to which another ring structure is fused, forming a bicyclo or spiro structure, or a 5- to 7-membered sultone structure to which another ring structure is fused, forming a bicyclo or spiro structure, is more preferred. Resin (A) preferably has a repeating unit having a lactone group or sultone group formed by removing one or more hydrogen atoms from a ring atom of a lactone structure represented by any one of formulas (LC1-1) to (LC1-21) below, or a sultone structure represented by any one of formulas (SL1-1) to (SL1-3) below, and the lactone group or sultone group may be directly bonded to the main chain. For example, the ring atom of the lactone group or sultone group may constitute the main chain of resin (A).

[0095]

[0096] The lactone structure or sultone structure may be formed by the substituent (Rb ２ ) may have a preferable substituent (Rb ２ ) includes an alkyl group having 1 to 8 carbon atoms, a cycloalkyl group having 4 to 7 carbon atoms, an alkoxy group having 1 to 8 carbon atoms, an alkoxycarbonyl group having 1 to 8 carbon atoms, a carboxyl group, a halogen atom, a cyano group, and an acid-decomposable group. n2 represents an integer of 0 to 4. When n2 is 2 or more, a plurality of Rb ２ may be different, and a plurality of Rb ２ They may be bonded to each other to form a ring.

[0097] Examples of repeating units having a group containing a lactone structure represented by any one of formulas (LC1-1) to (LC1-21) or a sultone structure represented by any one of formulas (SL1-1) to (SL1-3) include repeating units represented by the following formula (AI):

[0098]

[0099] In formula (AI), Rb ０represents a hydrogen atom, a halogen atom, or an alkyl group having 1 to 4 carbon atoms. ０ Preferred substituents that the alkyl group of Rb may have include a hydroxyl group and a halogen atom. ０ Examples of the halogen atom in Rb include a fluorine atom, a chlorine atom, a bromine atom, and an iodine atom. ０ is preferably a hydrogen atom or a methyl group. Ab represents a single bond, an alkylene group, a divalent linking group having a monocyclic or polycyclic alicyclic hydrocarbon structure, an ether group, an ester group, a carbonyl group, a carboxyl group, or a divalent linking group formed by combining these. Among these, Ab is preferably a single bond or -Ab １ -CO ２ A linking group represented by - is preferred. １ is a linear or branched alkylene group, or a monocyclic or polycyclic cycloalkylene group, and is preferably a methylene group, an ethylene group, a cyclohexylene group, an adamantylene group, or a norbornylene group. V is a group obtained by removing one hydrogen atom from a ring member atom of a lactone structure represented by any of formulas (LC1-1) to (LC1-21), or a group obtained by removing one hydrogen atom from a ring member atom of a sultone structure represented by any of formulas (SL1-1) to (SL1-3).

[0100] When optical isomers exist in the repeating unit having a lactone group or a sultone group, any optical isomer may be used. One optical isomer may be used alone, or multiple optical isomers may be used in combination. When one optical isomer is primarily used, its optical purity (ee) is preferably 90 or more, more preferably 95 or more.

[0101] The carbonate group is preferably a cyclic carbonate ester group. The repeating unit having a cyclic carbonate ester group is preferably a repeating unit represented by the following formula (A-1):

[0102]

[0103] In formula (A-1), R Ａ １represents a hydrogen atom, a halogen atom, or a monovalent organic group (preferably a methyl group); n represents an integer of 0 or more. Ａ ２ represents a substituent. When n is 2 or more, a plurality of R Ａ ２ may be the same or different. A represents a single bond or a divalent linking group. The divalent linking group is preferably an alkylene group, a divalent linking group having a monocyclic or polycyclic alicyclic hydrocarbon structure, an ether group, an ester group, a carbonyl group, a carboxyl group, or a divalent linking group formed by combining these. Z represents an atomic group which forms a monocyclic or polycyclic ring together with the group represented by -O-CO-O- in the formula.

[0104] When the resin (A) contains the unit Y, the content of the unit Y is preferably 1 mol% or more, more preferably 10 mol% or more, based on all repeating units in the resin (A), and the upper limit thereof is preferably 85 mol% or less, more preferably 80 mol% or less, even more preferably 70 mol% or less, and particularly preferably 60 mol% or less, based on all repeating units in the resin (A).

[0105] (Repeating unit having a photoacid generating group) The resin (A) may have, as a repeating unit other than the above, a repeating unit having a group that generates an acid upon irradiation with actinic rays or radiation (also referred to as a "photoacid generating group"). Examples of the repeating unit having a photoacid generating group include a repeating unit represented by formula (4).

[0106]

[0107] R ４１ represents a hydrogen atom or a methyl group. ４１ represents a single bond or a divalent linking group. ４２ represents a divalent linking group. ４０ represents a structural moiety that is decomposed by irradiation with actinic rays or radiation to generate an acid in the side chain.

[0108] Examples of the repeating unit represented by formula (4) include the repeating units described in paragraphs

[0094] to

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

[0094] of WO 2018 / 193954 A.

[0109] The content of the repeating unit having a photoacid generating group is preferably 1 mol% or more, more preferably 5 mol% or more, based on the total repeating units in the resin (A), and the upper limit thereof is preferably 40 mol% or less, more preferably 35 mol% or less, and even more preferably 30 mol% or less, based on the total repeating units in the resin (A).

[0110] (Repeating unit represented by formula (V-1) or the following formula (V-2)) The resin (A) may have a repeating unit represented by the following formula (V-1) or the following formula (V-2). The repeating units represented by the following formula (V-1) and the following formula (V-2) are preferably repeating units different from the above-mentioned repeating units.

[0111]

[0112] In the formula, R ６ and R ７ each independently represents a hydrogen atom, a hydroxyl group, an alkyl group, an alkoxy group, an acyloxy group, a cyano group, a nitro group, an amino group, a halogen atom, an ester group (-OCOR or -COOR: R is an alkyl group or a fluorinated alkyl group having 1 to 6 carbon atoms), or a carboxyl group. As the alkyl group, a linear, branched or cyclic alkyl group having 1 to 10 carbon atoms is preferred. ３ represents an integer of 0 to 6. ４ represents an integer of 0 to 4. ４ is a methylene group, an oxygen atom, or a sulfur atom. Examples of repeating units represented by formula (V-1) or (V-2) are shown below. Examples of repeating units represented by formula (V-1) or (V-2) include the repeating units described in paragraph

[0100] of WO 2018 / 193954.

[0113] Resin (A) may also use the "repeating units for reducing the mobility of the main chain" described in paragraphs

[0292] to

[0308] of WO 2023 / 106171.

[0114] (Repeating unit having at least one group selected from a lactone group, a sultone group, a carbonate group, a hydroxyl group, a cyano group, and an alkali-soluble group) The resin (A) may have a repeating unit having at least one group selected from a lactone group, a sultone group, a carbonate group, a hydroxyl group, a cyano group, and an alkali-soluble group. Examples of the repeating unit having a lactone group, a sultone group, or a carbonate group contained in the resin (A) include the repeating units described above in <Repeating unit having a lactone group, a sultone group, or a carbonate group>. The preferred content is also as described above in <Repeating unit having a lactone group, a sultone group, or a carbonate group>.

[0115] The resin (A) may have a repeating unit having a hydroxyl group or a cyano group. This improves substrate adhesion and developer affinity. The repeating unit having a hydroxyl group or a cyano group is preferably a repeating unit having an alicyclic hydrocarbon structure substituted with a hydroxyl group or a cyano group. The repeating unit having a hydroxyl group or a cyano group preferably does not have an acid-decomposable group. Examples of repeating units having a hydroxyl group or a cyano group include those described in paragraphs

[0081] to

[0084] of JP 2014-098921 A.

[0116] The resin (A) may have a repeating unit having an alkali-soluble group. Examples of the alkali-soluble group include a carboxyl group, a sulfonamide group, a sulfonylimide group, a bissulfonylimide group, and an aliphatic alcohol group (e.g., a hexafluoroisopropanol group) substituted at the α-position with an electron-withdrawing group, with a carboxyl group being preferred. When the resin (A) contains a repeating unit having an alkali-soluble group, the resolution in contact hole applications is improved. Examples of repeating units having an alkali-soluble group include those described in paragraphs

[0085] and

[0086] of JP 2014-098921 A.

[0117] (Repeating unit having an alicyclic hydrocarbon structure and not exhibiting acid decomposability) Resin (A) may have a repeating unit having an alicyclic hydrocarbon structure and not exhibiting acid decomposability. This can reduce elution of low-molecular-weight components from the resist film into the immersion liquid during immersion exposure. Examples of repeating units having an alicyclic hydrocarbon structure and not exhibiting acid decomposability include repeating units derived from 1-adamantyl(meth)acrylate, diamantyl(meth)acrylate, tricyclodecanyl(meth)acrylate, or cyclohexyl(meth)acrylate.

[0118] (Repeating Unit Represented by Formula (III) Having Neither a Hydroxyl Group nor a Cyano Group) The resin (A) may have a repeating unit represented by formula (III) having neither a hydroxyl group nor a cyano group.

[0119]

[0120] In formula (III), R ５ represents a hydrocarbon group having at least one cyclic structure and having neither a hydroxyl group nor a cyano group. Ra represents a hydrogen atom, an alkyl group, or a —CH ２ -O-Ra ２ represents a group. ２ represents a hydrogen atom, an alkyl group, or an acyl group. Examples of the repeating unit represented by formula (III) that does not have either a hydroxyl group or a cyano group include those described in paragraphs

[0087] to

[0094] of JP 2014-098921 A.

[0121] (Other Repeating Units) Furthermore, the resin (A) may have a repeating unit other than the repeating units described above. For example, the resin (A) may have a repeating unit selected from the group consisting of a repeating unit having an oxathiane ring group, a repeating unit having an oxazolone ring group, a repeating unit having a dioxane ring group, and a repeating unit having a hydantoin ring group.

[0122] In addition to the repeating structural units described above, the resin (A) may have various repeating structural units for the purpose of adjusting dry etching resistance, suitability for a standard developer, substrate adhesion, resist profile, resolution, heat resistance, sensitivity, and the like.

[0123] As the resin (A), particularly when the composition of the present invention is used as an actinic ray-sensitive or radiation-sensitive resin composition for ArF, it is preferable that all of the repeating units are composed of repeating units derived from a compound having an ethylenically unsaturated bond. In particular, it is also preferable that all of the repeating units are composed of (meth)acrylate repeating units. When all of the repeating units are composed of (meth)acrylate repeating units, any of those in which all of the repeating units are methacrylate repeating units, all of the repeating units are acrylate repeating units, or all of the repeating units are a combination of methacrylate repeating units and acrylate repeating units can be used, and it is preferable that the acrylate repeating units account for 50 mol% or less of the total repeating units.

[0124] Resin (A) can be synthesized according to a conventional method (e.g., radical polymerization). The weight average molecular weight (Mw) of resin (A), as measured by GPC in terms of polystyrene, is preferably 30,000 or less, more preferably 1,000 to 30,000, even more preferably 3,000 to 30,000, and particularly preferably 5,000 to 15,000. The dispersity (molecular weight distribution, Mw / Mn) of resin (A) is preferably 1 to 5, more preferably 1 to 3, even more preferably 1.2 to 3.0, and particularly preferably 1.2 to 2.0. The smaller the dispersity, the better the resolution and resist shape, and furthermore, the smoother the sidewalls of the resist pattern and the better the roughness.

[0125] In the actinic ray-sensitive or radiation-sensitive resin composition, the content of the resin (A) is preferably 30.0 to 99.9 mass%, more preferably 40.0 to 99.9 mass%, and even more preferably 60.0 to 90.0 mass%, based on the total solid content of the actinic ray-sensitive or radiation-sensitive resin composition. The resin (A) may be used alone or in combination.

[0126] [Actinic Ray- or Radiation-Sensitive Acid Generator (Q1)] The acid generator (Q1) contained in the composition of the present invention will be described. The acid generator (Q1) is an onium salt compound having a structure (hereinafter also referred to as a specific structure) in which three or more iodine atoms and at least two or more atoms selected from oxygen atoms and sulfur atoms are bonded to the same aromatic ring. The acid generator (Q1) is a compound (photoacid generator) that generates an acid upon irradiation with actinic rays or radiation. The acid generator (Q1) can be used as a photoacid generator or as an acid diffusion controller (photodegradable quencher).

[0127] The acid generator (Q1) is an onium salt compound having a cation moiety and an anion moiety. The acid generator (Q1) has at least one specific structure, and may have two or more specific structures. The acid generator (Q1) preferably has one or two specific structures. The acid generator (Q1) may have the specific structure in the cation moiety, the anion moiety, or both the cation moiety and the anion moiety.

[0128] The anion moiety of the acid generator (Q1) is preferably an organic anion, and the cation moiety is preferably an organic cation.

[0129] The acid generator (Q1) is preferably a compound that generates an organic acid upon exposure to light. 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, aralkylcarboxylic acids, etc.), methide acids (tris(alkylsulfonyl)methide acids, etc.), sulfonamidic acids, sulfonimide acids (bis(alkylsulfonyl)imide acids, etc.), and carbonylsulfonylimide acids.

[0130] That is, the acid generator (Q1) converts to a sulfo group (—SO ３ H), carboxy group (-COOH), methide acid group, sulfonamide group (-SO ２ NH-), sulfonimide group (-SO ２ -NH-SO ２ -), and carbonylsulfonylimido group (-SO２ Preferably, the compound is an acid-generating compound having at least one group selected from the group consisting of —NH—CO—.

[0131] In this specification, the methide acid group refers to a group represented by the following general formula (M1).

[0132]

[0133] In general formula (M1), X １ ~X ３ are each independently -SO ２ -, -CO ２ * represents a bond.

[0134] The acid generator (Q1) has three or more iodine atoms in the same aromatic ring. The number of iodine atoms is not particularly limited as long as it is three or more, but is preferably four or more, and more preferably four.

[0135] In the acid generator (Q1), at least two atoms selected from an oxygen atom and a sulfur atom are further bonded to the aromatic ring. The group containing an oxygen atom bonded to the aromatic ring is not particularly limited as long as it contains an oxygen atom, but may include *-O-**, *-OH, *-O-CO-**, *-O-SO ２ The group containing a sulfur atom bonded to the aromatic ring is not particularly limited as long as it contains a sulfur atom, but examples thereof include *-S-**, *-SO ２ -**, etc. * represents a bond to an aromatic ring having three or more iodine atoms, and ** represents a bond to another group in the acid generator (Q1).

[0136] The number of at least two atoms selected from oxygen atoms and sulfur atoms bonded to the aromatic ring is not particularly limited as long as it is 2 or more, but is preferably 2 to 3, and more preferably 2. Furthermore, the atom bonded to the aromatic ring may be either an oxygen atom or a sulfur atom, or may be both an oxygen atom and a sulfur atom, but is preferably an oxygen atom.

[0137] In the acid generator (Q1), the aromatic ring having three or more iodine atoms and bonded to at least two or more atoms selected from oxygen atoms and sulfur atoms may be a monocyclic or polycyclic ring. Specifically, it is more preferable that it represents an aromatic hydrocarbon ring having 6 to 20 carbon atoms, such as a benzene ring, a naphthalene ring, or an anthracene ring, and is preferably a benzene ring.

[0138] The acid generator (Q1) is preferably an onium salt compound having a structure in which four or more iodine atoms and at least two or more atoms selected from oxygen atoms and sulfur atoms are bonded to the same aromatic ring. The onium salt compound preferably contains an organic anion having a structure in which four or more iodine atoms and at least two or more atoms selected from oxygen atoms and sulfur atoms are bonded to the same aromatic ring. The acid generator (Q1) is also preferably an onium salt compound having a structure in which three or more iodine atoms and two or more oxygen atoms are bonded to the same aromatic ring.

[0139] One preferred embodiment of the acid generator (Q1) is one in which the acid generator (Q1) contains an organic anion having a structure in which three or more iodine atoms and at least two or more atoms selected from oxygen atoms and sulfur atoms are bonded to the same aromatic ring, and it is more preferred that the acid generator (Q1) contains an organic anion having a structure in which four or more iodine atoms and at least two or more atoms selected from oxygen atoms and sulfur atoms are bonded to the same aromatic ring.

[0140] The anion moiety of the acid generator (Q1) is preferably an organic anion represented by the following general formula (1A).

[0141]

[0142] In general formula (1A), Y １ is -O-, -S-, or -SO ２ - represents. １ R each independently represents a hydrogen atom or an organic group. １ Two of R may be bonded to each other to form a ring structure together with other atoms in general formula (1A). ２ is COO －or an organic group. m1 represents an integer of 3 to 8. p1 represents an integer of 0 to 2. n1 represents an integer that satisfies 2≦n1≦(6+2p1-m1). q1 represents an integer that satisfies 0≦q1≦(6+2p1-m1-n1). １ and R ２ At least one of them has an anionic moiety.

[0143] In general formula (1A), Y １ is -O-, -S-, or -SO ２ It represents -, and preferably represents -O-.

[0144] In general formula (1A), R １ R each independently represents a hydrogen atom or an organic group. １ The organic group represented by is not particularly limited, but is preferably an organic group having 1 to 100 carbon atoms. １ preferably contains a hydrocarbon group, and preferably contains at least one of an aliphatic hydrocarbon group (preferably an aliphatic hydrocarbon group having 1 to 10 carbon atoms) and an aromatic hydrocarbon group (preferably an aromatic hydrocarbon group having 6 to 20 carbon atoms). The aliphatic hydrocarbon group may be a saturated hydrocarbon group or an unsaturated hydrocarbon group, and may be chain-like (straight-chain or branched-chain) or cyclic (alicyclic hydrocarbon group). The aliphatic hydrocarbon group may also contain a heteroatom (for example, an oxygen atom, a nitrogen atom, a sulfur atom, etc.). When the aliphatic hydrocarbon group contains an oxygen atom, for example, the chain of the chain-like aliphatic hydrocarbon group may contain -O- or -C(=O)O- in the chain or at the end, or the ring of the cyclic aliphatic hydrocarbon group may contain -O- or -C(=O)O- in the ring. R １ is -NR Ｑ１ -, -O-, -S-, -C(=O)-, -C(=O)O-, -S(=O)-, and -S(=O) ２ - may contain at least one selected from the group consisting of Ｑ１ represents a hydrogen atom, an alkyl group (for example, an alkyl group having 1 to 10 carbon atoms), a cycloalkyl group (for example, a cycloalkyl group having 3 to 20 carbon atoms), or an aryl group (for example, an aryl group having 6 to 20 carbon atoms).

[0145] R １may have an anionic moiety. The anionic moiety may be —SO ３ － , -COO － , -SO ２ N － -, -SO ２ -N － -SO ２ -, -SO ２ -N － Examples thereof include at least one group selected from —CO— and groups represented by the following general formula (M2).

[0146]

[0147] In general formula (M2), X １ ~X ３ are each independently -SO ２ -, -CO ２ * represents a bond.

[0148] R １ may further comprise one or more specific structures of the present invention.

[0149] R １ When two of the groups bond to each other to form a ring structure, the ring structure formed is preferably a 5-membered or 6-membered ring, and more preferably a 6-membered ring.

[0150] In general formula (1A), R ２ is COO － or an organic group. ２ The organic group represented by is not particularly limited, but is preferably an organic group having 1 to 100 carbon atoms. １ The organic group represented by R ２ may have an anionic moiety. The anionic moiety may be R １ The anionic moiety may be the same as the anionic moiety that R ２ may further comprise one or more specific structures of the present invention.

[0151] In general formula (1A), m1 represents an integer of 3 to 8, preferably 3 or 4, and more preferably 4. p1 represents an integer of 0 to 2, preferably 0. n1 represents an integer that satisfies 2≦n1≦(6+2p1-m1), and preferably 2 or 3. q1 represents an integer that satisfies 0≦q1≦(6+2p1-m1-n1), and preferably 0 or 1.

[0152] The number of anionic moieties contained in general formula (1A) is one or more, and may be two or more, and is preferably one or two.

[0153] The organic anion represented by the above general formula (1A) is preferably an organic anion represented by the following general formula (1B):

[0154]

[0155] In general formula (1B), R １ R each independently represents a hydrogen atom or an organic group. １ Two of R may be bonded to each other to form a ring structure together with other atoms in general formula (1B). ２ is COO － or an organic group. m1 represents an integer of 3 to 8. p1 represents an integer of 0 to 2. n1 represents an integer that satisfies 2≦n1≦(6+2p1-m1). q1 represents an integer that satisfies 0≦q1≦(6+2p1-m1-n1). １ and R ２ At least one of them has an anionic moiety.

[0156] R in general formula (1B) １ , R ２ , m1, n1, p1, and q1 are R in the general formula (1A) １ , R ２ , m1, n1, p1, and q1, and preferred examples thereof are also the same.

[0157] The organic anion represented by the general formula (1A) is also preferably an organic anion represented by the following general formula (1C):

[0158]

[0159] In general formula (1C), Y １is -O-, -S-, or -SO ２ - represents. １ R each independently represents a hydrogen atom or an organic group. １ Two of R may be bonded to each other to form a ring structure together with other atoms in general formula (1C). ２ is COO － or an organic group. m11 represents 3 or 4. n11 represents 2 or 3. q11 represents 0 or 1. However, m11 + n11 + q11 is 5 or 6. １ and R ２ At least one of them has an anionic moiety.

[0160] Y in general formula (1C) １ , R １ and R ２ represents Y in the general formula (1A). １ , R １ and R ２ is synonymous with.

[0161] The organic anion represented by the general formula (1A) is more preferably an organic anion represented by the following general formula (1D):

[0162]

[0163] In general formula (1D), R １ Each of R independently represents a hydrogen atom or an organic group. １ may be bonded to each other to form a ring structure together with other atoms in general formula (1D). １ At least one of them has an anionic moiety.

[0164] R in general formula (1D) １ represents R in the above general formula (1A). １ is synonymous with.

[0165] The organic anion represented by the general formula (1A) is also preferably an organic anion represented by the following general formula (1E):

[0166]

[0167] In general formula (1E), Y １ are each independently —O—, —S—, or —SO２ - represents. １１ａ represents an organic group having at least one anionic moiety. １１ｂ represents a hydrogen atom. １１ａ and R １１ｂ may be bonded to each other to form a ring structure.

[0168] R １１ａ The organic group represented by is R in the above general formula (1A). １ Examples of organic groups include:

[0169] When the acid generator (Q1) is used as an acid diffusion controller, the organic anion represented by the general formula (1A) above is more preferably an organic anion represented by the following general formula (1F) or (1G):

[0170]

[0171] In general formula (1E), R １２ R each independently represents a hydrogen atom or an organic group. １２ Two of these may be bonded to each other to form a ring structure together with other atoms in general formula (1F).

[0172] R １２ The organic group represented by is R in the above general formula (1A). １ Examples of organic groups include R １２ It is preferred that the compound does not have an anionic moiety.

[0173]

[0174] In general formula (1G), R １３ａ is -COO － Also -SO ２ -N － represents an organic group having —CO—. １３ｂ represents a hydrogen atom. １３ａ and R １３ｂ may be bonded to each other to form a ring structure.

[0175] R １３ａ The organic group represented by is R in the above general formula (1A). １ The organic groups include, but are not limited to, —COO － Also -SO ２ -N－ It has —CO—.

[0176] Examples of organic anions having specific structures are shown below, but are not limited to these: Me represents a methyl group.

[0177]

[0178]

[0179]

[0180]

[0181]

[0182] When the acid generator (Q1) has a specific structure in the cation moiety, it may have an anion moiety without a specific structure. The anion moiety without a specific structure may be an anion moiety such as X described in the compound (B) that generates an acid upon irradiation with actinic rays or radiation, which will be described later. － and the anions in Compound (I) and Compound (II).

[0183] The acid generator (Q1) preferably has a halogen atom in the cation moiety (excluding cases where the halogen atom is a monovalent iodine cation). Examples of the halogen atom include a fluorine atom, a chlorine atom, a bromine atom, and an iodine atom, and a fluorine atom or an iodine atom is preferred. By having a halogen atom in the cation moiety, it is possible to increase the absorption efficiency of EUV light or an electron beam and the solubility of the acid generator (Q1) in a developer, resulting in improved roughness performance and defect suppression.

[0184] The cationic moiety of the acid generator (Q1) is preferably a sulfonium cation or an iodonium cation, that is, the acid generator (Q1) preferably has a sulfonium cation or an iodonium cation.

[0185] Another preferred embodiment of the acid generator (Q1) is one that contains an organic cation selected from a sulfonium cation and an iodonium cation, which has a structure in which three or more iodine atoms and at least two or more atoms selected from oxygen atoms and sulfur atoms are bonded to the same aromatic ring.

[0186] The cationic moiety of the acid generator (Q1) is preferably an organic cation represented by the following general formula (2A).

[0187]

[0188] In general formula (2A), Y ２ is -O-, -S-, or -SO ２ - represents. ３ R each independently represents a hydrogen atom or an organic group. ３ Two of R may be bonded to each other to form a ring structure together with other atoms in general formula (2A). ４ is COO － or an organic group. m2 represents an integer of 3 to 8. p2 represents an integer of 0 to 2. n2 represents an integer that satisfies 2≦n2≦(6+2p2-m2). q2 represents an integer that satisfies 0≦q2≦(6+2p2-m2-n2). ３ and R ４ One of the groups has a cationic moiety.

[0189] In general formula (2A), Y ２ is -O-, -S-, or -SO ２ It represents -, and preferably represents -O-.

[0190] In general formula (2A), R ３ R each independently represents a hydrogen atom or an organic group. ３ The organic group represented by is not particularly limited, but is preferably an organic group having 1 to 100 carbon atoms. ３preferably contains a hydrocarbon group, and preferably contains at least one of an aliphatic hydrocarbon group (preferably an aliphatic hydrocarbon group having 1 to 10 carbon atoms) and an aromatic hydrocarbon group (preferably an aromatic hydrocarbon group having 6 to 20 carbon atoms). The aliphatic hydrocarbon group may be a saturated hydrocarbon group or an unsaturated hydrocarbon group, and may be chain-like (straight-chain or branched-chain) or cyclic (alicyclic hydrocarbon group). The aliphatic hydrocarbon group may also contain a heteroatom (for example, an oxygen atom, a nitrogen atom, a sulfur atom, etc.). When the aliphatic hydrocarbon group contains an oxygen atom, for example, the chain of the chain-like aliphatic hydrocarbon group may contain -O- or -C(=O)O- in the chain or at the end, or the ring of the cyclic aliphatic hydrocarbon group may contain -O- or -C(=O)O- in the ring. R ３ is -NR Ｑ１ -, -O-, -S-, -C(=O)-, -C(=O)O-, -S(=O)-, and -S(=O) ２ - may contain at least one selected from the group consisting of Ｑ１ represents a hydrogen atom, an alkyl group (for example, an alkyl group having 1 to 10 carbon atoms), a cycloalkyl group (for example, a cycloalkyl group having 3 to 20 carbon atoms), or an aryl group (for example, an aryl group having 6 to 20 carbon atoms).

[0191] R ３ may have a cationic moiety. Examples of the cationic moiety include groups represented by the following general formula (M3) or (M4).

[0192]

[0193] In the general formulas (M3) and (4), * represents a bond.

[0194] R ３ may further comprise one or more specific structures of the present invention.

[0195] R ３ When two of the groups bond to each other to form a ring structure, the ring structure formed is preferably a 5-membered or 6-membered ring, and more preferably a 6-membered ring.

[0196] In general formula (2A), R ４ is COO － or an organic group.４ The organic group represented by is not particularly limited, but is preferably an organic group having 1 to 100 carbon atoms. ３ The organic group represented by R ４ may have a cationic moiety. The cationic moiety may be R ３ The cationic moiety is the same as the anionic moiety that R ４ may further comprise one or more specific structures of the present invention.

[0197] In general formula (2A), m2 represents an integer of 3 to 8, preferably 3 or 4, and more preferably 4. p2 represents an integer of 0 to 2, preferably 0. n2 represents an integer that satisfies 2≦n2≦(6+2p2−m2), and preferably 2 or 3. q2 represents an integer that satisfies 0≦q2≦(6+2p2−m2−n2), and preferably 0 or 1.

[0198] The organic cation represented by the above general formula (2A) is preferably an organic cation represented by the following general formula (2B):

[0199]

[0200] In general formula (2B), R ３ R each independently represents a hydrogen atom or an organic group. ３ Two of R may be bonded to each other to form a ring structure together with other atoms in general formula (2B). ４ represents an organic group. m2 represents an integer of 3 to 8. p2 represents an integer of 0 to 2. n2 represents an integer that satisfies 2≦n2≦(6+2p2-m2). q2 represents an integer that satisfies 0≦q2≦(6+2p2-m2-n2). ３ and R ４ One of the groups has a cationic moiety.

[0201] R in general formula (2B) ３ , R ４ , m2, n2, p2, and q2 are R in the general formula (2A) ３ , R ４ , m2, n2, p2, and q2, and preferred examples thereof are also the same.

[0202] The organic cation represented by the above general formula (2A) is also preferably an organic cation represented by the following general formula (2C):

[0203]

[0204] In general formula (2C), Y ２ is -O-, -S-, or -SO ２ - represents. ３ R each independently represents a hydrogen atom or an organic group. ３ Two of R may be bonded to each other to form a ring structure together with other atoms in general formula (2C). ４ is COO － or an organic group. m21 represents 3 or 4. n21 represents 2 or 3. q21 represents 0 or 1. However, m21 + n21 + q21 is 5 or 6. ３ and R ４ At least one of these has a cationic moiety.

[0205] Y in general formula (2C) ２ , R ３ and R ４ represents Y in the general formula (2A). ２ , R ３ and R ４ is synonymous with.

[0206] The organic cation represented by the above general formula (2A) is more preferably an organic cation represented by the following general formula (2D).

[0207]

[0208] In general formula (2D), R ３ Each of R independently represents a hydrogen atom or an organic group. ３ may be bonded to each other to form a ring structure together with other atoms in general formula (2D). ３ At least one of these has a cationic moiety.

[0209] R in general formula (2D) ３ represents R in the above general formula (2A). ３ is synonymous with.

[0210] The organic cation represented by the above general formula (2A) is also preferably an organic cation represented by the following general formula (2E).

[0211]

[0212] In general formula (2E), Y ２ are each independently —O—, —S—, or —SO ２ L represents a divalent linking group. １ represents an arylene group. ２ and Ar ３ represents an aryl group.

[0213] Y in general formula (2E) ２ represents Y in the general formula (2A). ２ is synonymous with.

[0214] The divalent linking group represented by L is preferably an alkylene group (preferably an alkylene group having 1 to 10 carbon atoms). The alkylene group may contain —O— or —C(═O)O— in the chain or at the end.

[0215] Ar ２ and Ar ３ Examples of the aryl group represented by include R in formula (ZaI) described in the compound (B) that generates an acid upon irradiation with actinic rays or radiation, which will be described later. ２０１ ~R ２０３ Aryl groups such as １ Examples of the arylene group represented by the formula include Ar ２ and Ar ３ Examples of such groups include groups in which one arbitrary hydrogen atom has been removed from an aryl group such as the above.

[0216] Examples of organic cations having specific structures are shown below, but the invention is not limited to these.

[0217]

[0218] When the acid generator (Q1) has a specific structure in the anion moiety, it may have a cation moiety without a specific structure. The cation moiety without a specific structure may be any of the M compounds described in the compound (B) that generates an acid upon irradiation with actinic rays or radiation, which will be described later. ＋Examples include cations represented by the following formula:

[0219] In one preferred embodiment, the acid generator (Q1) is an onium salt compound that contains an anion moiety made of an organic anion having a structure in which three or more iodine atoms and at least two or more atoms selected from oxygen atoms and sulfur atoms are bonded to the same aromatic ring, and a cation moiety that has a sulfonium cation or an iodonium cation, and is preferably a compound represented by the following general formula (3A):

[0220]

[0221] In general formula (3A), Y １ is -O-, -S-, or -SO ２ - represents. １ R each independently represents a hydrogen atom or an organic group. １ Two of R may be bonded to each other to form a ring structure together with other atoms in general formula (3A). ２ is COO － or an organic group. m1 represents an integer of 3 to 8. p1 represents an integer of 0 to 2. n1 represents an integer that satisfies 2≦n1≦(6+2p1-m1). q1 represents an integer that satisfies 0≦q1≦(6+2p1-m1-n1). １ and R ２ At least one of them has an anionic moiety. ＋ represents a sulfonium cation or an iodonium cation. １ and R ２ represents the same number as the total number of anionic sites possessed by the

[0222] Y in general formula (3A) １ , R １ , R ２ , m1, n1, p1, and q1 are each independently selected from the group consisting of Y in the general formula (1A). １ , R １ , R ２ , m1, n1, p1, and q1, and preferred examples thereof are also the same.

[0223] Examples of the sulfonium cation or iodonium cation in general formula (3A) include sulfonium cations or iodonium cations corresponding to the above-mentioned general formula (2A), cations represented by formula (ZaI) and formula (ZaII) described below, and the like.

[0224] Another preferred embodiment of the acid generator (Q1) is an onium salt compound that contains a cation moiety containing a sulfonium cation or an iodonium cation, and that has a structure in which three or more iodine atoms and at least two or more atoms selected from oxygen atoms and sulfur atoms are bonded to the same aromatic ring, and that contains an organic anion moiety. The acid generator (Q1) is preferably a compound represented by the following general formula (4A):

[0225]

[0226] In general formula (4A), Y ２ is -O-, -S-, or -SO ２ - represents. ３ R each independently represents a hydrogen atom or an organic group. ３ Two of R may be bonded to each other to form a ring structure together with other atoms in general formula (4A). ４ is COO － or an organic group. m2 represents an integer of 3 to 8. p2 represents an integer of 0 to 2. n2 represents an integer that satisfies 2≦n2≦(6+2p2-m2). q2 represents an integer that satisfies 0≦q2≦(6+2p2-m2-n2). ３ and R ４ has a cation moiety represented by the above general formula (M3) or general formula (M4). ｕ－ represents an organic anion, and u represents the total number of anionic sites possessed by the organic anion.

[0227] Y in general formula (4A) ２ , R ３ , R ４ , m2, n2, p2, and q2 are each independently selected from the group consisting of Y in the general formula (2A). ２ , R ３ , R ４ , m2, n2, p2, and q2, and preferred examples thereof are also the same.

[0228] The organic anion (Xa ｕ－ ) may be an organic anion represented by the general formula (1A) above, or X described in the compound (B) that generates an acid upon irradiation with actinic rays or radiation described below. － and the anions in Compound (I) and Compound (II).

[0229] The acid generator (Q1) can be synthesized by referring to a known method. Specific synthesis examples are shown in the Examples described later. In the acid generator (Q1), the total valence of the anions in the anion moiety is the same as the total valence of the cations in the cation moiety.

[0230] The content of the acid generator (Q1) is preferably 1.0 mass% or more, more preferably 10.0 mass% or more, and even more preferably 15.0 mass% or more, based on the total solid content of the composition of the present invention. The upper limit of the content of the acid generator (Q1) is not particularly limited, but is usually 80.0 mass% or less, preferably 70.0 mass% or less, and more preferably 65.0 mass% or less, based on the total solid content of the composition. One type of acid generator (Q1) may be used, or two or more types may be used.

[0231] The present invention also relates to an onium salt compound containing an anion moiety consisting of an organic anion having a structure in which three or more iodine atoms and at least two or more atoms selected from oxygen atoms and sulfur atoms are bonded to the same aromatic ring, and a cation moiety having a sulfonium cation or an iodonium cation. The explanation of the organic anion having a specific structure and the cation moiety having a sulfonium cation or an iodonium cation can be cited from the explanation of the acid generator (Q1) above.

[0232] The present invention also relates to an onium salt compound containing a cation moiety containing a sulfonium cation or iodonium cation having a structure in which three or more iodine atoms and at least two or more atoms selected from oxygen atoms and sulfur atoms are bonded to the same aromatic ring, and an organic anion moiety. The explanation of the sulfonium cation or iodonium cation having a specific structure and the organic anion moiety can be cited from the explanation of the acid generator (Q1) above.

[0233] [Actinic ray- or radiation-sensitive acid generator (Q2)] The composition of the present invention preferably contains an actinic ray- or radiation-sensitive acid generator (Q2) (also referred to as "actinic ray- or radiation-sensitive acid generator (Q2)" or simply "acid generator (Q2)") that generates, upon exposure, an acid weaker than that generated by the actinic ray- or radiation-sensitive acid generator (Q1).

[0234] In the acid generators (Q1) and (Q2), the compound (B) that generates an acid upon irradiation with actinic rays or radiation (described below), and the photodegradable quencher (compound (CC)) of the present invention, the strength of the acid generated upon exposure is determined based on the magnitude of the acid dissociation constant (pKa) determined by the method described above. When there are multiple acid dissociation constants, the smallest one among them is used for evaluation.

[0235] The acid generator (Q2) may be a photoacid generator or a photodegradable quencher. The acid generator (Q2) may be a compound corresponding to the above-mentioned acid generator (Q1), or may be a compound other than the above-mentioned acid generator (Q1), such as compound (B) or compound (CC).

[0236] [Compound (B) that generates an acid upon irradiation with actinic rays or radiation] The composition of the present invention may further contain a compound (B) that generates an acid upon irradiation with actinic rays or radiation and is different from the acid generator (Q1). The compound (B) may be the acid generator (Q2) described above. The compound (B) may be in the form of a low molecular weight compound or may be incorporated into a part of a polymer. Furthermore, the form of a low molecular weight compound and the form of being incorporated into a part of a polymer may be used in combination. When the compound (B) is in the form of a low molecular weight compound, the molecular weight of the compound (B) is preferably 5,000 or less, more preferably 4,000 or less, and even more preferably 3,000 or less. The lower limit is not particularly limited, but is preferably 100 or more. When the compound (B) is in the form of being incorporated into a part of a polymer, it may be incorporated into a part of the resin (A) or into a resin different from the resin (A). The compound (B) is preferably in the form of a low molecular weight compound.

[0237] Examples of the compound (B) include "M ＋ X － ", and it is preferably a compound that generates an organic acid upon exposure. Examples of the organic acid include sulfonic acids (aliphatic sulfonic acids, aromatic sulfonic acids, camphorsulfonic acids, etc.), carboxylic acids (aliphatic carboxylic acids, aromatic carboxylic acids, aralkyl carboxylic acids, etc.), carbonylsulfonylimide acids, bis(alkylsulfonyl)imide acids, and tris(alkylsulfonyl)methide acids.

[0238] "M ＋ X － In the compound represented by the formula ", M ＋ represents a cation, preferably an organic cation.

[0239] M ＋ is preferably a sulfonium cation or an iodonium cation. ＋The cation represented by formula (ZaI) is not particularly limited. The valence of the cation may be monovalent or divalent or higher. 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)").

[0240]

[0241] 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.

[0242] 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.

[0243] First, the cation (ZaI-1) will be described. The cation (ZaI-1) is R in the above formula (ZaI). ２０１ ~R ２０３ is an arylsulfonium cation, in which at least one of R is an aryl group. ２０１ ~R ２０３ may all be aryl groups, or R ２０１ ~R ２０３ A part of R may be an aryl group, and the rest may be an alkyl group or a cycloalkyl group.２０１ ~R ２０３ is an aryl group, and R ２０１ ~R ２０３ The remaining two of R may be bonded to form a ring structure, and the ring may contain an oxygen atom, a sulfur atom, an ester group, an amide group, or a carbonyl group. ２０１ ~R ２０３ Examples of groups formed by combining two of the above include alkylene groups in which one or more methylene groups may be substituted with an oxygen atom, a sulfur atom, an ester group, an amide group, and / or a carbonyl group (e.g., butylene group, pentylene group, and —CH ２ -CH ２ -O-CH ２ -CH ２ The arylsulfonium cations include triarylsulfonium cations, diarylalkylsulfonium cations, aryldialkylsulfonium cations, diarylcycloalkylsulfonium cations, and aryldicycloalkylsulfonium cations.

[0244] 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.

[0245] R ２０１ ~R ２０３Preferred substituents that the aryl group, alkyl group, and cycloalkyl group may have include alkyl groups (e.g., having 1 to 15 carbon atoms), cycloalkyl groups (e.g., having 3 to 15 carbon atoms), aryl groups (e.g., having 6 to 14 carbon atoms), alkoxy groups (e.g., having 1 to 15 carbon atoms), cycloalkylalkoxy groups (e.g., having 1 to 15 carbon atoms), halogen atoms (e.g., fluorine and iodine), hydroxyl groups, carboxyl groups, ester groups, sulfinyl groups, sulfonyl groups, alkylthio groups, and phenylthio groups. The above substituents may further have substituents if possible, and it is also preferred that the alkyl group has a halogen atom as a substituent to form a halogenated alkyl group such as a trifluoromethyl group. It is also preferred that the above substituents, when combined in any manner, form an acid-decomposable group.

[0246] 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.

[0247] R ２０１ ~R ２０３ Examples of the alkyl group and cycloalkyl group in R include linear alkyl groups having 1 to 10 carbon atoms or branched alkyl groups having 3 to 10 carbon atoms (e.g., methyl, ethyl, propyl, butyl, and pentyl groups), and cycloalkyl groups having 3 to 10 carbon atoms (e.g., cyclopentyl, cyclohexyl, and norbornyl groups). ２０１ ~R ２０３may be further substituted with a halogen atom, 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.

[0248] Next, the cation (ZaI-3b) will be described. The cation (ZaI-3b) is a cation represented by the following formula (ZaI-3b).

[0249]

[0250] 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.

[0251] 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 ｙmay 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.

[0252] R １ｃ ~R ５ｃ Two or more of the following, R ６ｃ and R ７ｃ , and R ｘ and R ｙ Examples of the group formed by bonding of R include alkylene groups such as butylene and pentylene. A methylene group in this alkylene group may be substituted with a heteroatom such as an oxygen atom. ５ｃ and R ６ｃ , and R ５ｃ and R ｘ The group formed by bonding is preferably a single bond or an alkylene group. Examples of the alkylene group include a methylene group and an ethylene group.

[0253] R １ｃ ~R ５ｃ , R ６ｃ , R ７ｃ , R ｘ , R ｙ , and R １ｃ ~R ５ｃ Two or more of the following, R ５ｃ and R ６ｃ , R ６ｃ and R ７ｃ , R ５ｃ and R ｘ , and R ｘ and R ｙ The ring formed by bonding together may have a substituent.

[0254] Next, the cation (ZaI-4b) will be described. The cation (ZaI-4b) is a cation represented by the following formula (ZaI-4b).

[0255]

[0256] 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.

[0257] In formula (ZaI-4b), R １３ , R １４ , and R １５ The alkyl group in R may be linear or branched. The number of carbon atoms in the alkyl group is preferably 1 to 10. The alkyl group is preferably a methyl group, an ethyl group, an n-butyl group, a t-butyl group, or the like. １３ ~R １５ , and R ｘ and R ｙIt is also preferred that each of the substituents independently form an acid-decomposable group by any combination of the substituents.

[0258] 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).

[0259] R ２０４ and R ２０５ The aryl group, alkyl group, and cycloalkyl group in R may each independently have a substituent. ２０４ and R ２０５ Examples of the substituents that the aryl group, alkyl group, and cycloalkyl group may have include alkyl groups (e.g., having 1 to 15 carbon atoms), cycloalkyl groups (e.g., having 3 to 15 carbon atoms), aryl groups (e.g., having 6 to 15 carbon atoms), alkoxy groups (e.g., having 1 to 15 carbon atoms), halogen atoms, hydroxyl groups, and phenylthio groups. ２０４ and R ２０５ It is also preferred that the substituents independently form an acid-decomposable group by any combination of the substituents.

[0260] Below is M ＋Specific examples of the cation represented by the formula (I) are shown below, but the present invention is not limited thereto.

[0261]

[0262]

[0263]

[0264] "M ＋ X － In the compound represented by the formula "X － represents an anion, preferably an organic anion. The organic anion is not particularly limited, and examples thereof include monovalent or divalent or higher organic anions. The organic anion is preferably an anion having a significantly low ability to cause a nucleophilic reaction, and more preferably a non-nucleophilic anion.

[0265] 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.

[0266] 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).

[0267] 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.

[0268] 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).

[0269] 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.

[0270] An example of the sulfonylimide anion is a saccharin anion.

[0271] 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.

[0272] 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.

[0273] The non-nucleophilic anion is also preferably an anion represented by the following formula (AN1).

[0274]

[0275] In formula (AN1), R １ and R ２ each independently represents a hydrogen atom or a substituent. The substituent is not particularly limited, but a group that is not an electron-withdrawing group is preferred. Examples of groups that are not electron-withdrawing groups include hydrocarbon groups, hydroxyl groups, oxyhydrocarbon groups, oxycarbonyl hydrocarbon groups, amino groups, hydrocarbon-substituted amino groups, and hydrocarbon-substituted amide groups. Examples of groups that are not electron-withdrawing groups include, each independently, -R', -OH, -OR', -OCOR', -NH ２ , -NR' ２ , —NHR′, or —NHCOR′ is preferred, where R′ is a monovalent hydrocarbon group.

[0276] 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 R２ are each independently preferably a hydrocarbon group (preferably a cycloalkyl group) or a hydrogen atom.

[0277] L represents a divalent linking group. When a plurality of L's are present, they may be the same or different. Examples of the divalent linking group include -O-CO-O-, -COO-, -CONH-, -CO-, -O-, -S-, -SO-, and -SO ２ Examples of the divalent linking group include -, an alkylene group (preferably having 1 to 6 carbon atoms), a cycloalkylene group (preferably having 3 to 15 carbon atoms), an alkenylene group (preferably having 2 to 6 carbon atoms), and a divalent linking group formed by combining a plurality of these groups. Among these, examples of the divalent linking group include -O-CO-O-, -COO-, -CONH-, -CO-, -O-, and -SO ２ -, -O-CO-O-alkylene group-, -COO-alkylene group-, or -CONH-alkylene group- is preferred, and -O-CO-O-, -O-CO-O-alkylene group-, -COO-, -CONH-, or -SO ２ - or -COO-alkylene group- is more preferred.

[0278] 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)

[0279] 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 R２ａ 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.

[0280] In formula (AN1), R ３represents 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).

[0281] Among them, R ３ is preferably an organic group having a cyclic structure. The cyclic structure may be monocyclic or polycyclic and may have a substituent. The ring in the organic group having a cyclic structure is preferably directly bonded to L in formula (AN1). The organic group having a cyclic structure may or may not have a heteroatom (oxygen atom, sulfur atom, and / or nitrogen atom, etc.). The heteroatom may be substituted for one or more of the carbon atoms forming the cyclic structure. The organic group having a cyclic structure is preferably, for example, a hydrocarbon group having a cyclic structure, a lactone ring group, or a sultone ring group. Among these, the organic group having a cyclic structure is preferably a hydrocarbon group having a cyclic structure. The hydrocarbon group having a cyclic structure is preferably a monocyclic or polycyclic cycloalkyl group. These groups may have a substituent. The cycloalkyl group may be monocyclic (e.g., a cyclohexyl group) or polycyclic (e.g., an adamantyl group), and preferably has 5 to 12 carbon atoms. As the lactone group and sultone group, for example, a group in which one hydrogen atom has been removed from a ring atom constituting the lactone structure or sultone structure in any of the structures represented by the above-mentioned formulae (LC1-1) to (LC1-21) and the structures represented by the above-mentioned formulae (SL1-1) to (SL1-3) is preferred.

[0282] 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.

[0283] The non-nucleophilic anion is also preferably an anion represented by the following formula (AN2).

[0284]

[0285] 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.

[0286] 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.

[0287] 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.

[0288] L represents a divalent linking group, and is defined the same as L in formula (AN1).

[0289] 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.

[0290] 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.

[0291] 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.

[0292] The anion represented by formula (AN2) is SO ３ － -CF ２ -CH ２ -OCO-(L) ｑ’ -W, SO ３ － -CF ２ -CHF-CH ２ -OCO-(L) ｑ’ -W, SO ３ － -CF ２ -COO-(L) ｑ’ -W, SO ３ － -CF ２ -CF ２ -CH ２ -CH ２ - (L) ｑ -W or SO ３ － -CF ２ -CH(CF ３ ) -OCO-(L) ｑ’ -W is preferred. Here, L, q and W are the same as those in formula (AN2). q' represents an integer of 0 to 10.

[0293] The non-nucleophilic anion is also preferably an aromatic sulfonate anion represented by the following formula (AN3).

[0294]

[0295] 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.

[0296] 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.

[0297] 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).

[0298] 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.

[0299] It is also preferable that the compound (B) is at least one selected from the group consisting of the compounds (I) to (II).

[0300] (Compound (I)) Compound (I) is a compound having one or more structural moieties X and one or more structural moieties Y, which generates an acid containing the first acidic moiety derived from the structural moiety X and the second acidic moiety derived from the structural moiety Y when irradiated with actinic rays or radiation. Structural moiety X: Anionic moiety A １ － and the cationic moiety M １ ＋ and by irradiation with actinic rays or radiation, HA １ Structural moiety Y: anionic moiety A, which forms a first acidic moiety represented by the formula: ２ － and the cationic moiety M ２ ＋ and by irradiation with actinic rays or radiation, HA ２ The compound (I) satisfies the following condition I:

[0301] Condition I: In the compound (I), the cationic moiety M in the structural moiety X １ ＋ and the cationic moiety M in the structural moiety Y ２ ＋ H ＋ The compound PI in which the cation moiety M in the structural moiety X is replaced by １ ＋ H ＋ HA is replaced by １ and the cationic moiety M in the structural moiety Y. ２ ＋ H ＋ HA is replaced by ２ and an acid dissociation constant a2 derived from the acidic site represented by the formula (I), and the acid dissociation constant a2 is greater than the acid dissociation constant a1.

[0302] Condition I will be explained in more detail below. For example, when compound (I) is an acid-generating compound having one of the first acidic sites derived from the structural moiety X and one of the second acidic sites derived from the structural moiety Y, compound PI is "HA １ and H.A.２ The acid dissociation constant a1 and the acid dissociation constant a2 of the compound PI correspond to "a compound having the following structure." More specifically, when the acid dissociation constant of the compound PI is calculated, the acid dissociation constant a1 and the acid dissociation constant a2 of the compound PI correspond to "a compound having the following structure." １ － and H.A. ２ The pKa at which the compound becomes "a compound having the above formula (A)" is the acid dissociation constant a1, １ － and H.A. ２ "A compound having １ － and A ２ － The pKa at which the compound becomes "a compound having the above formula (I)" is the acid dissociation constant a2.

[0303] For example, when compound (I) is an acid-generating compound having two of the first acidic sites derived from the structural site X and one of the second acidic sites derived from the structural site Y, compound PI is a compound having two HAs. １ and one HA ２ When the acid dissociation constant of compound PI is calculated, compound PI corresponds to "a compound having one A １ － and one HA １ and one HA ２ and the acid dissociation constant when "a compound having one A １ － and one HA １ and one HA ２ "Compound having two A １ － and one HA ２ The acid dissociation constant when the compound is a compound having two A's corresponds to the acid dissociation constant a1 described above. １ － and one HA ２ "Compound having two A １ － and A ２ － In other words, in the case of compound PI, the acid dissociation constant when the compound becomes a compound having the cation moiety M in the structural moiety X corresponds to the acid dissociation constant a2. １ ＋ H ＋ HA is replaced by１ When the compound PI has a plurality of acid dissociation constants derived from the acidic moiety represented by the formula (I), the value of the acid dissociation constant a2 is larger than the largest value of the plurality of acid dissociation constants a1. １ － and one HA １ and one HA ２ The acid dissociation constant when the compound is aa is defined as "a compound having one A １ － and one HA １ and one HA ２ "Compound having two A １ － and one HA ２ When the acid dissociation constant when the compound becomes "a compound having the formula (I)" is ab, the relationship between aa and ab satisfies aa<ab.

[0304] The acid dissociation constants a1 and a2 are determined by the above-mentioned method for measuring an acid dissociation constant. The compound PI corresponds to an acid generated when compound (I) is irradiated with actinic rays or radiation. When compound (I) has two or more structural moieties X, the structural moieties X may be the same or different. In addition, when two or more of the above A １ － and two or more of the above M １ ＋ In compound (I), the above A １ － and the above A ２ － , and the above M １ ＋ and the above M ２ ＋ may be the same or different, but １ － and the above A ２ － are preferably different from each other.

[0305] In the compound PI, the difference (absolute value) between the acid dissociation constant a1 (the maximum value when there are multiple acid dissociation constants a1) and the acid dissociation constant a2 is preferably 0.1 or more, more preferably 0.5 or more, and even more preferably 1.0 or more. The upper limit of the difference (absolute value) between the acid dissociation constant a1 (the maximum value when there are multiple acid dissociation constants a1) and the acid dissociation constant a2 is not particularly limited, but is, for example, 16 or less.

[0306] In the compound PI, the acid dissociation constant a2 is preferably not more than 20, more preferably not more than 15. The lower limit of the acid dissociation constant a2 is preferably not less than −4.0.

[0307] In the compound PI, the acid dissociation constant a1 is preferably 2.0 or less, and more preferably 0 or less. The lower limit of the acid dissociation constant a1 is preferably −20.0 or more.

[0308] Anion site A １ － and anionic moiety A ２ － is a structural moiety containing a negatively charged atom or atomic group, and examples thereof include structural moieties selected from the group consisting of formulae (AA-1) to (AA-3) and formulae (BB-1) to (BB-6) shown below. １ － As the anionic moiety A, those capable of forming an acidic moiety with a small acid dissociation constant are preferred, and among these, any of formulas (AA-1) to (AA-3) is more preferred, and any of formulas (AA-1) and (AA-3) is even more preferred. ２ － As the anion moiety A １ － Preferably, it is one that can form an acidic site with a larger acid dissociation constant than the above, more preferably any of formulas (BB-1) to (BB-6), and even more preferably any of formulas (BB-1) and (BB-4). In the following formulas (AA-1) to (AA-3) and formulas (BB-1) to (BB-6), * represents a bonding position. In formula (AA-2), R Ａ represents a monovalent organic group. ＡThe monovalent organic group represented by the formula (I) is not particularly limited, but examples thereof include a cyano group, a trifluoromethyl group, and a methanesulfonyl group.

[0309]

[0310]

[0311] Cationic moiety M １ ＋ and cationic moiety M ２ ＋ is a structural moiety containing a positively charged atom or atomic group, and examples thereof include monovalent organic cations. ＋ Examples of the organic cation include those represented by the following formula:

[0312] (Compound (II)) Compound (II) is a compound having two or more of the above structural moieties X and one or more of the following structural moieties Z, which generates an acid containing two or more of the first acidic moieties derived from the structural moiety X and the structural moiety Z upon irradiation with actinic rays or radiation. Structural moiety Z: a ​​nonionic moiety capable of neutralizing an acid

[0313] In compound (II), the definition of the structural moiety X and A １ － and M １ ＋ The definition of the structural moiety X in the compound (I) and the definition of A １ － and M １ ＋ The definition and preferred embodiments are also the same.

[0314] In the compound (II), the cation moiety M in the structural moiety X １ ＋ H ＋ In the compound PII, the cationic moiety M in the structural moiety X is replaced by １ ＋ H ＋ HA is replaced by １The preferred range of the acid dissociation constant a1 derived from the acidic moiety represented by the formula (I) is the same as the acid dissociation constant a1 in the compound PI. In addition, when the compound (II) is, for example, a compound that generates an acid having two of the first acidic moieties derived from the structural moiety X and the structural moiety Z, the compound PII is a compound that generates an acid having two HAs. １ When the acid dissociation constant of this compound PII was calculated, it was found that the compound PII has "one A １ － and one HA １ and the acid dissociation constant when "a compound having one A １ － and one HA １ "Compound having two A １ － The acid dissociation constant when the compound becomes "a compound having the formula (I)" corresponds to the acid dissociation constant a1.

[0315] The acid dissociation constant a1 is determined by the above-mentioned method for measuring an acid dissociation constant. The compound PII corresponds to the acid generated when the compound (II) is irradiated with actinic rays or radiation. The two or more structural moieties X may be the same or different. １ － and two or more of the above M １ ＋ may be the same or different.

[0316] The nonionic moiety capable of neutralizing an acid in the structural moiety Z is not particularly limited, and is preferably, for example, a moiety containing a group capable of electrostatically interacting with a proton or a functional group having electrons. Examples of the group capable of electrostatically interacting with a proton or the functional group having electrons include functional groups having a macrocyclic structure such as cyclic polyethers, and functional groups having a nitrogen atom with an unshared electron pair that does not contribute to π-conjugation. The nitrogen atom with an unshared electron pair that does not contribute to π-conjugation is, for example, a nitrogen atom having a partial structure shown in the following formula:

[0317]

[0318] Examples of the partial structure of a functional group having a group or electron capable of electrostatically interacting with a proton include a crown ether structure, an azacrown ether structure, a primary amine structure, a secondary amine structure, a tertiary amine structure, a pyridine structure, an imidazole structure, and a pyrazine structure. Of these, a primary amine structure, a secondary amine structure, a tertiary amine structure, and a tertiary amine structure are preferred.

[0319] Examples of moieties other than cations that Compound (I) and Compound (II) may have are shown below.

[0320]

[0321]

[0322] When the composition of the present invention contains compound (B), the content of compound (B) is not particularly limited, but is preferably 0.5 mass% or more, more preferably 1.0 mass% or more, based on the total solid content of the composition of the present invention.When the composition of the present invention contains compound (B), the content of compound (B) is preferably 60.0 mass% or less, more preferably 50.0 mass% or less, and even more preferably 40.0 mass% or less, based on the total solid content of the composition of the present invention.Compound (B) may be used alone or in combination of two or more.

[0323] [Acid Diffusion Controller] The composition of the present invention may contain an acid diffusion controller (also referred to as "acid diffusion controller (C)" or "compound (C)") different from the acid generator (Q1). The acid diffusion controller may be an onium salt compound. The acid diffusion controller is preferably a compound different from the resin (A). Furthermore, the acid diffusion controller (C) may be the same compound as or a different compound from the photoacid generator (B) described above. The acid diffusion controller (C) may be the acid generator (Q2) described above. The acid diffusion controller (C) can trap acid generated from the photoacid generator or the like upon exposure and act as a quencher to suppress reaction of the acid-decomposable resin in unexposed areas due to excess generated acid. The type of acid diffusion controller (C) is not particularly limited, and examples include a basic compound (CA), a low-molecular-weight compound (CB) having a nitrogen atom and a group that is cleaved by the action of an acid, and a compound (CC) whose acid diffusion control ability is reduced or lost upon irradiation with actinic rays or radiation. Examples of the compound (CC) include an onium salt compound (CD) that is a weak acid relative to the photoacid generator, and a basic compound (CE) whose basicity is reduced or eliminated by irradiation with actinic rays or radiation. Specific examples of the basic compound (CA) include those described in paragraphs

[0132] to

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

[0137] to

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

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

[0156] to

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

[0305] to

[0314] of WO 2020 / 158337.

[0324] 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.

[0325] Among the acid diffusion controllers, the compound (CC) is also referred to as a photodegradable quencher. Acid diffusion controllers other than the compound (CC) are also referred to as non-photodegradable quenchers. The acid diffusion controller (C) may be a photodegradable quencher or a non-photodegradable quencher. A photodegradable quencher and a non-photodegradable quencher may be used in combination as the acid diffusion controller (C).

[0326] When the composition of the present invention contains an acid diffusion controller (C), the type of acid diffusion controller (C) contained in the composition of the present invention may be one or two or more. When the composition of the present invention contains an acid diffusion controller (C), the content of the acid diffusion controller (C) is preferably 0.1 to 15.0 mass %, more preferably 1.0 to 15.0 mass %, based on the total solid content of the composition of the present invention.

[0327] [Hydrophobic Resin] The composition of the present invention may further contain a hydrophobic resin (also referred to as "hydrophobic resin (E)") different from resin (A). The hydrophobic resin (E) is preferably designed so as to be unevenly distributed on the surface of the resist film, but unlike surfactants, it does not necessarily have to have a hydrophilic group in its molecule, and it does not necessarily have to contribute to uniform mixing of polar and non-polar substances. Effects of adding hydrophobic resin (E) include control of the static and dynamic contact angles of water on the resist film surface, and suppression of outgassing.

[0328] The hydrophobic resin (E) contains fluorine atoms, silicon atoms, and CH atoms contained in the side chain portion of the resin in order to be unevenly distributed on the surface layer of the film. ３It is preferable to have one or more of the partial structures, and more preferably two or more. The hydrophobic resin preferably has a hydrocarbon group having 5 or more carbon atoms. These groups may be present in the main chain of the resin or may be substituted on a side chain. Examples of the hydrophobic resin (E) include the compounds described in paragraphs

[0275] to

[0279] of WO 2020 / 004306.

[0329] When the composition of the present invention contains the hydrophobic resin (E), the content of the hydrophobic resin (E) is preferably 0.01 to 20.0 mass%, more preferably 0.1 to 15.0 mass%, based on the total solid content of the composition of the present invention.

[0330] [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.

[0331] The surfactant may be used alone or in combination of two or more.

[0332] When the composition of the present invention contains a surfactant, the content of the surfactant is preferably from 0.0001 to 2.0 mass%, more preferably from 0.0005 to 1.0 mass%, and still more preferably from 0.1 to 1.0 mass%, relative to the total solid content of the composition of the present invention.

[0333] [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).

[0334] 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.

[0335] 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.

[0336] 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.

[0337] [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 phenolic compound having a molecular weight of 1,000 or less, or an alicyclic or aliphatic compound containing a carboxyl group).

[0338] 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.

[0339] The composition of the present invention is suitable for use as a photosensitive composition for EUV exposure. EUV has a wavelength of 13.5 nm, which is shorter than ArF (wavelength 193 nm) light and the like, and therefore the number of incident photons is smaller when exposed at the same sensitivity. As a result, the effect of "photon shot noise," in which the number of photons varies stochastically, is significant, leading to worsening of line edge roughness (LER) and bridge defects. One way to reduce photon shot noise is to increase the exposure dose to increase the number of incident photons, but this comes at a trade-off with the demand for higher sensitivity.

[0340] When the value A calculated by the following formula (1) is high, the resist film formed from the resist composition has a high absorption efficiency for EUV and electron beams, which is effective in reducing photon shot noise. The value A represents the mass ratio of the resist film to the absorption efficiency for EUV and electron beams. Formula (1): A = ([H] x 0.04 + [C] x 1.0 + [N] x 2.1 + [O] x 3.6 + [F] x 5.6 + [S] x 1.5 + [I] x 39.5) / ([H] x 1 + [C] x 12 + [N] x 14 + [O] x 16 + [F] x 19 + [S] x 32 + [I] x 127). The value A is preferably 0.120 or greater. There is no particular upper limit to the A value, but if the A value is too large, the EUV and electron beam transmittance of the resist film decreases, the optical image profile in the resist film deteriorates, and as a result, it becomes difficult to obtain a good pattern shape. Therefore, the A value is preferably 0.240 or less, and more preferably 0.220 or less.

[0341] In formula (1), [H] represents the molar ratio of hydrogen atoms derived from all solids to all atoms in all solids in the actinic ray-sensitive or radiation-sensitive resin composition, [C] represents the molar ratio of carbon atoms derived from all solids to all atoms in all solids in the actinic ray-sensitive or radiation-sensitive resin composition, [N] represents the molar ratio of nitrogen atoms derived from all solids to all atoms in all solids in the actinic ray-sensitive or radiation-sensitive resin composition, and [O] represents the molar ratio of nitrogen atoms derived from all solids to all atoms in all solids in the actinic ray-sensitive or radiation-sensitive resin composition. [F] represents the molar ratio of oxygen atoms derived from all solids to all atoms in all solids, [F] represents the molar ratio of fluorine atoms derived from all solids to all atoms in all solids in the actinic ray- or radiation-sensitive resin composition, [S] represents the molar ratio of sulfur atoms derived from all solids to all atoms in all solids in the actinic ray- or radiation-sensitive resin composition, and [I] represents the molar ratio of iodine atoms derived from all solids to all atoms in all solids in the actinic ray- or radiation-sensitive resin composition. For example, when a resist composition contains an acid-decomposable resin, a photoacid generator, an acid diffusion controller, and a solvent, the acid-decomposable resin, the photoacid generator, and the acid diffusion controller correspond to the solids. In other words, the total atoms in all solids correspond to the sum of all atoms derived from the resin, all atoms derived from the photoacid generator, and all atoms derived from the acid diffusion controller. For example, [H] represents the molar ratio of hydrogen atoms derived from all solids to all atoms in all solids. Explaining based on the above example, [H] represents the molar ratio of the sum of hydrogen atoms derived from the acid-decomposable resin, the photoacid generator, and the acid diffusion controller to the sum of all atoms derived from the acid-decomposable resin, the photoacid generator, and the acid diffusion controller.

[0342] The A value can be calculated by calculating the atomic ratio of the components contained in the resist composition when the structures and contents of the components of the total solid content of the resist composition are known. Even when the components are unknown, the atomic ratio of the components can be calculated by analytical techniques such as elemental analysis of a resist film obtained by evaporating the solvent component of the resist composition.

[0343] [Actinic ray- or radiation-sensitive film, pattern forming method] The procedure of the pattern forming method using the composition of the present invention is not particularly limited, but it preferably includes the following steps: Step 1: forming an actinic ray- or radiation-sensitive film on a substrate from the actinic ray- or radiation-sensitive resin composition Step 2: exposing the actinic ray- or radiation-sensitive film Step 3: developing the exposed actinic ray- or radiation-sensitive film with a developer The procedure of each of the above steps will be described in detail below.

[0344] (Step 1: Actinic Ray- or Radiation-Sensitive Film Forming Step) Step 1 is a step of forming an actinic ray- or radiation-sensitive film on a substrate using an actinic ray- or radiation-sensitive resin composition.

[0345] An example of a method for forming an actinic ray-sensitive or radiation-sensitive film (preferably a resist film) on a substrate using an actinic ray-sensitive or radiation-sensitive resin composition is a method of coating the composition of the present invention on a substrate. It is preferable to filter the composition of the present invention as needed before coating. 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.

[0346] The composition of the present invention can be applied to a substrate (e.g., silicon, silicon dioxide-coated) such as those used in the manufacture of integrated circuit devices by a suitable 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 an actinic ray-sensitive or radiation-sensitive film. If necessary, various undercoating films (inorganic film, organic film, anti-reflective film) may be formed under the actinic ray-sensitive or radiation-sensitive film.

[0347] 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.

[0348] The thickness of the actinic ray-sensitive or radiation-sensitive 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 actinic ray-sensitive or radiation-sensitive 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 actinic ray-sensitive or radiation-sensitive film is more preferably 10 to 120 nm, and even more preferably 15 to 90 nm.

[0349] A top coat may be formed on top of the actinic ray-sensitive or radiation-sensitive film using a top coat composition. It is preferable that the top coat composition does not mix with the actinic ray-sensitive or radiation-sensitive film and can be uniformly applied to the actinic ray-sensitive or radiation-sensitive 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 actinic ray-sensitive or radiation-sensitive 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 described above. 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.

[0350] (Step 2: Exposure Step) Step 2 is a step of exposing the actinic ray-sensitive or radiation-sensitive film. Examples of the exposure method include a method of irradiating the formed actinic ray-sensitive or radiation-sensitive film with actinic rays or radiation through a predetermined mask. Examples of actinic rays or radiation include infrared light, visible light, ultraviolet light, far ultraviolet light, extreme ultraviolet light, X-rays, and electron beams, and include far ultraviolet light with a wavelength of preferably 250 nm or less, more preferably 220 nm or less, and 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.

[0351] 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.

[0352] (Step 3: Development Step) Step 3 is a step of developing the exposed actinic ray-sensitive or radiation-sensitive film with a developer to form a pattern. The developer may be an alkaline developer or a developer containing an organic solvent (hereinafter also referred to as an organic developer).

[0353] 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.

[0354] 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.

[0355] 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.

[0356] 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.

[0357] Preferred embodiments of the organic developer include the following embodiments (OD1) and (OD2). (OD1) An embodiment in which the organic developer is n-butyl acetate. (OD2) An embodiment in which the organic developer is a mixed solvent of n-butyl acetate and a hydrocarbon having 11 or more carbon atoms. The mixed solvent of (OD2) above is also referred to as mixed solvent (OD2). The hydrocarbon having 11 or more carbon atoms in mixed solvent (OD2) is preferably an alkane, more preferably an alkane having 11 to 15 carbon atoms, even more preferably an alkane having 11 to 13 carbon atoms, particularly preferably undecane or dodecane, and most preferably undecane. Note that when structural isomers exist, such as undecane and dodecane, the hydrocarbon having 11 or more carbon atoms may contain the structural isomer. The hydrocarbon having 11 or more carbon atoms contained in mixed solvent (OD2) may be one type or two or more types. The content of hydrocarbons having 11 or more carbon atoms in the mixed solvent (OD2) (the total amount when multiple hydrocarbons having 11 or more carbon atoms are contained) is preferably 1% by mass or more and 35% by mass or less, more preferably 5% by mass or more and 30% by mass or less, and even more preferably 10% by mass or more and 25% by mass or less, based on 100% by mass of the entire mixed solvent (OD2).

[0358] The content of n-butyl acetate in the mixed solvent (OD2) is preferably 65% ​​by mass or more and 99% by mass or less, more preferably 70% by mass or more and 95% by mass or less, and even more preferably 75% by mass or more and 90% by mass or less, with the entire mixed solvent (OD2) being 100% by mass.

[0359] A particularly preferred embodiment of the mixed solvent (OD2) is one containing n-butyl acetate and undecane, with the mass ratio of "n-butyl acetate / undecane" being "90 / 10".

[0360] The developer may contain other components in addition to the components described above. Examples of other components include surfactants, antioxidants, basic compounds, etc. The content of other components in the developer is preferably 0% by mass or more and 5% by mass or less, more preferably 0% by mass or more and 1% by mass or less, even more preferably 0% by mass or more and 0.5% by mass or less, based on 100% by mass of the entire developer, and particularly preferably 0% by mass (i.e., no other components are contained).

[0361] (Other Steps) The pattern formation method preferably includes, after step 3, a step of cleaning with a rinse liquid.

[0362] 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.

[0363] 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.

[0364] 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).

[0365] 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.

[0366] The composition of the present specification and various materials used in the pattern formation method of the present specification (e.g., solvent, developer, rinse, anti-reflective coating-forming composition, top coat-forming composition, 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.

[0367] 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.

[0368] 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).

[0369] 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.

[0370] 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.

[0371] [Method for Manufacturing an Electronic Device] The present 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 the present specification include those installed in electrical and electronic devices (such as home appliances, office automation (OA), media-related devices, optical devices, and communication devices).

[0372] 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.

[0373] [Various Components of Actinic Ray-Sensitive or Radiation-Sensitive Resin Composition] [Resin A] Resins A (Resins A-1 to A-38) shown in Table 7 are shown below. Resins A were synthesized in accordance with the synthesis method of Resin A-1 (Synthesis Example 1) described below. Table 1 shows the composition ratio (mol %), weight average molecular weight (Mw), and dispersity (Mw / Mn) of each repeating unit. The weight average molecular weight (Mw) and dispersity (Mw / Mn) of Resins A-1 to A-38 were measured by GPC (carrier: tetrahydrofuran (THF)) (amounts calculated as polystyrene). The composition ratios (mol %) of the resins are as follows: １３ Measurement was performed by C-NMR (nuclear magnetic resonance).

[0374]

[0375] The structures of monomers MA-1 to MA-27 and MB-1 to MB-35 corresponding to the repeating units constituting the resins shown in Table 1 are shown below.

[0376]

[0377]

[0378] Synthesis Example 1: Synthesis of Resin A-1 Propylene glycol monomethyl ether acetate (28 g) was heated to 80°C under a nitrogen stream. While stirring this liquid, a mixed solution of a monomer represented by MA-16 (30 g), a monomer represented by MB-10 (38 g), propylene glycol monomethyl ether acetate (112 g), and dimethyl 2,2'-azobisisobutyrate [V-601, Fujifilm Wako Pure Chemical Industries, Ltd.] (5.7 g) was added dropwise over 6 hours to obtain a reaction liquid. After completion of the dropwise addition, the reaction liquid was stirred at 80°C for an additional 2 hours. The obtained reaction liquid was allowed to cool and then reprecipitated with a large amount of a mixed solvent of heptane and ethyl acetate (heptane:ethyl acetate = 9:1, mass ratio), followed by filtration. The obtained solid was vacuum dried to obtain 58 g of Resin A-1. The weight average molecular weight (Mw: polystyrene equivalent) of the obtained resin A-1 determined by GPC (carrier: tetrahydrofuran (THF)) was 8,500, and the dispersity (Mw / Mn) was 1.60. １３ The molar ratio of repeating units measured by C-NMR (nuclear magnetic resonance) was 50 / 50.

[0379] Other resins (A) used in the examples were also synthesized in the same manner as above.

[0380] [Photoacid Generator B] The structures of photoacid generator B (compounds B-1 to B-30) and comparative compounds (compounds B'-1 to B'-4) shown in Table 7 are shown below. Photoacid generator B is a compound that corresponds to acid generator (Q1). In Table 7, the comparative compounds are also listed in the photoacid generator B column for convenience. Me represents a methyl group. Table 2 also shows the pKa of the acids generated by exposure of compounds B-1 to B-30 and compounds B'-1 to B'-4. When there are multiple pKa values, the smallest value is listed.

[0381]

[0382]

[0383]

[0384]

[0385]

[0386] Synthesis Example 2: Synthesis of Compound B-1 Synthesis of Compound B-1-b B-1-a (15.0 g) was dissolved in chloroform (300.0 g) and stirred at 25°C under a nitrogen stream, while N-iodosuccinimide (67.8 g) was added in portions. After cooling to 0°C, trifluoromethanesulfonic acid (10.9 g) was added dropwise, followed by stirring at 65°C for 2 hours. Thereafter, N-iodosuccinimide (16.5 g) was added in portions, followed by stirring at 65°C for an additional 1 hour. After cooling to 0°C, an aqueous solution of sodium thiosulfate (46.9 g) dissolved in distilled water (375.0 g) was added dropwise, followed by stirring for 1 hour. The organic layer was extracted and washed with a 1 mol / L aqueous sodium thiosulfate solution (200.0 g), and then washed three times with distilled water (200.0 g). After concentrating the organic layer, a large amount of methanol was added and the mixture was stirred, and the precipitated solid was collected by filtration to obtain B-1-b (50.5 g).

[0387]

[0388] (Synthesis of Compound B-1-c) B-1-b (50.0 g), tetrahydrofuran (443.0 g), and distilled water (195.0 g) were mixed and stirred at 0°C, and anhydrous lithium hydroxide (3.5 g) was added in portions. The reaction solution was stirred at 25°C for 3 hours, and then a 1 mol / L aqueous hydrochloric acid solution was added until the pH of the aqueous layer reached 2, followed by stirring for 1 hour. Ethyl acetate (500.0 g) was added to extract the organic layer, which was then washed three times with distilled water (300.0 g). The organic layer was concentrated, and then ethyl acetate (150.0 g) was added to the residue and stirred, and the precipitated solid was collected by filtration to obtain B-1-c (48.0 g).

[0389]

[0390] (Synthesis of Compound B-1-d) B-1-c (40.0 g), toluene (120.0 g), and N,N-dimethylformamide (2.1 g) were mixed and stirred at 60° C., to which thionyl chloride (13.9 g) was added dropwise. The reaction solution was stirred at 60° C. for 3 hours, and then the solvent was distilled off under reduced pressure to obtain B-1-d (41.0 g).

[0391]

[0392] <Synthesis of Compound B-1-f> B-1-e (6.0 g), dichloromethane (40.0 g), and distilled water (30.0 g) were mixed and stirred at 0°C, and then a 25% aqueous solution of N,N,N-trimethyladamantan-1-aminium hydroxide (32.7 g) was added dropwise, followed by the addition of B-1-d (14.2 g) in portions. The reaction solution was stirred at 0°C for 1 hour, and then dichloromethane (480.0 g) and distilled water (200.0 g) were added and stirred at 25°C for an additional 1 hour. The organic layer was extracted and washed three times with distilled water (200.0 g), and then the organic layer was filtered. The filtrate was concentrated, and a large amount of ethyl acetate was added to the residue and stirred, and the precipitated solid was collected by filtration. Methanol (80.0 g) was added to the obtained solid and stirred, and the solid was collected by filtration, yielding B-1-f (10.3 g).

[0393]

[0394] <Synthesis of Compound B-1> B-1-f (10.3 g), B-1-g (8.4 g), dichloromethane (100.0 g), and distilled water (100.0 g) were mixed and stirred at 25°C for 1 hour. The organic layer was extracted and washed eight times with distilled water (100.0 g). After concentrating the organic layer, diisopropyl ether (200.0 g) was added to the residue and stirred, and the precipitated solid was collected by filtration to obtain B-1 (12.8 g).

[0395]

[0396] Regarding the obtained B-1 １ H-NMR was measured. １ H NMR (400MHz, (CD ３ ) ２ SO) 4.20 (dd, 1H), 4.40 (dd, 1H), 4.71 (t, 1H), 7.90-8.40 (m, 24H)

[0397] Other compounds (B) used in the examples were also synthesized in the same manner as above.

[0398] [Photoacid Generator C Other Than B] The structures of photoacid generators C (compounds C-1 to C-35) shown in Table 7 are shown below. Photoacid generator C is a compound that does not fall under the category of acid generator (Q1). Table 3 also shows the pKa of the acid generated by exposure of compounds C-1 to C-35. When compounds have multiple pKa values, the smallest value is shown.

[0399]

[0400]

[0401]

[0402]

[0403]

[0404] [Photodegradable Quencher D] The structures of photodegradable quencher D (compounds D-1 to D-6) and comparative compounds (compounds D'-1 to D'-2) shown in Table 7 are shown below. Photodegradable quencher D is a compound that corresponds to acid generator (Q1). In Table 7, the comparative compounds are also listed in the photodegradable quencher D column for convenience. Me represents a methyl group. Table 4 also shows the pKa of the acids generated by exposure of compounds D-1 to D-6 and compounds D'-1 to D'-2.

[0405]

[0406]

[0407]

[0408] [Photodegradable quencher E other than D] The structures of photodegradable quenchers E (compounds E-1 to E-24) shown in Table 7 are shown below. Photodegradable quenchers E are compounds that do not fall under the category of acid generator (Q1). Table 5 also shows the pKa of the acids generated by exposure to compounds E-1 to E-24.

[0409]

[0410]

[0411]

[0412]

[0413] [Non-photodegradable quencher G] The structures of the non-photodegradable quenchers G (compounds G-1 to G-5) shown in Table 7 are shown below.

[0414]

[0415] [Resin I] Resins I (Resins I-1 to I-8) shown in Table 7 are shown below. Resins I-1 to I-8 were synthesized in accordance with the synthesis method for Resin A-1 described above (Synthesis Example 1). Table 6 shows the composition ratio (mass % ratio; corresponding from left to right), weight average molecular weight (Mw), and dispersity (Mw / Mn) of each repeating unit shown below. The weight average molecular weight (Mw) and dispersity (Mw / Mn) of Resins I-1 to I-8 were measured by GPC (carrier: tetrahydrofuran (THF)) (amounts calculated as polystyrene). The composition ratios (mass % ratios) of the resins are as follows: １３ Measurement was performed by C-NMR (nuclear magnetic resonance).

[0416]

[0417] The structural formulas of Resins I-1 to I-8 shown in Table 6 are shown below.

[0418]

[0419] [Surfactants] The surfactants shown in Table 7 are as follows: H-1: Megafac F176 (manufactured by DIC Corporation, fluorochemical surfactant) H-2: Megafac R08 (manufactured by DIC Corporation, fluorine and silicon surfactant) H-3: PF656 (manufactured by OMNOVA, fluorochemical surfactant)

[0420] [Solvents] The solvents shown in Table 7 are as follows: F-1: Propylene glycol monomethyl ether acetate (PGMEA) F-2: Propylene glycol monomethyl ether (PGME) F-3: Propylene glycol monoethyl ether (PGEE) F-4: Cyclohexanone F-5: Cyclopentanone F-6: 2-heptanone F-7: Ethyl lactate F-8: γ-butyrolactone F-9: Propylene carbonate

[0421] [Preparation of Resist Compositions] The components shown in Table 7 were mixed to a solids concentration of 2.0% by mass. The resulting mixture was then filtered by first passing it through a polyethylene filter with a pore size of 50 nm, then a nylon filter with a pore size of 10 nm, and finally a polyethylene filter with a pore size of 5 nm, in that order, to prepare resist compositions (Re-1 to Re-48, CRe-1 to CRe-6). Note that the solids refer to all components other than the solvent. The resulting resist compositions were used in the examples and comparative examples. In the tables, the "Content" column indicates the content (% by mass) of each component relative to the total solids in the resist composition. The mixing ratio of the solvents refers to the proportion (mass ratio) of each solvent when the total solvent is taken as 100.

[0422]

[0423]

[0424] [Pattern Formation] [EUV Exposure, Organic Solvent Development] An underlayer film-forming composition AL412 (manufactured by Brewer Science) was applied to a 12-inch diameter silicon wafer and baked at 205°C for 60 seconds to form a 20 nm thick underlayer film. A resist composition shown in Tables 8 and 9 was applied thereon and baked at 100°C for 60 seconds to form a 30 nm thick resist film. Using an EUV exposure device (manufactured by Exitech, Micro Exposure Tool, NA 0.3, Quadrupol, outer sigma 0.68, inner sigma 0.36), the silicon wafer having the resulting resist film was subjected to pattern irradiation so that the average line width of the resulting pattern was 14 nm. A mask with a line size of 14 nm and a line:space ratio of 1:1 was used as the reticle. The exposed resist film was baked at 90° C. for 60 seconds, then developed for 30 seconds with the developer shown in Tables 8 and 9, and spin-dried to obtain a negative pattern.

[0425] [Evaluation] <Defect evaluation (defect suppression)> The number of defects per silicon wafer was counted using UVision 5 (manufactured by AMAT Corporation) and SEMVision G4 (manufactured by AMAT Corporation) for the patterns obtained by the above-mentioned method, and the pattern was evaluated according to the following evaluation criteria: The fewer the number of defects, the better the defect suppression, and a rating of "E" or higher is considered to be acceptable.

[0426] "A": The number of defects is 50 or less. "B": The number of defects is more than 50 and less than 100. "C": The number of defects is more than 100 and less than 200. "D": The number of defects is more than 200 and less than 300. "E": The number of defects is more than 300 and less than 500. "F": The number of defects is more than 500.

[0427] <Roughness Performance> Roughness performance was evaluated by line width roughness (LWR performance, nm). The pattern obtained by the above method was observed from above the pattern using a critical dimension scanning electron microscope (SEM (Hitachi, Ltd. S-9380II)). The line width of the pattern was observed at 250 points, and its standard deviation (σ) was determined. The measurement variation in line width was evaluated using 3σ, and the value of 3σ was taken as LWR (nm). The smaller the LWR value, the better the LWR performance. The LWR performance (nm) is preferably 3.0 nm or less, more preferably 2.8 nm or less, even more preferably 2.6 nm or less, even more preferably 2.4 nm or less, particularly preferably 2.2 nm or less, and most preferably 2.0 nm or less.

[0428] The evaluation results are shown in Tables 8 and 9 below.

[0429]

[0430]

[0431]

[0432]

[0433] The developers in Tables 8 and 9 are as follows: K-1: n-butyl acetate K-2: n-butyl acetate / undecane mixed solution (mass ratio: n-butyl acetate / undecane=90 / 10)

[0434] As shown in Tables 8 and 9, the resist compositions of the present invention were confirmed to exhibit excellent LWR performance and defect suppression properties when patterns were formed by organic solvent development. On the other hand, the resist compositions of the comparative examples were insufficient in these areas.

[0435] [EUV Exposure, Alkaline Aqueous Solution Development] An underlayer film-forming composition AL412 (manufactured by Brewer Science) was applied to a silicon wafer with a diameter of 12 inches and baked at 205°C for 60 seconds to form a 20 nm thick underlayer film. A resist composition shown in Table 10 was applied thereon and baked at 100°C for 60 seconds to form a 30 nm thick resist film. Using an EUV exposure device (manufactured by Exitech, Micro Exposure Tool, NA 0.3, Quadrupol, outer sigma 0.68, inner sigma 0.36), the silicon wafer having the resulting resist film was subjected to pattern irradiation so that the average line width of the resulting pattern was 14 nm. A mask with a line size of 14 nm and a line:space ratio of 1:1 was used as the reticle. The exposed resist film was baked at 90°C for 60 seconds, developed with a tetramethylammonium hydroxide aqueous solution (2.38% by mass) for 30 seconds, and then rinsed with pure water for 30 seconds. The resist film was then spin-dried to obtain a positive-tone pattern. The resulting positive-tone pattern was used to evaluate the LWR performance and defect suppression properties in the same manner as described above.

[0436] The evaluation results are shown in Table 10 below.

[0437]

[0438]

[0439] As shown in Table 10 above, the resist compositions of the present invention were confirmed to exhibit excellent LWR performance and defect suppression properties even when patterns were formed by alkaline development. On the other hand, the resist compositions of the comparative examples were insufficient in these areas.

[0440] According to the present invention, it is possible to provide an actinic ray-sensitive or radiation-sensitive resin composition that is excellent in roughness performance and can suppress the occurrence of defects in the formation of ultrafine patterns (for example, LS patterns with line widths of 16 nm or less), an actinic ray-sensitive or radiation-sensitive resin film formed from the actinic ray-sensitive or radiation-sensitive resin composition, a pattern formation method using the actinic ray-sensitive or radiation-sensitive resin composition, and a method for manufacturing an electronic device. Furthermore, according to the present invention, it is possible to provide a compound that can be suitably used in the actinic ray-sensitive or radiation-sensitive resin composition.

[0441] Although the present invention has been described in detail and with reference to specific embodiments, it will be apparent to those skilled in the art that various changes and modifications can be made without departing from the spirit and scope of the present invention. This application is based on a Japanese patent application (Patent Application No. 2023-223501) filed on December 28, 2023, the contents of which are incorporated herein by reference.

Claims

1. (A) A resin and (Q1) a photoactive or radiation-sensitive acid generator which is an onium salt compound having a structure in which at least two atoms selected from three or more iodine atoms, oxygen atoms, and sulfur atoms are bonded to the same aromatic ring. A photoactive or radiation-sensitive resin composition containing the same.

2. The photoactive or radiation-sensitive resin composition according to claim 1, wherein the photoactive or radiation-sensitive acid generator (Q1) contains an organic anion having a structure in which at least two atoms selected from three or more iodine atoms, oxygen atoms, and sulfur atoms are bonded to the same aromatic ring.

3. The photoactive or radiation-sensitive resin composition according to claim 1, wherein the photoactive or radiation-sensitive acid generator (Q1) is a compound that generates an acid having at least one group selected from a sulfo group, a carboxy group, a methidoic acid group, a sulfonamide group, a sulfonimide group, and a carbonylsulfonylimide group upon exposure.

4. The photoactive or radiation-sensitive resin composition according to claim 1, wherein the photoactive or radiation-sensitive acid generator (Q1) has a sulfonium cation or an iodonium cation.

5. The photoactive or radiation-sensitive resin composition according to claim 1, wherein the resin (A) contains a repeating unit having an acid-decomposable group.

6. The photoactive or radiation-sensitive resin composition according to claim 1, wherein the resin (A) contains a repeating unit having a hydroxyl group bonded to an aromatic ring.

7. The photoactive or radiation-sensitive resin composition according to claim 1, wherein the aromatic ring in the photoactive or radiation-sensitive acid generator (Q1) is a benzene ring.

8. The photoactive or radiation-sensitive resin composition according to claim 1, wherein the photoactive or radiation-sensitive acid generator (Q1) is an onium salt compound having a structure in which at least two atoms selected from four or more iodine atoms, oxygen atoms, and sulfur atoms are bonded to the same aromatic ring.

9. The photoactive or radiation-sensitive resin composition according to claim 8, wherein the onium salt compound contains an organic anion having a structure in which at least two atoms selected from four or more iodine atoms, oxygen atoms, and sulfur atoms are bonded to the same aromatic ring.

10. The photoactive ray-sensitive or radiation-sensitive acid generator (Q1) is an onium salt compound having a structure in which three or more iodine atoms and two or more oxygen atoms are bonded to the same aromatic ring. The photoactive ray-sensitive or radiation-sensitive resin composition according to claim 1.

11. The photosensitive ray- or radiation-sensitive acid generator (Q1) contains an organic anion represented by the following general formula (1D), and the photosensitive ray- or radiation-sensitive resin composition according to claim 1. In the general formula (1D), R １ each independently represents a hydrogen atom or an organic group. Two Rs １ may be bonded to each other to form a ring structure together with other atoms in the general formula (1D). Among two Rs １ , at least one has an anion site.

12. The photoactive ray-sensitive or radiation-sensitive acid generator (Q1) has a halogen atom in the cation moiety (however, excluding the case where the halogen atom is a monovalent iodine cation). The photoactive ray-sensitive or radiation-sensitive resin composition according to claim 1.

13. The photoactive ray-sensitive or radiation-sensitive acid generator (Q1) has a structure in which three or more iodine atoms and at least two or more atoms selected from oxygen atoms and sulfur atoms are bonded to the same aromatic ring, and contains an organic cation selected from a sulfonium cation and an iodonium cation. The photoactive ray-sensitive or radiation-sensitive resin composition according to claim 1.

14. The photoactive ray-sensitive or radiation-sensitive acid generator (Q1) contains a photoactive ray-sensitive or radiation-sensitive acid generator (Q2) that generates an acid weaker than that generated by exposure. The photoactive ray-sensitive or radiation-sensitive resin composition according to claim 1.

15. A photoactive ray-sensitive or radiation-sensitive film formed from the photoactive ray-sensitive or radiation-sensitive resin composition according to any one of claims 1 to 14.

16. A step of forming a photoactive ray-sensitive or radiation-sensitive film on a substrate using the photoactive ray-sensitive or radiation-sensitive resin composition according to any one of claims 1 to 14; a step of exposing the photoactive ray-sensitive or radiation-sensitive film; and a step of developing the exposed photoactive ray-sensitive or radiation-sensitive film using a developer to form a pattern. A patterning method comprising these steps.

17. A method for manufacturing an electronic device, including the patterning method according to claim 16.

18. An anion moiety composed of an organic anion having a structure in which three or more iodine atoms and at least two or more atoms selected from oxygen atoms and sulfur atoms are bonded to the same aromatic ring, and a cation moiety having a sulfonium cation or an iodonium cation. An onium salt compound containing these moieties.

19. A cation moiety containing a sulfonium cation or an iodonium cation having a structure in which three or more iodine atoms and at least two or more atoms selected from oxygen atoms and sulfur atoms are bonded to the same aromatic ring, and an organic anion moiety. An onium salt compound containing these moieties.

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