Active light–sensitive or radiation-sensitive resin composition, active light–sensitive or radiation-sensitive film, pattern formation method, and production method for electronic device

Abstract

The present invention provides an active light–sensitive or radiation-sensitive resin composition that includes an acid-labile resin (A) and a compound (B) that generates an acid when irradiated with active light or radiation, an active light–sensitive or radiation-sensitive resin film that is formed from the composition, a pattern formation method that uses the composition, and a production method for an electronic device. Compound (B) includes structural moieties X and Y, which are described in the description, and generates an acid that includes a first acidic moiety derived from structural moiety X and a second acidic moiety derived from structural moiety Y when irradiated with active light or radiation. For compound (B), a compound PI obtained by replacing a cationic moiety with H+ has acid dissociation constants a1 and a2 that result from an acidic moiety, a2 being larger than a1, and an anionic moiety of structural moiety Y is represented by formula (1), which is described in the description.

Description

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

[0001] The present invention relates to an actinic ray-sensitive or radiation-sensitive resin composition, an actinic ray-sensitive or radiation-sensitive film, a pattern forming method, and a method for producing an electronic device.

[0002] In the manufacturing process of semiconductor devices such as ICs (integrated circuits) and LSIs (large-scale integrated circuits), microfabrication is performed by lithography using a photosensitive composition. Lithography methods include forming a resist film using a photosensitive composition, exposing the resulting film, and then developing it. In particular, in recent years, the use of EB (electron beam) and EUV (extreme ultraviolet) in addition to ArF excimer lasers for exposure has been investigated, and actinic ray-sensitive or radiation-sensitive resin compositions suitable for EUV exposure have been developed.

[0003] In the formation of resist patterns using EUV (wavelength 13.5 nm) or electron beams for the purpose of forming fine patterns, the requirements for various performances are becoming stricter than when conventional light such as ArF (wavelength 193 nm) is used.

[0004] Resist compositions used to form resist patterns using EUV, electron beams, or the like often contain a photoacid generator and a photodegradable base. However, in a resist film formed using the resist composition, the distribution of the photoacid generator and the photodegradable base varies, resulting in non-uniform concentrations of the acid generated upon exposure and variations in the solubility of the resist film in a developer. As a result, variations occur in the line width of the resulting resist pattern, resulting in poor roughness performance.

[0005] As a method for improving the deterioration of roughness performance caused by such fluctuations in the distribution of materials of a photoacid generator and a photodegradable base, for example, Patent Document 1 describes a resist composition containing a salt having a specific structure in which a photoacid generator and a photodegradable base are linked together.

[0006] Japanese Patent Application Publication No. 2019-014704

[0007] The salt described in Patent Document 1 has a carboxylate anion type moiety corresponding to a photodegradable base, is hydrophilic, and does not easily swell in a developer, and is highly basic and has a high acid-trapping ability, thereby increasing the deprotection contrast of the protecting group in the acid-decomposable group possessed by the resin, and therefore has excellent roughness performance. However, the present inventors have found through their studies that the hydrophilicity and high basicity of the salt reduces the solubility of the salt itself and the matrix of the salt and resin in a developer, resulting in defects in the pattern.

[0008] The present invention addresses the problem of providing an actinic ray-sensitive or radiation-sensitive resin composition that can suppress the occurrence of defects and has excellent roughness performance when forming an ultrafine pattern (for example, a line-and-space pattern with a line width of 25 nm or less, or a hole pattern with a hole diameter of 25 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 that uses the actinic ray-sensitive or radiation-sensitive resin composition, and a method for manufacturing an electronic device.

[0009] The present inventors have found that the above problems can be solved by the following configuration.

[0010] [1] An actinic ray-sensitive or radiation-sensitive resin composition comprising an acid-decomposable resin (A) and the following compound (B) that generates an acid upon irradiation with actinic rays or radiation: Compound (B): A compound having the following structural moiety X and the following structural moiety Y, which generates an acid containing the following first acidic moiety derived from the following structural moiety X and the following second acidic moiety derived from the following structural moiety Y upon irradiation with actinic rays or radiation: Structural moiety X: Anionic moiety A １ － and the cationic moiety M １＋ and HA is produced by irradiation with actinic rays or radiation. 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 HA is produced by irradiation with actinic rays or radiation. ２ However, the compound (B) satisfies the following conditions I and II. Condition I: In the compound (B), the cationic moiety M in the structural moiety X is 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 Condition II: In the compound (B), the anion moiety A in the structural moiety Y has an acid dissociation constant a2 (pKa) derived from the acid moiety represented by the following formula: ２ － is an anionic moiety containing a partial structure represented by the following formula (1).

[0011]

[0012] In formula (1), * represents the bonding position to other atoms.

[0013] [2] The actinic ray-sensitive or radiation-sensitive resin composition according to [1], wherein the acid dissociation constant a1 (pKa) is −1.00 or less.

[0014] [3] In the compound (B), the anion moiety A in the structural moiety X １ －is an anionic moiety containing a partial structure represented by any one of the following formulas (2) to (5):

[0015]

[0016] In formula (2), X ２ represents a hydrogen atom, a halogen atom, or an organic group. * represents the bonding position to other atoms.

[0017]

[0018] In formula (3), X ３ represents an electron-withdrawing group. n represents an integer of 1 to 4. When n is an integer of 2 or more, a plurality of X ３ may be the same or different. * indicates the bonding position to other atoms.

[0019]

[0020] In formula (4), * represents the bonding position to other atoms.

[0021]

[0022] In formula (5), * represents the bonding position to other atoms.

[0023] [4] The actinic ray-sensitive or radiation-sensitive resin composition according to any one of [1] to [3], wherein the compound (B) has a halogen atom at the cation site.

[0024] [5] The actinic ray-sensitive or radiation-sensitive resin composition according to any one of [1] to [4], wherein the acid-decomposable resin (A) contains a repeating unit having a phenolic hydroxyl group. [6] 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 [5].

[0025] [7] 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 [5]; exposing the actinic ray-sensitive or radiation-sensitive film; and developing the exposed actinic ray-sensitive or radiation-sensitive film with a developer to form a pattern. [8] A method for producing an electronic device, comprising the pattern forming method according to [7].

[0026] According to the present invention, it is possible to provide an actinic ray-sensitive or radiation-sensitive resin composition that can suppress the occurrence of defects and has excellent roughness performance in the formation of an ultrafine pattern (for example, a line-and-space pattern with a line width of 25 nm or less, or a hole pattern with a hole diameter of 25 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 that uses the actinic ray-sensitive or radiation-sensitive resin composition, and a method for manufacturing an electronic device.

[0027] The present invention will be described in detail below. The following description of the constituent elements may be based on a representative embodiment of the present invention, but the present invention is not limited to such an embodiment. In the description of groups (atomic groups) in this specification, a notation that does not specify substituted or unsubstituted includes not only groups that have no substituents but also groups that have a substituent, unless it is contrary to the spirit of the present invention. For example, the term "alkyl group" includes not only alkyl groups that have no substituents (unsubstituted alkyl groups) but also alkyl groups that have a substituent (substituted alkyl groups). Furthermore, in this specification, the term "organic group" refers to a group containing at least one carbon atom. Unless otherwise specified, a monovalent substituent is preferred as the substituent.

[0028] In this specification, when it is said that a compound "may have a substituent," the type of the substituent, the position of the substituent, and the number of the substituent are not particularly limited. The number of the substituents may be, for example, one, two, three, or more. Examples of the substituent include a monovalent non-metallic atomic group excluding a hydrogen atom, and can be selected from, for example, the following substituents T:

[0029] (Substituent T) Examples of the substituent T include halogen atoms such as fluorine atom, chlorine atom, bromine atom, and iodine atom; alkoxy groups such as methoxy group, ethoxy group, and tert-butoxy group; aryloxy groups such as phenoxy group and p-tolyloxy group; alkoxycarbonyl groups such as methoxycarbonyl group, butoxycarbonyl group, and phenoxycarbonyl group; acyloxy groups such as acetoxy group, propionyloxy group, and benzoyloxy group; acyl groups such as acetyl group, benzoyl group, isobutyryl group, acryloyl group, methacryloyl group, and methoxalyl group; Examples of the alkylsulfanyl group include alkylsulfanyl groups such as a phenylsulfanyl group and a tert-butylsulfanyl group; arylsulfanyl groups such as a phenylsulfanyl group and a p-tolylsulfanyl group; alkyl groups; cycloalkyl groups; aryl groups; heteroaryl groups; hydroxyl groups; carboxy groups; formyl groups; sulfo groups; cyano groups; alkylaminocarbonyl groups; arylaminocarbonyl groups; sulfonamide groups; silyl groups; amino groups; monoalkylamino groups; dialkylamino groups; arylamino groups, nitro groups; formyl groups; and combinations thereof.

[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: Extreme Ultraviolet), X-rays, and electron beams (EB: Electron Beam). In this specification, "light" refers to actinic rays or radiation. In this specification, unless otherwise specified, "exposure" includes not only exposure using the bright line spectrum of a mercury lamp, far ultraviolet rays typified by excimer lasers, extreme ultraviolet rays, and X-rays, but also drawing using particle beams such as electron beams and ion beams. 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, the bonding direction of a divalent linking 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 "X-CO-O-Z" or "X-O-CO-Z".

[0032] In this specification, (meth)acrylate refers to acrylate and methacrylate, and (meth)acrylic refers to acrylic and methacrylic. In this specification, the weight average molecular weight (Mw), number average molecular weight (Mn), and molecular weight dispersity (also referred to as "molecular weight distribution") (Mw / Mn) are defined as polystyrene-equivalent values ​​measured by GPC (Gel Permeation Chromatography) measurement 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 this specification, the acid dissociation constant (pKa) refers to the pKa in an aqueous solution, and specifically, is a value determined by calculation based on a database of Hammett's substituent constants and known literature values ​​using the following software package 1. Software package 1: Advanced Chemistry Development (ACD / Labs) Software V8.14 for Solaris (1994-2007 ACD / Labs).

[0034] The pKa can also be calculated by molecular orbital calculation. ＋ 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.

[0035] 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.

[0036] In this specification, the term "solid content" refers to components that form an actinic ray-sensitive or radiation-sensitive film (typically a resist 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.

[0037] [Actinic ray-sensitive or radiation-sensitive resin composition] The actinic ray-sensitive or radiation-sensitive resin composition of the present invention will be described below. The actinic ray-sensitive or radiation-sensitive resin composition of the present invention (hereinafter also referred to as "the composition of the present invention") contains an acid-decomposable resin (A) and the following compound (B) that generates an acid upon irradiation with actinic rays or radiation. Compound (B): A compound having the following structural moiety X and the following structural moiety Y, which generates an acid containing the following first acidic moiety derived from the following structural moiety X and the following second acidic moiety derived from the following structural moiety Y upon irradiation with actinic rays or radiation. Structural moiety X: Anionic moiety A １ － and the cationic moiety M １ ＋ and HA is produced by irradiation with actinic rays or radiation. 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 HA is produced by irradiation with actinic rays or radiation. ２ However, the compound (B) satisfies the following conditions I and II. Condition I: In the compound (B), the cationic moiety M in the structural moiety X is 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 the acid dissociation constant a2 is greater than the acid dissociation constant a1. ２ － is an anionic moiety containing a partial structure represented by the following formula (1).

[0038]

[0039] In formula (1), * represents the bonding position to other atoms.

[0040] The reason why the composition of the present invention can suppress the occurrence of defects and achieve excellent roughness performance in the formation of ultrafine patterns (for example, line-and-space patterns with line widths of 25 nm or less and hole patterns with hole diameters of 25 nm or less) is not entirely clear, but the present inventors speculate as follows. Compound (B) contained in the composition of the present invention is a compound having both the functions of a photoacid generator and a photodegradable base, and the moiety corresponding to the photodegradable base is a salicylate anion type. By being in the salicylate anion type, compound (B) has appropriate hydrophilicity and appropriate basicity. Therefore, it is believed that the composition can improve roughness performance while suppressing the occurrence of defects that would occur in carboxylate anion types such as the salt described in Patent Document 1.

[0041] 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.

[0042] [Compound (B)] The compound (B) (hereinafter also referred to as "photoacid generator (B)") contained in the composition of the present invention will be described. Compound (B) is a compound having the structural moiety X and the structural moiety Y, and is a compound that 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 upon irradiation with actinic rays or radiation. However, compound (B) satisfies the above conditions I and II.

[0043] Compound (B) is a compound having the structural moiety X and the structural moiety Y. Compound (B) may have at least one of the structural moiety X and at least one of the structural moiety Y, and is preferably a compound having one of the structural moieties X and one of the structural moieties Y, or a compound having two of the structural moieties X and one of the structural moieties Y.

[0044] Condition I will be explained in more detail below. For example, when compound (B) 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.

[0045] For example, when compound (B) 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 － The acid dissociation constant when the compound PI 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 by １ When the compound PI has a plurality of acid dissociation constants derived from the acidic moiety represented by the formula (I), the value of the acid dissociation constant a2 is larger than the largest value of the plurality of acid dissociation constants a1. １ － and one HA １ and one HA ２ The acid dissociation constant when the compound is aa is defined as "a compound having one A １ － and one HA １ and one HA ２ "Compound having two A １ － and one HA 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.

[0046] 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 the compound (B) is irradiated with actinic rays or radiation. When the compound (B) has two or more structural moieties X, the structural moieties X may be the same or different. In addition, when the compound (B) has two or more structural moieties X, the structural moieties X may be the same or different. １ － and two or more of the above M １ ＋ In the compound (B), 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.

[0047] 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 0.10 or more, more preferably 0.50 or more, and even more preferably 1.00 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.

[0048] In the compound PI, the acid dissociation constant a2 is determined by the reaction of an anion moiety containing a partial structure represented by the formula (1) described below with H ＋ and the acid dissociation constant a2 is preferably 20 or less, more preferably 15 or less. The lower limit of the acid dissociation constant a2 is preferably −4.00 or more.

[0049] In the compound PI, the acid dissociation constant a1 is preferably 2.00 or less, more preferably 0 or less, and even more preferably −1.00 or less. The lower limit of the acid dissociation constant a1 is preferably −20.00 or more.

[0050] Anion site A ２ － In the compound (B), the anion moiety A in the structural moiety Y is ２ － is an anionic moiety containing a partial structure represented by the following formula (1), as shown in Condition II.

[0051]

[0052] In formula (1), * represents the bonding position to other atoms.

[0053] In a preferred embodiment, the anionic moiety containing the partial structure represented by the above formula (1) is preferably an anionic functional group represented by the below-described formula (1a).

[0054] Next, the anion site A １ － The anion site A １ － is a structural moiety containing a negatively charged atom or atomic group, and the anionic moiety A ２ － Examples of suitable structural moieties include those that can form an acidic moiety with a smaller acid dissociation constant than those shown in formulas (CC-1) to (CC-7) below. In formulas (CC-1) to (CC-7) below, * represents a bonding position. In formula (CC-2), R Ａ represents a monovalent organic group. Ａ The monovalent organic group represented by the formula (I) is not particularly limited, but examples thereof include a cyano group, a trifluoromethyl group, and a methanesulfonyl group.

[0055]

[0056] Anion site A １ － is preferably an anionic moiety containing a partial structure represented by any one of the following formulas (2) to (5):

[0057]

[0058] In formula (2), X ２ represents a hydrogen atom, a halogen atom, or an organic group. * represents the bonding position to other atoms.

[0059]

[0060] In formula (3), X ３ represents an electron-withdrawing group. n represents an integer of 1 to 4. When n is an integer of 2 or more, a plurality of X ３ may be the same or different. * indicates the bonding position to other atoms.

[0061]

[0062] In formula (4), * represents the bonding position to other atoms.

[0063]

[0064] In formula (5), * represents the bonding position to other atoms.

[0065] In formula (2), X ２ represents a hydrogen atom, a halogen atom or an organic group. ２ Examples of the halogen atom represented by X include a fluorine atom, a chlorine atom, a bromine atom, and an iodine atom, and a fluorine atom is preferred. ２ Examples of the organic group represented by the formula (I) include alkyl groups having 1 to 15 carbon atoms which may have a fluorine atom, preferably perfluoroalkyl groups having 1 to 10 carbon atoms, and more preferably perfluoroalkyl groups having 1 to 6 carbon atoms.

[0066] X ２ preferably represents a halogen atom, more preferably a fluorine atom.

[0067] In formula (3), X ３ represents an electron-withdrawing group. ３ Examples of the electron-withdrawing group represented by X include a group selected from the group consisting of a halogen atom (preferably a fluorine atom, a chlorine atom, a bromine atom, or an iodine atom), a halogenated hydrocarbon group, an alkoxycarbonyl group, an acyl group, an acyloxy group, a cyano group, a nitro group, and a heterocyclic group, or an aryl group substituted with a group selected from the above group. ３ preferably has a Hammett's substituent constant σp value of 0.05 or more, is more preferably a halogen atom, a halogenated hydrocarbon group, a cyano group, or a nitro group, is still more preferably a fluorine atom, a fluorinated hydrocarbon group, a cyano group, or a nitro group, is still more preferably a fluorine atom or a fluorinated hydrocarbon group (preferably a fluoroalkyl group having 1 to 10 carbon atoms), and is particularly preferably a fluorine atom.

[0068] Here, the Hammett's substituent constant σ is a numerical representation of the effect of a substituent on the acid dissociation equilibrium constant of a substituted benzoic acid, and is a parameter indicating the strength of the electron-withdrawing and electron-donating properties of the substituent. The Hammett's substituent constant σp value in this specification means the substituent constant σ when the substituent is located at the para position of the benzoic acid. The Hammett's substituent constant σp value of each group in this specification is the value described in the literature "Hansch et al., Chemical Reviews, 1991, Vol. 91, No. 2, 165-195." For groups for which the Hammett's substituent constant σp value is not shown in the above-mentioned literature, the Hammett's substituent constant σp value can be calculated using the software "ACD / ChemSketch (ACD / Labs 8.00 Release Product Version: 8.08)" based on the difference between the pKa of benzoic acid and the pKa of a benzoic acid derivative having a substituent at the para position.

[0069] In formula (3), n represents an integer of 1 to 4, with 3 or 4 being preferred.

[0070] Cationic moiety M １ ＋ and cationic moiety M ２ ＋ is a structural moiety containing a positively charged atom or atomic group, such as a monovalent organic cation.

[0071] The compound (B) preferably has a halogen atom at the cation site, and M １ ＋ and M ２ ＋ However, it is preferable that the compound (B) has a halogen atom. Examples of the halogen atom present in the cationic moiety include a fluorine atom, a chlorine atom, a bromine atom, and an iodine atom, and a fluorine atom and an iodine atom are preferred. By having a halogen atom in the cationic moiety, it is possible to increase the absorption efficiency of EUV light and electron beams and the solubility of the compound (B) in a developer, and as a result, it is possible to improve roughness performance and defect suppression properties.

[0072] M １ ＋ and M ２ ＋is preferably a sulfonium cation or an iodonium cation. １ ＋ and M ２ ＋ 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)").

[0073]

[0074] 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.

[0075] 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.

[0076] 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 ~R２０３ 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.

[0077] 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.

[0078] R ２０１ ~R ２０３ Preferred substituents that the aryl group, alkyl group, and cycloalkyl group may have include alkyl groups (e.g., having 1 to 15 carbon atoms), cycloalkyl groups (e.g., having 3 to 15 carbon atoms), aryl groups (e.g., having 6 to 14 carbon atoms), alkoxy groups (e.g., having 1 to 15 carbon atoms), cycloalkylalkoxy groups (e.g., having 1 to 15 carbon atoms), halogen atoms (e.g., fluorine and iodine), hydroxyl groups, carboxyl groups, ester groups, sulfanyl 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 groups have halogen atoms as substituents to form halogenated alkyl groups such as trifluoromethyl groups. It is also preferred that the above substituents, when combined in any manner, form an acid-decomposable group.

[0079] 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.

[0080] R ２０１ ~R ２０３ Examples of the alkyl group and cycloalkyl group in R include linear alkyl groups having 1 to 10 carbon atoms or branched alkyl groups having 3 to 10 carbon atoms (e.g., methyl, ethyl, propyl, butyl, and pentyl groups), and cycloalkyl groups having 3 to 10 carbon atoms (e.g., cyclopentyl, cyclohexyl, and norbornyl groups). ２０１ ~R ２０３ may be further substituted with a halogen atom, an alkoxy group (e.g., having 1 to 5 carbon atoms), a hydroxyl group, a cyano group, or a nitro group. ２０１ ~R ２０３ It is also preferred that the substituents independently form an acid-decomposable group by any combination of the substituents.

[0081] Next, the cation (ZaI-3b) will be described. The cation (ZaI-3b) is a cation represented by the following formula (ZaI-3b).

[0082]

[0083] In formula (ZaI-3b), R １ｃ ~R ５ｃ R each independently represents a hydrogen atom, an alkyl group, a cycloalkyl group, an aryl group, an alkoxy group, an aryloxy group, an alkoxycarbonyl group, an alkylcarbonyloxy group, a cycloalkylcarbonyloxy group, a halogen atom, a hydroxyl group, a nitro group, an alkylthio group, or an arylthio group. ６ｃ and R ７ｃR each independently represents a hydrogen atom, an alkyl group (for example, a t-butyl group), a cycloalkyl group, a halogen atom, a cyano group, or an aryl group. ｘ and R ｙ R each independently represents an alkyl group, a cycloalkyl group, a 2-oxoalkyl group, a 2-oxocycloalkyl group, an alkoxycarbonylalkyl group, an allyl group, or a vinyl group. １ｃ ~R ７ｃ , and R ｘ and R ｙ It is also preferred that the substituents independently form an acid-decomposable group by any combination of the substituents.

[0084] R １ｃ ~R ５ｃ Two or more of the following, R ５ｃ and R ６ｃ , R ６ｃ and R ７ｃ , R ５ｃ and R ｘ , and R ｘ and R ｙ may be bonded to each other to form a ring, and each of these rings may independently contain an oxygen atom, a sulfur atom, a ketone group, an ester bond, or an amide bond. Examples of the ring include aromatic or non-aromatic hydrocarbon rings, aromatic or non-aromatic heterocycles, and polycyclic fused rings formed by combining two or more of these rings. Examples of the ring include 3- to 10-membered rings, preferably 4- to 8-membered rings, and more preferably 5- or 6-membered rings.

[0085] R １ｃ ~R ５ｃ Two or more of the following, R ６ｃ and R ７ｃ , and R ｘ and R ｙ Examples of the group formed by bonding of R include alkylene groups such as butylene and pentylene. A methylene group in this alkylene group may be substituted with a heteroatom such as an oxygen atom. ５ｃ and R ６ｃ , and R ５ｃ and R ｘThe group formed by bonding is preferably a single bond or an alkylene group. Examples of the alkylene group include a methylene group and an ethylene group.

[0086] 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.

[0087] Next, the cation (ZaI-4b) will be described. The cation (ZaI-4b) is a cation represented by the following formula (ZaI-4b).

[0088]

[0089] 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.

[0090] In formula (ZaI-4b), R １３ , R １４ , and R １５ The alkyl group in R may be linear or branched. The number of carbon atoms in the alkyl group is preferably 1 to 10. The alkyl group is preferably a methyl group, an ethyl group, an n-butyl group, a t-butyl group, or the like. １３ ~R １５ , and R ｘ and R ｙ It is also preferred that each of the substituents independently form an acid-decomposable group by any combination of the substituents.

[0091] Next, formula (ZaII) will be described. In formula (ZaII), R ２０４ and R ２０５ R each independently represents an aryl group, an alkyl group, or a cycloalkyl group. ２０４ and R ２０５ The aryl group in R is preferably a phenyl group or a naphthyl group, and more preferably a phenyl group. ２０４ and R ２０５ The aryl group in R may be an aryl group having a heterocycle containing an oxygen atom, a nitrogen atom, a sulfur atom, or the like. Examples of the skeleton of the aryl group having a heterocycle include pyrrole, furan, thiophene, indole, benzofuran, and benzothiophene. ２０４ and R ２０５The alkyl group and cycloalkyl group are preferably a linear alkyl group having 1 to 10 carbon atoms or a branched alkyl group having 3 to 10 carbon atoms (e.g., methyl, ethyl, propyl, butyl, or pentyl), or a cycloalkyl group having 3 to 10 carbon atoms (e.g., cyclopentyl, cyclohexyl, or norbornyl).

[0092] 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.

[0093] Below is M １ ＋ and M ２ ＋ Specific examples of the cation represented by the formula (I) are shown below, but the present invention is not limited thereto.

[0094]

[0095]

[0096]

[0097]

[0098]

[0099] There are no particular limitations on the compound (B), but when the compound (B) is a compound having one each of the structural moieties X and Y, examples thereof include compounds represented by the following general formula (B-1): １１ ＋ A １１ － -L１ -A １２ － M １２ ＋ (B-1)

[0100] In general formula (B-1), “M １１ ＋ A １１ － " and "A １２ － M １２ ＋ " correspond to the structural moiety X and the structural moiety Y, respectively. The compound represented by general formula (B-1) can be converted into HA by irradiation with actinic rays or radiation. １１ -L １ -A １２ It generates an acid represented by "M １１ ＋ A １１ － " is HA １１ and forming a first acidic site represented by "A １２ － M １２ ＋ " is an HA having a structure different from the first acidic site. １２ The second acidic site is formed.

[0101] In general formula (B-1), M １１ ＋ and M １２ ＋ A each independently represents an organic cation. １１ － and A １２ － each independently represents an anionic functional group. １２ － A １１ － represents a structure different from the anionic functional group represented by １ represents a single bond or a divalent linking group. １１ ＋ and M １２ ＋ The organic cation represented by H ＋ Compound PIa (HA) １１ -L １-A １２ In H), A １２ The acid dissociation constant a2 derived from the acidic site represented by H is １１ The preferred values ​​of the acid dissociation constant a1 and the acid dissociation constant a2 are as described above. １２ － is an anionic functional group containing a partial structure represented by the above formula (1).

[0102] In general formula (B-1), M １１ ＋ and M １２ ＋ The organic cation represented by the formula １ ＋ and M ２ ＋ The same applies to preferred examples.

[0103] In general formula (B-1), A １２ － The anionic functional group represented by the formula (1) is an anionic functional group containing a partial structure represented by the formula (1), and is preferably an anionic functional group represented by the following formula (1a):

[0104]

[0105] In formula (1a), Ra represents a monovalent substituent. * represents L １ represents the bonding position with na. na represents 0 or 1. nb represents an integer of 0 to (4+2×na-1). When nb is an integer of 2 or more, multiple Ra may be the same or different.

[0106] In formula (1a), Ra represents a monovalent substituent such as a halogen atom, a hydroxy group, an alkyl group, an alkoxy group, an alkoxycarbonyl group, an aryl group, an aryloxy group, or an aryloxycarbonyl group.

[0107] Examples of the halogen atom represented by Ra include a fluorine atom, a chlorine atom, a bromine atom, and an iodine atom. The halogen atom is preferably a fluorine atom or an iodine atom, and more preferably an iodine atom. Examples of the alkyl group represented by Ra include linear or branched alkyl groups having 1 to 15 carbon atoms, such as a methyl group, an ethyl group, an n-propyl group, an isopropyl group, an n-butyl group, an isobutyl group, and a t-butyl group. Examples of the alkyl group in the alkoxy group or alkoxycarbonyl group represented by Ra include the same groups as the alkyl group represented by Ra above. Examples of the aryl group represented by Ra include aryl groups having 6 to 15 carbon atoms, such as a phenyl group or a naphthyl group. Examples of the aryl group in the aryloxy group or aryloxycarbonyl group represented by Ra include the same groups as the aryl group represented by Ra above.

[0108] The monovalent substituent may further have a substituent. Examples of the further substituent include a halogen atom, a hydroxy group, an alkyl group, a cycloalkyl group, an alkoxy group, an alkoxycarbonyl group, an aryl group, an aryloxy group, and an aryloxycarbonyl group. The cycloalkyl group may have a heteroatom such as an oxygen atom as a ring member atom. The halogen atom is preferably a fluorine atom, a chlorine atom, a bromine atom, or an iodine atom, more preferably a fluorine atom or an iodine atom, and even more preferably an iodine atom. The iodine atom is preferably directly bonded to the aromatic ring. The further substituent may further have a substituent. Examples of the further substituent include a halogen atom. The halogen atom is preferably a fluorine atom, a chlorine atom, a bromine atom, or an iodine atom, more preferably a fluorine atom or an iodine atom, and even more preferably an iodine atom. The iodine atom is preferably directly bonded to the aromatic ring.

[0109] In formula (1a), na represents 0 or 1, and is preferably 0. nb represents an integer of 0 to (4+2×na−1), and is preferably 0 to 2.

[0110] In general formula (B-1), A １１ －Examples of the anionic functional group represented by the formula (CC-1) include anionic functional groups containing a partial structure selected from the group consisting of the above formulae (CC-1) to (CC-7), and are preferably anionic functional groups containing a partial structure represented by any one of the above formulae (2) to (5), and more preferably anionic functional groups selected from the group consisting of the above formulae (2), (3), and the following formulae (4a), (5a), and (5b):

[0111]

[0112] In formula (4a), X ４ represents an organic group. １ represents the bonding position with

[0113]

[0114] In formula (5a), X ５ represents a halogen atom or an organic group. １ represents the bonding position with

[0115]

[0116] In formula (5b), X ６ represents an organic group. １ represents the bonding position with

[0117] In formula (4a), X ４ represents an organic group. ４ The organic group represented by X is preferably an alkyl group, a cycloalkyl group, or an aryl group. ４ The number of carbon atoms in the alkyl group represented by is preferably 1 to 15, more preferably 1 to 10. The alkyl group may have a substituent. The substituent is preferably a fluorine atom or a cyano group. When the alkyl group has a fluorine atom as a substituent, it may be a perfluoroalkyl group. Furthermore, a carbon atom in the alkyl group may be substituted with a carbonyl group.

[0118] X ４ The number of carbon atoms in the cycloalkyl group represented by the formula (I) is preferably 3 to 15, and more preferably 3 to 10. The cycloalkyl group may have a substituent. Examples of the substituent include the same groups as the substituents that the alkyl group may have.

[0119] X ４ The aryl group represented by is preferably a phenyl group or a naphthyl group, and more preferably a phenyl group. The aryl group may have a substituent. Preferred examples of the substituent include a fluorine atom, a perfluoroalkyl group (e.g., preferably having 1 to 10 carbon atoms, more preferably having 1 to 6 carbon atoms), or a cyano group.

[0120] In formula (5a), X ５ represents a halogen atom or an organic group. ５ The halogen atom represented by X is preferably a fluorine atom. ５ The organic group represented by X in the above formula (4a) is ４ The preferred examples are also the same.

[0121] In formula (5b), X ６ represents an organic group. ６ The organic group represented by X in the above formula (4a) is ４ The preferred examples are also the same.

[0122] In general formula (B-1), L １ represents a single bond or a divalent linking group. １ The divalent linking group represented by the formula (I) is not particularly limited, and may be —CO—, —NR—, —CO ２ -, -O-, -S-, -SO-, -SO ２Examples of the alkylene group include alkylene groups (preferably having 1 to 6 carbon atoms, which may be linear or branched), cycloalkylene groups (preferably having 3 to 15 carbon atoms), alkenylene groups (preferably having 2 to 6 carbon atoms), divalent aliphatic heterocyclic groups (preferably a 5- to 10-membered ring having at least one N atom, O atom, S atom, or Se atom in the ring structure, more preferably a 5- to 7-membered ring, and even more preferably a 5- to 6-membered ring), divalent aromatic heterocyclic groups (preferably a 5- to 10-membered ring having at least one N atom, O atom, S atom, or Se atom in the ring structure, more preferably a 5- to 7-membered ring, and even more preferably a 5- to 6-membered ring), divalent aromatic hydrocarbon ring groups (preferably a 6- to 10-membered ring, and even more preferably a 6-membered ring), and divalent linking groups combining a plurality of these. The R may be a hydrogen atom or a monovalent organic group. The monovalent organic group is not particularly limited, but an alkyl group (preferably having 1 to 6 carbon atoms) is preferred. The alkylene group, the cycloalkylene group, the alkenylene group, the divalent aliphatic heterocyclic group, the divalent aromatic heterocyclic group, and the divalent aromatic hydrocarbon ring group may be substituted with a substituent, such as a halogen atom (preferably a fluorine atom).

[0123] When compound (B) is a compound having two or more of the structural moieties X and the structural moiety Y, examples thereof include compounds represented by the following general formula (B-2).

[0124]

[0125] In general formula (B-2), “M ２１ ＋ A ２１ － " and "A ２２ － M ２２ ＋ " correspond to the structural moiety X and the structural moiety Y, respectively. The compound represented by general formula (B-2) generates an acid represented by the following general formula (B-2-1) when irradiated with actinic rays or radiation. ２１ ＋ A ２１ － " is HA ２１ and forming a first acidic site represented by "A ２２－ M ２２ ＋ " is an HA having a structure different from the first acidic site. ２２ The second acidic site is formed.

[0126]

[0127] In general formula (B-2), M ２１ ＋ and M ２２ ＋ A each independently represents an organic cation. ２１ － and A ２２ － each independently represents an anionic functional group. ２２ － A ２１ － represents a structure different from the anionic functional group represented by ２ represents an organic group having a valence of (n1+n2), n1 represents an integer of 2 or more, and n2 represents an integer of 1 or more. However, in the general formula (B-2) below, M ２１ ＋ and M ２２ ＋ The organic cation represented by H ＋ In the compound PIIa (corresponding to the compound represented by the above general formula (B-2-1)), A ２２ The acid dissociation constant a2 derived from the acidic site represented by H is ２１ The preferred values ​​of the acid dissociation constant a1 and the acid dissociation constant a2 are as described above. ２２ － is an anionic functional group containing a partial structure represented by the above formula (1).

[0128] In the above general formula (B-2), M ２１ ＋ , M ２２ ＋ , A ２１ － , and A ２２ － are each M in the above general formula (B-1).１１ ＋ , M １２ ＋ , A １１ － , and A １２ － In the general formula (B-2), n1 M ２１ ＋ n1 A's ２１ － and each represent the same group.

[0129] In the above general formula (B-2), L ２ The (n1+n2)-valent organic group represented by the formula (I) is not particularly limited, and examples thereof include groups represented by the following formula (A1) and the following formula (A2). In the following formulas (A1) and (A2), at least two of the * symbols represent A. ２１ － At least one * represents a bonding position with A ２２ － represents the bonding position with

[0130]

[0131] In the above (A1) and (A2), T １ represents a trivalent hydrocarbon ring group or a trivalent heterocyclic group, T ２ represents a carbon atom, a tetravalent hydrocarbon ring group, or a tetravalent heterocyclic group.

[0132] The hydrocarbon ring group may be an aromatic hydrocarbon ring group or an aliphatic hydrocarbon ring group. The number of carbon atoms contained in the hydrocarbon ring group is preferably 6 to 18, more preferably 6 to 14. The heterocyclic group may be an aromatic heterocyclic group or an aliphatic heterocyclic group. The heterocyclic ring is preferably a 5- to 10-membered ring having at least one N atom, O atom, S atom, or Se atom in the ring structure, more preferably a 5- to 7-membered ring, and even more preferably a 5- or 6-membered ring.

[0133] In addition, in the above (A1) and (A2), L ２１ and L ２２ each independently represents a single bond or a divalent linking group. ２１ and L ２２Examples of the divalent linking group represented by the formula (B-1) include L １ n1 represents an integer of 2 or more. The upper limit is not particularly limited, but is, for example, 6 or less, preferably 4 or less, and more preferably 3 or less. n2 represents an integer of 1 or more. The upper limit is not particularly limited, but is, for example, 3 or less, preferably 2 or less.

[0134] When compound (B) is a compound having two or more of the structural moieties X and the structural moiety Y, it is also preferable that the compound is, for example, a compound represented by the following general formula (B-3).

[0135]

[0136] In general formula (B-3), “M ３１ ＋ A ３１ － " and "A ３２ － M ３２ ＋ " correspond to the structural moiety X and the structural moiety Y, respectively. The compound represented by general formula (B-3) generates an acid represented by the following general formula (B-3-1) when irradiated with actinic rays or radiation. ３１ ＋ A ３１ － " is HA ３１ and forming a first acidic site represented by "A ３２ － M ３２ ＋ " is an HA having a structure different from the first acidic site. ３２ The second acidic site is formed.

[0137]

[0138] In general formula (B-3), M ３１ ＋ and M ３２ ＋ A each independently represents an organic cation. ３１ － and A ３２ － each independently represents an anionic functional group.３２ － A ３１ － represents a structure different from the anionic functional group represented by ３ represents a single bond or a divalent linking group, and n3 represents an integer of 2 or more. ３１ ＋ and M ３２ ＋ The organic cation represented by H ＋ In the compound PIIIa (corresponding to the compound represented by the above general formula (B-3-1)), A ３２ The acid dissociation constant a2 derived from the acidic site represented by H is ３１ The preferred values ​​of the acid dissociation constant a1 and the acid dissociation constant a2 are as described above. ３２ － is an anionic functional group containing a partial structure represented by the above formula (1).

[0139] In the above general formula (B-3), M ３１ ＋ , M ３２ ＋ , and A ３１ － are each M in the above general formula (B-1). １１ ＋ , M １２ ＋ , and A １１ － The same definition and preferred embodiments are also the same.

[0140] In general formula (B-3), A ３２ － The anionic functional group represented by the formula (1) is an anionic functional group containing a partial structure represented by the formula (1), and is preferably an anionic functional group represented by the following formula (1b):

[0141]

[0142] In formula (1b), Rb represents a monovalent substituent. ３represents the bonding position with nc. nc represents 0 or 1. nd represents an integer of 2 or 3. ne represents an integer of 0 to (4+2×nc-nd). When ne is an integer of 2 or greater, multiple Rb's may be the same or different.

[0143] In formula (1b), Rb has the same meaning as Ra in formula (1a), and preferred examples are also the same.

[0144] In formula (1b), nc represents 0 or 1, and is preferably 0. nd represents an integer of 2 or 3, and is preferably 2. ne represents an integer of 0 to (4+2×nc−nd), and is preferably 0 to 2.

[0145] In the above general formula (B-3), L ３ Examples of the divalent linking group represented by the formula (B-1) include L １ Examples of the divalent linking group include:

[0146] Specific examples of the structure other than the cation moiety in compound (B) are shown below, but the present invention is not limited to these.

[0147]

[0148]

[0149]

[0150]

[0151] The content of compound (B) in the composition of the present invention is not particularly limited, but is preferably 90 mass% or less, more preferably 80 mass% or less, and even more preferably 70 mass% or less, based on the total solid content of the composition of the present invention.The content of compound (B) in the composition of the present invention is not particularly limited, but is preferably 5 mass% or more, more preferably 10 mass% or more, and even more preferably 15 mass% or more, 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.

[0152] [Acid-Decomposable Resin (A)] The composition of the present invention contains an acid-decomposable resin (A) (also referred to as "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.

[0153] (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.

[0154] 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)

[0155] In formula (Y1) and formula (Y2), Rx １ ~Rx ３ Rx each independently represents an alkyl group (linear or branched), a cycloalkyl group (monocyclic or polycyclic), an alkenyl group (linear or branched), or an aryl group (monocyclic or polycyclic). １ ~Rx ３ When all of Rx are alkyl groups (linear or branched), １ ~Rx ３ At least two of Rx are preferably methyl groups. １ ~Rx ３ each independently preferably represents a linear or branched alkyl group, and Rx １ ~Rx ３ More preferably, Rx each independently represents a linear alkyl group. １ ~Rx ３ may be bonded to form a monocyclic or polycyclic ring. １ ~Rx ３ The alkyl group of Rx is preferably an alkyl group having 1 to 5 carbon atoms, such as a methyl group, an ethyl group, an n-propyl group, an isopropyl group, an n-butyl group, an isobutyl group, or a t-butyl group. １ ~Rx ３ The cycloalkyl group 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 ~Rx３ The aryl group in Rx is preferably an aryl group having 6 to 10 carbon atoms, and examples thereof include a phenyl group, a naphthyl group, and an anthryl group. １ ~Rx ３ The alkenyl group of Rx is preferably a vinyl group. １ ~Rx ３ The ring formed by combining the two is preferably a cycloalkyl group. １ ~Rx ３ The cycloalkyl group formed by bonding the two is preferably a monocyclic cycloalkyl group such as a cyclopentyl group or a cyclohexyl group, or a polycyclic cycloalkyl group such as a norbornyl group, a tetracyclodecanyl group, a tetracyclododecanyl group, or an adamantyl group, and more preferably a monocyclic cycloalkyl group having 5 to 6 carbon atoms. １ ~Rx 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.

[0156] In formula (Y3), R ３６ ~R ３８ R each independently represents a hydrogen atom or a monovalent organic group. ３７ and R ３８may be bonded to each other to form a ring. Examples of the monovalent organic group include an alkyl group, a cycloalkyl group, an aryl group, an aralkyl group, and an alkenyl group. ３６ is also preferably a hydrogen atom. The alkyl group, cycloalkyl group, aryl group, and aralkyl group may contain a heteroatom such as an oxygen atom and / or a group 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.

[0157] Formula (Y3) is preferably a group represented by the following formula (Y3-1).

[0158]

[0159] Here, L １ and L ２Each independently represents a hydrogen atom, an alkyl group, a cycloalkyl group, an aryl group, or a group combining these (for example, a group combining an alkyl group and an aryl group). M represents a single bond or a divalent linking group. Q represents an alkyl group that may contain a heteroatom, a cycloalkyl group that may contain a heteroatom, an aryl group that may contain a heteroatom, an amino group, an ammonium group, a mercapto group, a cyano group, an aldehyde group, or a group combining these (for example, a group combining an alkyl group and a cycloalkyl group). In the alkyl group and the cycloalkyl group, for example, one of the methylene groups may be replaced with a heteroatom such as an oxygen atom, or a group containing a heteroatom such as a carbonyl group. In addition, L １ and L ２ It is preferred that one of Q, M, and L is a hydrogen atom, and the other is an alkyl group, a cycloalkyl group, an aryl group, or a group in which an alkylene group and an aryl group are combined. １ At least two of the groups may be bonded to form a ring (preferably a 5- or 6-membered ring). 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.

[0160] When the actinic ray-sensitive or radiation-sensitive resin composition is, for example, a resist composition for EUV exposure, L １ and L ２It 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.

[0161] 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.

[0162] 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.

[0163] 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.

[0164] The repeating unit having an acid-decomposable group is also preferably a repeating unit represented by formula (A).

[0165]

[0166] L １ represents a divalent linking group which may have a fluorine atom or an iodine atom, R １ represents a hydrogen atom, a fluorine atom, an iodine atom, an alkyl group which may have a fluorine atom or an iodine atom, or an aryl group which may have a fluorine atom or an iodine atom; R ２ represents a leaving group which is eliminated by the action of an acid and may have a fluorine atom or an iodine atom. １ , R １ , and R ２ At least one of L has a fluorine atom or an iodine atom. １ Examples of the divalent linking group which may have a fluorine atom or an iodine atom and is represented by the formula: ２ -, hydrocarbon groups which may have a fluorine atom or an iodine atom (for example, alkylene groups, cycloalkylene groups, alkenylene groups, arylene groups, etc.), and linking groups in which a plurality of these groups are linked together. １As the alkylene group, -CO-, an arylene group, or -arylene group-alkylene group having a fluorine atom or an iodine atom- is preferred, and -CO- or -arylene group-alkylene group having a fluorine atom or an iodine atom- is more preferred. As the arylene group, a phenylene group is preferred. The alkylene group may be linear or branched. The number of carbon atoms in the alkylene group is not particularly limited, but is preferably 1 to 10, and more preferably 1 to 3. The total number of fluorine atoms and iodine atoms contained in the alkylene group having a fluorine atom or an iodine atom is not particularly limited, but is preferably 2 or more, more preferably 2 to 10, and even more preferably 3 to 6.

[0167] 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.

[0168] R ２ Examples of the leaving group represented by the formulae (Y1) to (Y4) above, which may have a fluorine atom or an iodine atom, include leaving groups represented by the formulae (Y1) to (Y4) above, which have a fluorine atom or an iodine atom.

[0169] The repeating unit having an acid-decomposable group is also preferably a repeating unit represented by formula (AI).

[0170]

[0171] In formula (AI), Xa １ represents a hydrogen atom or an alkyl group which may have a substituent. T represents a single bond or a divalent linking group. Rx １ ~Rx ３each independently represents an alkyl group (linear or branched), a cycloalkyl group (monocyclic or polycyclic), an alkenyl group (linear or branched), or an aryl group (monocyclic or polycyclic). １ ~Rx ３ When all of Rx are alkyl groups (linear or branched), １ ~Rx ３ Preferably, at least two of Rx are methyl groups. １ ~Rx ３ may be bonded to form a monocyclic or polycyclic ring (such as a monocyclic or polycyclic cycloalkyl group).

[0172] 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.

[0173] 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.

[0174] Rx １ ~Rx ３The alkyl group of Rx is preferably an alkyl group having 1 to 4 carbon atoms, such as a methyl group, an ethyl group, an n-propyl group, an isopropyl group, an n-butyl group, an isobutyl group, or a t-butyl group. １ ~Rx ３ The cycloalkyl group of Rx is preferably a monocyclic cycloalkyl group such as a cyclopentyl group or a cyclohexyl group, or a polycyclic cycloalkyl group such as a norbornyl group, a tetracyclodecanyl group, a tetracyclododecanyl group, or an adamantyl group. １ ~Rx ３ The aryl group in Rx is preferably an aryl group having 6 to 10 carbon atoms, and examples thereof include a phenyl group, a naphthyl group, and an anthryl group. １ ~Rx ３ The alkenyl group of Rx is preferably a vinyl group. １ ~Rx ３ As the cycloalkyl group formed by combining the above two, a monocyclic cycloalkyl group such as a cyclopentyl group or a cyclohexyl group is preferred. Polycyclic cycloalkyl groups such as a norbornyl group, a tetracyclodecanyl group, a tetracyclododecanyl group, and an adamantyl group are also preferred. Among these, a monocyclic cycloalkyl group having 5 to 6 carbon atoms is preferred. Rx １ ~Rx ３ The cycloalkyl group formed by bonding these two may have, for example, one of the methylene groups constituting the ring replaced with a heteroatom such as an oxygen atom, a group containing a heteroatom such as a carbonyl group, or a vinylidene group. Furthermore, in these cycloalkyl groups, one or more of the ethylene groups constituting the cycloalkane ring may be replaced with a vinylene group. The repeating unit represented by formula (AI) can be, for example, Rx １ is a methyl group or an ethyl group, and Rx ２ and Rx ３ and are preferably bonded to form the above-mentioned cycloalkyl group.

[0175] 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.

[0176] 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).

[0177] 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.

[0178]

[0179] 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).

[0180] The alkyl group represented by Xb, which may have a substituent, is, for example, a methyl group or —CH ２ -R １１ Examples of the group include a group represented by the following formula: １１represents a halogen atom (such as a fluorine atom), a hydroxyl group, or a monovalent organic group, and examples thereof include an alkyl group having 5 or less carbon atoms which may be substituted with a halogen atom, an acyl group having 5 or less carbon atoms which may be substituted with a halogen atom, and an alkoxy group having 5 or less carbon atoms which may be substituted with a halogen atom, preferably an alkyl group having 3 or less carbon atoms, and more preferably a methyl group. Xb is preferably a hydrogen atom, a fluorine atom, a methyl group, a trifluoromethyl group, or a hydroxymethyl group.

[0181] 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.

[0182] 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.

[0183] 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.

[0184] 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)).

[0185] 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).

[0186] 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).

[0187] 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.

[0188] The resin (A) preferably has an acid group, and as described below, it preferably contains a repeating unit having an acid group, and more preferably contains a repeating unit having a phenolic hydroxyl 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.

[0189] 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.

[0190] (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.

[0191] The repeating unit having an acid group is preferably a repeating unit represented by the following formula (b1-1).

[0192]

[0193] 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).

[0194] 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).

[0195] (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.

[0196] The unit X is preferably a repeating unit represented by formula (C).

[0197]

[0198] 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.

[0199] 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).

[0200] 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.

[0201] (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.

[0202] 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).

[0203]

[0204] 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.

[0205] 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):

[0206]

[0207] 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).

[0208] 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.

[0209] 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):

[0210]

[0211] 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.

[0212] 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).

[0213] (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).

[0214]

[0215] 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.

[0216] 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.

[0217] 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).

[0218] (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.

[0219]

[0220] 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 the repeating unit represented by formula (V-1) or (V-2) include the repeating units described in paragraph

[0100] of WO 2018 / 193954.

[0221] 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.

[0222] (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>.

[0223] 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.

[0224] 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.

[0225] (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.

[0226] (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.

[0227]

[0228] 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.

[0229] (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.

[0230] 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.

[0231] 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.

[0232] 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.

[0233] 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.

[0234] [Compound (C) that generates an acid upon irradiation with actinic rays or radiation] The composition of the present invention may further contain a compound (C) (hereinafter also referred to as "photoacid generator (C)") that generates an acid upon irradiation with actinic rays or radiation and is different from compound (B). Compound (C) 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 compound (C) is in the form of a low molecular weight compound, the molecular weight of compound (C) is preferably 5,000 or less, more preferably 4,000 or less, and even more preferably 3,000 or less. There is no particular restriction on the lower limit, but 100 or more is preferred. When compound (C) is in the form of being incorporated into a part of a polymer, it may be incorporated into a part of resin (A) or into a resin different from resin (A). Compound (C) is preferably in the form of a low molecular weight compound.

[0235] Examples of the compound (C) 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.

[0236] "M ＋ X － In the compound represented by the formula ", M ＋ represents a cation, and preferably represents an organic cation. ＋ Specific examples and preferred ranges of M in the compound (B) are as follows: １ ＋ and M ２ ＋ The specific examples and preferred ranges are the same as those of the above.

[0237] "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.

[0238] 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.

[0239] 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).

[0240] 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.

[0241] 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).

[0242] 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.

[0243] An example of the sulfonylimide anion is a saccharin anion.

[0244] 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.

[0245] 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.

[0246] The non-nucleophilic anion is also preferably an anion represented by the following formula (AN1).

[0247]

[0248] 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.

[0249] 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.

[0250] 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.

[0251] 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)

[0252] 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.

[0253] 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).

[0254] 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.

[0255] 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.

[0256] The non-nucleophilic anion is also preferably an anion represented by the following formula (AN2).

[0257]

[0258] 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.

[0259] 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.

[0260] 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.

[0261] L represents a divalent linking group. The definition of L is the same as that of L in formula (AN1). When a plurality of L's are present, they may be the same or different.

[0262] 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.

[0263] 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.

[0264] 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.

[0265] 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.

[0266] The non-nucleophilic anion is also preferably an aromatic sulfonate anion represented by the following formula (AN3).

[0267]

[0268] 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.

[0269] 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.

[0270] 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).

[0271] 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.

[0272] It is also preferable that the compound (C) is at least one selected from the group consisting of the compounds (I) to (II).

[0273] (Compound (I)) Compound (I) has one or more of the following structural moieties X Ｃ and one or more of the following structural moieties Y Ｃand a compound having the following structural moiety X Ｃ and the following structural moiety Y Ｃ and a second acidic moiety derived from the structural moiety X: Ｃ : Anion site A １Ｃ － and the cationic moiety M １Ｃ ＋ and by irradiation with actinic rays or radiation, HA １Ｃ A structural moiety forming a first acidic site represented by the following structural moiety: Ｃ : Anion site A ２Ｃ － and the cationic moiety M ２Ｃ ＋ and by irradiation with actinic rays or radiation, HA ２Ｃ The compound (I) satisfies the following condition I: Ｃ However, compound (I) is a compound other than compound (B).

[0274] Condition I Ｃ In the compound (I), the structural moiety X Ｃ The cationic moiety M １Ｃ ＋ and the above structural site Y Ｃ The cationic moiety M ２Ｃ ＋ H ＋ Compound PI Ｃ The structural portion X Ｃ The cationic moiety M １Ｃ ＋ H ＋ HA is replaced by １Ｃ Acid dissociation constant a1 derived from the acidic site represented by Ｃ and the structural portion Y Ｃ The cationic moiety M ２Ｃ ＋ H ＋ HA is replaced by ２Ｃ Acid dissociation constant a2 derived from the acidic site represented by Ｃ and the acid dissociation constant a1 Ｃ than the above acid dissociation constant a2Ｃ is larger.

[0275] In the following, Condition I Ｃ The following will be explained in more detail. Ｃ and one of the first acidic moieties derived from the structural moiety Y Ｃ In the case where the compound is an acid-generating compound having one second acidic site derived from Ｃ "HA １Ｃ and H.A. ２Ｃ Compound PI corresponds to the compound having the formula: Ｃ Acid dissociation constant a1 Ｃ and acid dissociation constant a2 Ｃ More specifically, compound PI Ｃ When the acid dissociation constant of compound PI is calculated, Ｃ "A １Ｃ － and H.A. ２Ｃ The pKa of the compound having the acid dissociation constant a1 Ｃ and the above "A １Ｃ － and H.A. ２Ｃ "A compound having １Ｃ － and A ２Ｃ － The pKa of the compound having the acid dissociation constant a2 Ｃ is.

[0276] Compound (I) is, for example, Ｃ and two of the first acidic moieties derived from the structural moiety Y Ｃ In the case where the compound is an acid-generating compound having one of the second acidic sites derived from Ｃ "Two HA １Ｃ and one HA ２Ｃ Compound PI corresponds to the compound having the formula: Ｃ When the acid dissociation constant of compound PI is calculated, Ｃ "One A １Ｃ － and one HA １Ｃ and one HA ２Ｃ and the acid dissociation constant when "a compound having one A １Ｃ－ and one HA １Ｃ and one HA ２Ｃ "Compound having two A １Ｃ － and one HA ２Ｃ The acid dissociation constant when the compound is a compound having the above-mentioned acid dissociation constant a1 Ｃ It corresponds to "Two A １Ｃ － and one HA ２Ｃ "Compound having two A １Ｃ － and A ２Ｃ － The acid dissociation constant when the compound is a compound having the acid dissociation constant a2 Ｃ That is, compound PI Ｃ In the above, the structural portion X Ｃ The cationic moiety M １Ｃ ＋ H ＋ HA is replaced by １Ｃ When the compound has a plurality of acid dissociation constants derived from the acidic moiety represented by Ｃ The acid dissociation constant a2 is greater than the largest value of Ｃ The value of compound PI is larger. Ｃ "One A １Ｃ － and one HA １Ｃ and one HA ２Ｃ The acid dissociation constant when the compound is aa Ｃ and "One A １Ｃ － and one HA １Ｃ and one HA ２Ｃ "Compound having two A １Ｃ － and one HA ２Ｃ The acid dissociation constant when the compound having Ｃ When this is done, aa Ｃ and ab Ｃ The relationship between Ｃ <ab Ｃ Meet the following.

[0277] Acid dissociation constant a1 Ｃ and acid dissociation constant a2 Ｃis determined by the above-mentioned method for measuring the acid dissociation constant. Ｃ The term "compound (I)" refers to an acid generated when compound (I) is irradiated with actinic rays or radiation. Ｃ When the structural moiety X Ｃ may be the same or different. １Ｃ － and two or more of the above M １Ｃ ＋ In compound (I), the above A １Ｃ － and the above A ２Ｃ － , and the above M １Ｃ ＋ and the above M ２Ｃ ＋ may be the same or different, but １Ｃ － and the above A ２Ｃ － are preferably different from each other.

[0278] The above compound PI Ｃ In this case, the acid dissociation constant a Ｃ (acid dissociation constant a1 Ｃ If there are multiple, the maximum value) and the acid dissociation constant a2 Ｃ The difference (absolute value) between the acid dissociation constant 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. Ｃ (acid dissociation constant a1 Ｃ If there are multiple, the maximum value) and the acid dissociation constant a2 Ｃ The upper limit of the difference (absolute value) between is not particularly limited, but is, for example, 16 or less.

[0279] The above compound PI Ｃ In this case, the acid dissociation constant a2 Ｃ is preferably 20 or less, more preferably 15 or less. Ｃ The lower limit of is preferably −4.0 or more.

[0280] The above compound PI Ｃ In this case, the acid dissociation constant aＣ is preferably 2.0 or less, more preferably 0 or less. Ｃ The lower limit of is preferably −20.0 or more.

[0281] Anion site A １Ｃ － and anionic moiety A ２Ｃ － 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. １Ｃ － 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. ２Ｃ － As the anion moiety A １Ｃ － 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. Ａ The monovalent organic group represented by the formula (I) is not particularly limited, but examples thereof include a cyano group, a trifluoromethyl group, and a methanesulfonyl group.

[0282]

[0283]

[0284] Cationic moiety M １Ｃ ＋ and cationic moiety M ２Ｃ ＋ is a structural moiety containing a positively charged atom or atomic group, and examples thereof include monovalent organic cations. Examples of organic cations include M in the above-mentioned compound (B). １＋ and M ２ ＋ Examples of the organic cation include those represented by the following formula:

[0285] (Compound (II)) Compound (II) is a compound having two or more of the above structural moieties X Ｃ and one or more of the following structural moieties Z Ｃ and a compound having the structural moiety X Ｃ and two or more of the first acidic moieties derived from the structural moiety Z Ｃ The structural moiety Z is an acid-generating compound containing Ｃ : Non-ionic site capable of neutralizing acid

[0286] In compound (II), structural site X Ｃ The definition of A １Ｃ － and M １Ｃ ＋ The definition of is the structural moiety X in the compound (I) described above. Ｃ The definition of A １Ｃ － and M １Ｃ ＋ The definition and preferred embodiments are also the same.

[0287] In the compound (II), the structural moiety X Ｃ The cationic moiety M １Ｃ ＋ H ＋ Compound PII Ｃ In the above, the structural portion X Ｃ The cationic moiety M １Ｃ ＋ H ＋ HA is replaced by １Ｃ Acid dissociation constant a1 derived from the acidic site represented by Ｃ The preferred range of Ｃ Acid dissociation constant a1 Ｃ It should be noted that when compound (II) is, for example, a compound having the structural moiety X Ｃ and the structural moiety Z, Ｃ "Two HA １ＣThis compound PII corresponds to the compound having the formula: Ｃ When the acid dissociation constant of compound PII was calculated, Ｃ "One A １Ｃ － and one HA １Ｃ and the acid dissociation constant when "a compound having one A １Ｃ － and one HA １Ｃ "Compound having two A １Ｃ － The acid dissociation constant when the compound is a compound having the acid dissociation constant a1 Ｃ This applies to:

[0288] Acid dissociation constant a1 Ｃ is determined by the above-mentioned method for measuring the acid dissociation constant. Ｃ The term "X" refers to an acid generated when compound (II) is irradiated with actinic rays or radiation. Ｃ may be the same or different. １Ｃ － and two or more of the above M １Ｃ ＋ may be the same or different.

[0289] Structural part Z Ｃ The nonionic moiety capable of neutralizing an acid in the carboxylic acid is not particularly limited, and is preferably, for example, a moiety containing a group capable of electrostatically interacting with a proton or a functional group having an electron. Examples of the group capable of electrostatically interacting with a proton or the functional group having an electron include a functional group having a macrocyclic structure such as a cyclic polyether, or a functional group 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:

[0290]

[0291] 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.

[0292] Examples of moieties other than cations that Compound (I) and Compound (II) may have are shown below.

[0293]

[0294]

[0295] When the composition of the present invention contains compound (C), the content of compound (C) 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 (C), the content of compound (C) 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 (C) may be used alone or in combination of two or more.

[0296] [Acid Diffusion Controller] The composition of the present invention may contain an acid diffusion controller. The acid diffusion controller traps acid generated from a photoacid generator or the like upon exposure and acts 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 is not particularly limited, and examples include basic compounds (DA), low-molecular-weight compounds (DB) having a nitrogen atom and a group that is cleaved by the action of an acid, and compounds (DC) whose acid diffusion control ability is reduced or eliminated upon irradiation with actinic rays or radiation. Examples of compounds (DC) include onium salt compounds (DD) that are weakly acidic relative to the photoacid generator, and basic compounds (DE) whose basicity is reduced or eliminated upon irradiation with actinic rays or radiation. Specific examples of the basic compound (DA) include those described in paragraphs

[0132] to

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

[0137] to

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

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

[0156] to

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

[0305] to

[0314] of WO 2020 / 158337.

[0297] 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.

[0298] Among the acid diffusion controllers, the compound (DC) is also referred to as a photodegradable quencher. The compound (DC) is a compound different from the compound (B). Acid diffusion controllers other than the compound (DC) are also referred to as non-photodegradable quenchers. The acid diffusion controller may be a photodegradable quencher or a non-photodegradable quencher. Furthermore, a photodegradable quencher and a non-photodegradable quencher may be used in combination as the acid diffusion controller.

[0299] When the composition of the present invention contains an acid diffusion controller, the content of the acid diffusion controller (the total content if multiple types are present) is preferably 0.1 to 30.0 mass%, more preferably 0.1 to 15.0 mass%, and even more preferably 1.0 to 15.0 mass%, based on the total solids content of the composition of the present invention. In the composition of the present invention, the acid diffusion controller may be used alone or in combination of two or more types.

[0300] [Hydrophobic Resin] The composition of the present invention may further contain a hydrophobic resin (also referred to as "hydrophobic resin (I)") different from resin (A). The hydrophobic resin is preferably designed so as to be unevenly distributed on the surface of the actinic ray- or radiation-sensitive film (preferably a resist film) formed from the composition of the present invention. However, unlike surfactants, the hydrophobic resin does not necessarily have to have a hydrophilic group in its molecule, and does not necessarily have to contribute to uniform mixing of polar and non-polar substances. Effects of adding a hydrophobic resin include control of the static and dynamic contact angles of water on the resist film surface and suppression of outgassing.

[0301] The hydrophobic resin contains fluorine atoms, silicon atoms, and CH atoms contained in the side chain portion of the resin in order to be unevenly distributed on the surface layer of the film. ３ It is preferable to have one or more of the partial structures, and more preferably two or more. The hydrophobic resin preferably has a hydrocarbon group having 5 or more carbon atoms. These groups may be present in the main chain of the resin or may be substituted on a side chain. Examples of hydrophobic resins include the compounds described in paragraphs

[0275] to

[0279] of WO 2020 / 004306.

[0302] The hydrophobic resin may be used alone or in combination of two or more. When the composition of the present invention contains a hydrophobic resin, the content of the hydrophobic resin is preferably 0.01 to 20.0 mass %, more preferably 0.1 to 15.0 mass %, based on the total solid content of the composition of the present invention.

[0303] [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 silicone-based surfactant. Examples of the fluorine-based and / or silicone-based surfactant include the surfactants disclosed in paragraphs

[0218] and

[0219] of WO 2018 / 193954. One surfactant may be used alone, or two or more surfactants may be used. When the composition of the present invention contains a surfactant, the content of the surfactant is preferably 0.0001 to 2.0% by mass, more preferably 0.0005 to 1.0% by mass, and even more preferably 0.1 to 1.0% by mass, based on the total solids content of the composition of the present invention.

[0304] [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).

[0305] Details of the component (M1) and the component (M2) are described in paragraphs

[0218] to

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

[0306] 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.

[0307] 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, and more preferably 1 to 20% by mass. This further improves the coatability of the composition of the present invention. The term "solids" refers to all components other than the solvent, and as described above, refers to components that form an actinic ray-sensitive or radiation-sensitive film. The solids concentration is the mass percentage of the mass of components other than the solvent relative to the total mass of the composition of the present invention. "Total solids" refers to the total mass of components excluding the solvent from the entire composition of the present invention. As described above, the "solids" refers to components excluding the solvent, and may be solid or liquid at 25°C, for example.

[0308] [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).

[0309] 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.

[0310] 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 deterioration of 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.

[0311] [Actinic ray- or radiation-sensitive film, pattern forming method] The present invention also relates to an actinic ray- or radiation-sensitive film formed from the composition of the present invention. The actinic ray- or radiation-sensitive film of the present invention is preferably a resist film. The procedure of the pattern forming method using the composition of the present invention is not particularly limited, but preferably includes the following steps: Step 1: forming an actinic ray- or radiation-sensitive film on a substrate from an 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.

[0312] (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.

[0313] 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.

[0314] 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.

[0315] 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.

[0316] 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.

[0317] 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.

[0318] (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.

[0319] 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.

[0320] (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).

[0321] 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.

[0322] 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.

[0323] 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.

[0324] 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.

[0325] (Other Steps) The pattern formation method preferably includes, after step 3, a step of cleaning with a rinse liquid.

[0326] 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.

[0327] 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.

[0328] 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).

[0329] 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.

[0330] 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.

[0331] 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.

[0332] 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).

[0333] 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.

[0334] 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.

[0335] [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).

[0336] 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.

[0337] The various components used in the resist compositions of the examples and comparative examples are shown below.

[0338] [Resin (A)] Resins A (Resins A-1 to A-50) shown in Table 3 are shown below. Resins A were synthesized according to the synthesis method of Resin A-1 (Synthesis Example 1) described below or the synthesis method of Resin A-39 (Synthesis Example 2) described below. Table 1 shows the molar ratio, weight average molecular weight (Mw), and dispersity (Mw / Mn) of each repeating unit. In Table 1, the molar ratio of each repeating unit indicates the content (mol %) of each repeating unit relative to all repeating units. Each repeating unit is shown by the structure of the monomer corresponding to that repeating unit. The weight average molecular weight (Mw) and dispersity (Mw / Mn) of Resins A-1 to A-50 were measured by GPC (carrier: tetrahydrofuran (THF)) (amounts calculated as polystyrene). The composition ratios (weight % ratios) of the resins are as follows: １３ Measurement was performed by C-NMR (nuclear magnetic resonance).

[0339]

[0340]

[0341]

[0342] The structures of the monomers MA-1 to MA-25 and MB-1 to MB-35 corresponding to the repeating units shown in Table 1 are shown below.

[0343]

[0344]

[0345]

[0346]

[0347]

[0348] 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 the repeating units measured by C-NMR (nuclear magnetic resonance) was MB-10 / MA-16=50 / 50.

[0349] Synthesis Example 2: Synthesis of Resin A-39 Propylene glycol monomethyl ether acetate (22 g) was heated to 85°C under a nitrogen stream. While stirring this solution, a mixed solution of a monomer represented by MB-3 (6 g), a monomer represented by MB-20a (35 g), a monomer represented by MA-2 (27 g), propylene glycol monomethyl ether acetate (84 g), dimethyl 2,2'-azobisisobutyrate (V-601, manufactured by FUJIFILM Wako Pure Chemical Industries, Ltd.) (1.2 g), and methyl 4-cyano-4-[(dodecylsulfanylthiocarbonyl)sulfanyl]pentanoate (manufactured by FUJIFILM Wako Pure Chemical Industries, Ltd.) (4.4 g) was added dropwise over 6 hours. After completion of the dropwise addition, the reaction solution was stirred at 85°C for an additional 2 hours to obtain a polymerized solution. Methanol (100 g) and triethylamine (16 g) were added to the resulting polymerized solution, and the mixture was stirred at 50°C for 5 hours. After stirring was completed, the solution was allowed to cool to room temperature, and then ethyl acetate (650 g) and a 0.2 mol / L aqueous hydrochloric acid solution (400 mL) were added and stirred for 30 minutes to extract the organic layer. The extracted organic layer was washed five times with distilled water (400 mL). The washed organic layer was reprecipitated in a mixed solution of heptane / ethyl acetate = 9 / 1 (mass ratio) and then filtered. The obtained solid was dried in vacuum to obtain 38 g of resin A-39. The weight average molecular weight (Mw: polystyrene equivalent) of resin A-39 determined by GPC (carrier: tetrahydrofuran (THF)) was 10,000, and the dispersity (Mw / Mn) was 1.35. １３ The molar ratio of the repeating units measured by C-NMR (nuclear magnetic resonance) was MB-3 / MB-20 / MA-2=10 / 30 / 60.

[0350]

[0351] Resins A-2 to A-38 and resins A-40 to A-50 were synthesized in accordance with the synthesis method for resin A-1 (Synthesis Example 1).

[0352] [Photoacid Generator (B)] Compounds B-1 to B-40 were used as the photoacid generator (B). In the comparative example, a photoacid generator Ba-1, which is not a photoacid generator (B), was used. For convenience, Ba-1 is also listed in the column for photoacid generator (B) in Table 3 below. The numerical values ​​listed in the following structures are those obtained when the cation moiety is H. ＋ The acid dissociation constant (pKa) derived from each acidic site of the compound replaced with is calculated using the following software package 1. Software package 1: Advanced Chemistry Development (ACD / Labs) Software V8.14 for Solaris (1994-2007 ACD / Labs)

[0353]

[0354]

[0355]

[0356]

[0357]

[0358]

[0359]

[0360] A synthesis example of the photoacid generator (B) is shown below.

[0361] Synthesis Example 2: Synthesis of Compound B-1 Synthesis of Compound B-1-b B-1-a (225 g) was dissolved in acetone (475 g) and stirred at 0°C under a nitrogen stream, to which trifluoroacetic acid (275 g) and trifluoroacetic anhydride (460 g) were successively added dropwise. After the addition was completed, the mixture was stirred at 25°C for 20 hours. The reaction solution was added dropwise to 10% aqueous sodium bicarbonate solution (8585 g) and ethyl acetate (2000 g) stirred at 0°C, and then the aqueous layer was removed. The organic layer was washed with a saturated aqueous sodium chloride solution and then concentrated. Ethyl acetate (158 g) and n-hexane (293 g) were added to the resulting residue and stirred, and the resulting solid was collected by filtration. Ethyl acetate (200 g) was added to the solid and stirred for 1 hour, and the resulting white powder was collected by filtration and dried to obtain B-1-b (121 g).

[0362]

[0363] (Synthesis of Compound B-1-d) Cesium carbonate (106 g) and tetrahydrofuran (300 g) were stirred under a nitrogen stream at −15° C., to which B-1-c (74 g) was added dropwise, followed by the dropwise addition of a mixture of B-1-b (30 g) and tetrahydrofuran (300 g). After stirring for 8 hours, the reaction solution was added dropwise to a 1 mol / L aqueous hydrochloric acid solution (470 g), and n-hexane (200 ml) and ethyl acetate (200 ml) were added. The aqueous layer was removed, and the organic layer was washed with distilled water. The organic layer was concentrated and then subjected to column purification (hexane / ethyl acetate) to obtain B-1-d (70 g).

[0364]

[0365] (Synthesis of Compound B-1-e) B-1-d (36 g), trifluoroacetic acid (180 g), and distilled water (18 g) were stirred at 55° C. for 6 hours, and then distilled water (360 g) was added at 20° C. and stirred for 1 hour. The resulting solid was collected by filtration, washed with distilled water, and dried to obtain B-1-e (33 g).

[0366]

[0367] (Synthesis of Compound B-1-f) A mixed solution of sodium bicarbonate (23 g) and distilled water (170 g) was added dropwise to B-1-e (37 g) and tetrahydrofuran (130 g) while stirring at 40°C, and the mixture was stirred for 3 hours. After tetrahydrofuran was distilled off, the aqueous layer was washed twice with ethyl acetate (150 g). After 1 mol / L aqueous hydrochloric acid solution (142 g) was added dropwise to the obtained aqueous solution at 0°C, the aqueous layer was washed twice with ethyl acetate (150 g). A 7% aqueous sodium bicarbonate solution (256 g) was added dropwise to the obtained aqueous solution at room temperature, and the mixture was stirred to obtain an aqueous sodium bicarbonate solution of B-1-f (36 g).

[0368]

[0369] (Synthesis of Compound B-1) Methylene chloride (360 g) and B-1-g (66 g) were added to the aqueous sodium bicarbonate solution of B-1-f (36 g) obtained above, and the mixture was stirred at 25°C for 1 hour. Ethyl acetate (100 g) was added to the obtained reaction solution, and the mixture was allowed to stand. The aqueous layer was then removed, and the organic layer was washed with distilled water. The obtained organic layer was concentrated, and diisopropyl ether (500 g) was added and the mixture was stirred for 1 hour. The obtained white solid was filtered and dried to obtain B-1 (62 g).

[0370]

[0371] The resulting B-1 was identified by NMR (Nuclear Magnetic Resonance). １ H NMR (400MHz, (CD ３ ) ２ CO) 6.45-6.57 (m, 2H) 7.79 (d, 1H), 8.15-8.45 (m, 24H)

[0372] Other compounds (B) used in the examples were also synthesized in the same manner as above.

[0373] [Photoacid Generator (C)] The structures of the photoacid generators (C) (compounds C-1 to C-47) shown in Table 3 are shown below. The photoacid generators (C) are compounds different from the photoacid generators (B).

[0374]

[0375]

[0376]

[0377]

[0378]

[0379]

[0380]

[0381]

[0382] [Photodegradable Quencher (D)] The structures of the photodegradable quenchers (D) (compounds D-1 to D-28) shown in Table 3 are shown below.

[0383]

[0384]

[0385]

[0386]

[0387] [Non-photodegradable quencher (G)] The structures of the non-photodegradable quenchers (G) (compounds G-1 to G-5) shown in Table 3 are shown below.

[0388]

[0389] [Hydrophobic Resin (I)] Hydrophobic resins I (resins I-1 to I-8) shown in Table 3 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 2 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).

[0390]

[0391] The structural formulas of resins I-1 to I-8 shown in Table 2 are shown below.

[0392]

[0393] [Surfactants] The surfactants shown in Table 3 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)

[0394] [Solvents] The solvents shown in Table 3 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

[0395] [Preparation of Resist Compositions] The components shown in Table 3 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-90, CRe-1 to CRe-2). Note that the solids refer to all components other than the solvent. The resulting resist compositions were used in the examples and comparative examples. Additionally, the "amount" column in the tables indicates the content (% by mass) of each component relative to the total solids in the resist composition.

[0396]

[0397]

[0398]

[0399]

[0400]

[0401]

[0402] [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 Table 4 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 n-butyl acetate for 30 seconds, and then spin-dried to obtain a negative pattern.

[0403] [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.

[0404] "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.

[0405] <Roughness Performance> Roughness performance was evaluated by line width roughness (LWR) performance. 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 calculated. 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.

[0406] The evaluation results are shown in the table below.

[0407]

[0408]

[0409]

[0410]

[0411]

[0412] As shown in Table 4 above, the resist compositions of the present invention were confirmed to have 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 performances.

[0413] [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 5 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 obtained positive-tone pattern was used to evaluate the LWR performance and defect suppression properties in the same manner as described above.

[0414] The evaluation results are shown in the table below.

[0415]

[0416]

[0417]

[0418]

[0419]

[0420] As shown in Table 5 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 performances.

[0421] [Pattern Formation by EB Exposure and Evaluation: Examples 3-1 to 3-90] When a resist film was formed using each of the resist compositions of the examples and then exposed to an electron beam to form a pattern, similar results to those obtained when patterning was performed by EUV exposure were obtained.

[0422] According to the present invention, it is possible to provide an actinic ray-sensitive or radiation-sensitive resin composition that can suppress the occurrence of defects and has excellent roughness performance in the formation of an ultrafine pattern (for example, a line-and-space pattern with a line width of 25 nm or less, or a hole pattern with a hole diameter of 25 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 that uses the actinic ray-sensitive or radiation-sensitive resin composition, and a method for manufacturing an electronic device.

[0423] 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 Japanese patent applications filed on September 6, 2023 (Patent Application No. 2023-144804), November 8, 2023 (Patent Application No. 2023-190956), December 22, 2023 (Patent Application No. 2023-217276), and April 26, 2024 (Patent Application No. 2024-072090), the contents of which are incorporated herein by reference.

Claims

1. An actinic ray-sensitive or radiation-sensitive resin composition comprising: an acid-decomposable resin (A); and the following compound (B) which generates an acid upon irradiation with actinic rays or radiation. Compound (B): A compound having the following structural moiety X and the following structural moiety Y, which generates an acid containing the following first acidic moiety derived from the following structural moiety X and the following second acidic moiety derived from the following structural moiety Y upon irradiation with actinic rays or radiation. Structural moiety X: Anionic moiety A １ － and the cationic moiety M １ ＋ and HA is produced by irradiation with actinic rays or radiation. １ Structural moiety Y: an anionic moiety A forming a first acidic moiety represented by the formula: ２ － and the cationic moiety M ２ ＋ and HA is produced by irradiation with actinic rays or radiation. ２ The compound (B) satisfies the following conditions I and II. Condition I: In the compound (B), the cationic moiety M in the structural moiety X is １ ＋ and the cationic moiety M in the structural moiety Y. ２ ＋ H ＋ The compound PI in which the cationic moiety M in the structural moiety X is 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 the acid dissociation constant a2 (pKa) derived from the acidic site represented by the formula (1) is greater than the acid dissociation constant a1. ２ － is an anion moiety containing a partial structure represented by the following formula (1). In formula (1), * represents the bonding position to other atoms.

2. The actinic ray-sensitive or radiation-sensitive resin composition according to claim 1, wherein the acid dissociation constant a1 (pKa) is -1.00 or less.

3. The anion moiety A in the structural moiety X in the compound (B) １ － is an anion moiety containing a partial structure represented by any one of the following formulas (2) to (5): In formula (2), X ２ represents a hydrogen atom, a halogen atom or an organic group. * represents the bonding position to other atoms. In formula (3), X ３ represents an electron-withdrawing group. n represents an integer of 1 to 4. When n is an integer of 2 or more, a plurality of X ３ may be the same or different. * indicates the bonding position to other atoms. In formula (4), * represents the bonding position to other atoms. In formula (5), * represents the bonding position to other atoms.

4. The actinic ray-sensitive or radiation-sensitive resin composition according to claim 1 or 2, wherein the compound (B) has a halogen atom at the cation site.

5. The actinic ray-sensitive or radiation-sensitive resin composition according to claim 1 or 2, wherein the acid-decomposable resin (A) contains a repeating unit having a phenolic hydroxyl group.

6. An actinic ray-sensitive or radiation-sensitive film formed from the actinic ray-sensitive or radiation-sensitive resin composition according to claim 1 or 2.

7. 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 claim 1 or 2; exposing the actinic ray-sensitive or radiation-sensitive film; and developing the exposed actinic ray-sensitive or radiation-sensitive film with a developer to form a pattern.

8. A method for manufacturing an electronic device, comprising the pattern formation method according to claim 7.

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