TW202302669A - Active-ray-sensitive or radiation-sensitive resin composition, resist film, pattern formation method, method for manufacturing electronic device - Google Patents

Abstract

The present invention addresses the problem of providing an active light-sensitive or radiation-sensitive resin composition which exhibits excellent development defect suppressing performance. The present invention also addresses the problem of providing a resist film, a pattern forming method, and a method for producing an electronic device, each being related to the active light-sensitive or radiation-sensitive resin composition. An active light-sensitive or radiation-sensitive resin composition according to the present invention contains a resin that has a repeating unit A represented by formula (A), while additionally containing a compound that is represented by any one of formulae (1) to (4), wherein: the resin additionally comprises a group, the polarity of which is increased when decomposed by the action of an acid; and/or the resin additionally comprises a repeating unit a which has a residue formed by removing one or two hydrogen atoms from a compound that is represented by any one of formulae (1) to (4), with the content of the repeating unit a being 10% by mole or more relative to all repeating units in the resin.

Description

Actinic radiation-sensitive or radiation-sensitive resin composition, resist film, pattern forming method, and manufacturing method of electronic components

The present invention relates to an actinic radiation-sensitive or radiation-sensitive resin composition, a resist film, a method for forming a pattern, and a method for manufacturing electronic components.

As a pattern forming method, the following method is mentioned, for example. Expose the actinic ray-sensitive or radiation-sensitive resin film (hereinafter also referred to as "resist film") formed by using the actinic ray-sensitive or radiation-sensitive resin composition, and apply the resist in the area reflecting the exposure pattern. The solubility of the etchant film with respect to the developing solution changes. Then, development is performed using a developing solution (for example, an alkaline water-soluble developing solution or an organic solvent developing solution, etc.) to remove exposed or non-exposed portions in the resist film to obtain a desired pattern.

For example, Patent Document 1 discloses: a photoresist polymer comprising a repeating unit represented by the following chemical formula; a photoacid generator generating an acid; and a photoresist composition having an organic solvent, With respect to 100 parts by weight of the photoresist polymer, the content of the photoacid generator is 0.1 to 20 parts by weight, and the content of the organic solvent is 300 to 5000 parts by weight (claims 3 and 6) .

[先前技術文獻]  [專利文獻] [chemical formula 1]

[Prior Art Document] [Patent Document]

Patent Document 1: Japanese Patent Laid-Open No. 2008-111120

[Problems to be Solved by the Invention] The inventors of the present invention have found, as a result of research based on the photoresist composition (actinic radiation-sensitive or radiation-sensitive resin composition) described in Patent Document 1, that in particular When high-definition patterns are desired, photoresist composition is used for exposure treatment. After development treatment, there are many development defects in the pattern obtained, and there is room for further improvement. Hereinafter, when a pattern with few development defects is obtained at the time of image development, it is said that it is excellent in development defect suppression property.

Therefore, an object of the present invention is to provide an actinic radiation-sensitive or radiation-sensitive resin composition excellent in development defect suppression. In addition, the object of the present invention is to provide a resist film, a pattern forming method, and a method of manufacturing electronic components related to the above-mentioned actinic radiation-sensitive or radiation-sensitive resin composition. [Means to solve the problem]

The inventors of the present invention found that the aforementioned problems can be solved by the following configuration.

[1] An actinic radiation-sensitive or radiation-sensitive resin composition comprising a resin having a repeating unit A represented by the following chemical formula (A), wherein the actinic radiation-sensitive or radiation-sensitive resin composition satisfies the following conditions At least one of: further comprising a compound represented by any one of the chemical formulas (1) to (4), the aforementioned resin further has a group whose polarity is increased by decomposition by the action of an acid; and the aforementioned resin further has a repeating unit a , the aforementioned repeating unit a has a residue formed by removing one or two hydrogen atoms from the compound represented by any one of the aforementioned chemical formulas (1) to (4), and the content of the aforementioned repeating unit a is relative to the content of the aforementioned resin The total repeating unit is 10 mol% or more. [2] The actinic radiation-sensitive or radiation-sensitive resin composition as described in [1], the above-mentioned resin further has a repeating unit a, and the above-mentioned repeating unit a has any one of the above chemical formulas (1) to (4) The residue formed by removing one or two hydrogen atoms in the represented compound, the aforementioned residue includes at least one selected from the group consisting of groups represented by any one of the following chemical formulas (1a) to (4a) . [3] The actinic radiation-sensitive or radiation-sensitive resin composition as described in any one of [1] or [2], wherein the compound represented by any one of the aforementioned chemical formulas (1) to (4) has Substituents with σp exceeding 0.5 in Hammet's rule. [4] The actinic radiation-sensitive or radiation-sensitive resin composition as described in [1], which satisfies at least one of the following conditions: it further includes a compound represented by any one of the aforementioned chemical formulas (1) to (3) , the aforementioned resin further has a group whose polarity is increased by decomposing by the action of an acid; and, the aforementioned resin further has a repeating unit a, and the aforementioned repeating unit a has the In the residue formed by removing one or two hydrogen atoms in the compound, the content of the aforementioned repeating unit a is 10 mol% or more relative to all the repeating units of the aforementioned resin. [5] The actinic radiation-sensitive or radiation-sensitive resin composition as described in any one of [1] to [4], the aforementioned resin further has the aforementioned repeating unit a, and the aforementioned repeating unit a is greater than all the repeating units of the aforementioned resin The content of unit a is 40 mol % or more. [6] The actinic radiation-sensitive or radiation-sensitive resin composition as described in any one of [1] to [5], the aforementioned resin further includes a repeating unit b, and the aforementioned repeating unit b has the ability to be decomposed by the action of the aforementioned acid And the group with increased polarity. [7] The actinic radiation-sensitive or radiation-sensitive resin composition as described in any one of [1] to [6], the aforementioned resin further includes a repeating unit b, and the aforementioned repeating unit b has the ability to be decomposed by the action of the aforementioned acid As for the group with increased polarity, the repeating unit b includes at least one member selected from the group consisting of repeating units represented by any one of the following chemical formulas (M1) to (M5). [8] The actinic radiation-sensitive or radiation-sensitive resin composition as described in [7], wherein the repeating unit b is selected from the repeating unit represented by the aforementioned chemical formula (M4) and the repeating unit represented by the aforementioned chemical formula (M5) At least one of the group of units. [9] A resist film formed using the actinic radiation-sensitive or radiation-sensitive resin composition as described in any one of [1] to [8]. [10] A method for forming a pattern, comprising: using the composition of the actinic radiation-sensitive or radiation-sensitive resin described in any one of [1] to [8] to form a resist film on a substrate; a process of exposing the aforementioned resist film; and a process of developing the exposed resist film using a developing solution. 〔11〕 A method of manufacturing an electronic component, which includes the pattern forming method as described in [10]. [Invention effect]

According to the present invention, it is possible to provide an actinic radiation-sensitive or radiation-sensitive resin composition having excellent development defect suppression properties. In addition, according to the present invention, it is also possible to provide a resist film, a method for forming a pattern, and a method for manufacturing electronic components related to the above-mentioned actinic radiation-sensitive or radiation-sensitive resin composition.

Hereinafter, the present invention will be described in detail. The description of the constituent elements of the present invention described below may be based on representative embodiments of the present invention, but the present invention is not limited to these embodiments.

The meanings of the following symbols in this specification are shown here. "～" is used to mean that the numerical values described before and after it are used as the lower limit and upper limit. In the notation of the group (atomic group) in this specification, as long as it does not contradict the gist of the present invention, the notation of substitution and unsubstituted notation includes both groups without substituents and groups with substituents. For example, "alkyl" includes not only an alkyl group without a substituent (unsubstituted alkyl group), but also an alkyl group with a substituent (substituted alkyl group). "Organic radical" means a radical comprising at least one carbon atom. Unless otherwise stated, "substituent" refers to a monovalent substituent. Examples of substituents include halogen atoms such as fluorine, chlorine, bromine and iodine; alkoxy groups such as methoxy, ethoxy and tertiary butoxy; aryl groups such as phenoxy and p-tolyloxy; Oxygen; Alkoxycarbonyl such as methoxycarbonyl, butoxycarbonyl and phenoxycarbonyl; Acyloxy such as acetyloxy, propionyloxy and benzoyloxy; Acetyl, benzoyl, isobutyryl , acryl, methacryl and methyl oxalyl and other acyl groups; methylsulfonyl and tert-butylsulfonyl and other alkylsulfonyl groups; phenylsulfonyl and p-toluenesulfonyl, etc. Arylsulfonyl; Alkyl; Cycloalkyl; Aryl; Heteroaryl; Hydroxy; Carboxyl; Formyl; Sulfo; Cyano; Alkylaminocarbonyl; Arylaminocarbonyl; ; silicon group; amino group; monoalkylamino group; dialkylamino group; arylamine group; and combinations thereof. In this specification, these groups of substituents are also referred to as "substituent K". The so-called "actinic rays" or "radiation rays" refer to far ultraviolet rays, extreme ultraviolet rays (EUV light: Extreme Ultraviolet), X-rays and electron beams (EB: Electron beams) represented by the bright line spectrum of mercury lamps and excimer lasers. Beam) and so on. "Light" means actinic rays or radiation. The so-called "exposure", unless otherwise specified, includes not only the exposure using the bright line spectrum of the mercury lamp, the excimer laser as the representative of the far ultraviolet light, extreme ultraviolet light, X-ray and EUV light, but also the use of electron beam and Particle beams such as ion beams are depicted. The bonding direction of the divalent groups described in this specification is not particularly limited unless otherwise specified. For example, in a compound represented by the formula "X-Y-Z", when Y is -COO-, Y may be -CO-O- or -O-CO-. In addition, the aforementioned compound may be "X-CO-O-Z" or "X-O-CO-Z".

(Meth)acrylate means acrylate and methacrylate. (Meth)acrylic acid means acrylic acid and methacrylic acid.

The weight-average molecular weight (Mw), number-average molecular weight (Mn), and degree of dispersion (also referred to as "molecular weight distribution") (Mw/Mn) of the resin were measured using a GPC (Gel Permeation Chromatography) device (HLC manufactured by Tosoh Co., Ltd. -8120GPC) GPC measurement (solvent: tetrahydrofuran, flow rate (sample injection volume): 10 μL, column: TSK gel Multipore HXL-M manufactured by Tosoh, column temperature: 40° C., flow rate: 1.0 mL/min, Detector: defined by the polystyrene conversion value obtained from a differential refractive index detector (Refractive Index Detector).

The resin composition ratio (molar ratio or mass ratio) was measured by ¹³ C-NMR (nuclear magnetic resonance).

The so-called acid dissociation constant (pKa) refers to the pKa in aqueous solution. Specifically, it is obtained by calculating the value based on Hammett's substituent constant and a database of known literature values using the following software package 1. value. The pKa values described in this specification all represent values obtained by calculation using this software package. Package 1: Advanced Chemistry Development (ACD/Labs) Software V8.14 for Solaris (1994-2007 ACD/Labs).

On the other hand, pKa can also be obtained by molecular orbital calculation. As a specific method, a method calculated by calculating the H ⁺ dissociation free energy in an aqueous solution based on a thermodynamic cycle is mentioned. The calculation method of the H ⁺ dissociation free energy can be calculated using, for example, DFT (density functional theory), but there are various other methods reported in literature and the like, so the calculation method is not limited to this. In addition, there are various kinds of software that can implement DFT, for example, Gaussian16 is mentioned.

As mentioned above, "pKa" refers to the value calculated by using the software package 1 based on the Hammett substituent constant and the value of the database of known literature values. However, when the pKa cannot be calculated by this method The following refers to the value obtained by using Gaussian16 based on DFT (density functional theory). In addition, as mentioned above, pKa refers to "pKa in aqueous solution", and when the pKa in aqueous solution cannot be calculated, it is set to "pKa in dimethylsulfoxide (DMSO) solution".

"Solid content" refers to components that form a resist film and does not include a solvent. In addition, as long as it is a resist film forming component, even if its property is a liquid, it is regarded as a solid component.

"1 inch" means 25.4mm.

[Actinic radiation-sensitive or radiation-sensitive resin composition] The actinic radiation-sensitive or radiation-sensitive resin composition (hereinafter also referred to as "photoresist composition") of the present invention includes the chemical formula (A) The resin having repeating unit A (hereinafter also referred to as "resin A"), the actinic radiation-sensitive or radiation-sensitive resin composition satisfies at least one of the following conditions: it further includes any of the chemical formulas (1) to (4) One of the indicated compounds (hereinafter also referred to as "specific compound"), the resin further has a group whose polarity is increased by the decomposition of acid (hereinafter also referred to as "acid decomposable group") (requirement A); or , the resin further has a repeating unit a, and the repeating unit a has a residue (hereinafter also referred to as " Specific group"), the content of the repeating unit a is 10 mol% or more relative to all the repeating units of the resin (requirement B). The photoresist composition of the present invention only needs to satisfy the foregoing condition A or the foregoing condition B, and may also satisfy both the foregoing condition A and the foregoing condition B. For example, the photoresist composition comprising resin A further comprises a specific compound, the resin may comprise the aforementioned repeating unit a, the content of the aforementioned repeating unit a is more than 10 mol% relative to all the repeating units of the resin, and further has the acid A group that decomposes under the action of the action and increases in polarity.

Although the mechanism of action of improving the sensitivity to exposure by adopting such a configuration is not necessarily clear, the inventors of the present invention presume as follows. In a resist film formed using a typical chemically amplified photoresist composition, in the case of using a resin having an acid-decomposable group, for example, acid generated by a photoacid generator by exposure Acting on a resin having an acid-decomposable group causes decomposition of the acid-decomposable group in the resin A, which may change the polarity of the exposed portion. Under such circumstances, the inventors of the present invention have found that if the photoacid generator that receives light is difficult to decompose, the solubility of the photoacid generator in the developing solution becomes poor during development, and it tends to remain as a defect. . In the photoresist composition of the present invention, the specific compound or repeating unit a that can function as a photoacid generator has at least one substituent whose σp exceeds 0 in Hammet's law, so the polarization in the molecule tends to increase. Therefore, it is presumed that it is easy to decompose at the time of exposure, and furthermore, the solubility in a developing solution improves, and it is excellent in development defect suppression property. Hereinafter, the fact that the development defect suppression property is more excellent is called the effect of the present invention is more excellent.

Hereinafter, the photoresist composition of the present invention will be described in detail. The photoresist composition can be any one of positive photoresist composition and negative photoresist composition. In addition, it may be either one of a photoresist composition for alkaline image development and a photoresist composition for organic solvent image development. The photoresist composition can be a non-chemically amplified photoresist composition, or it can be used in a photoresist composition as a mechanism of a chemically amplified photoresist composition. Below, various components of the photoresist composition are described in detail.

[Specific compound] The specific compound is a compound represented by any one of the chemical formulas (1) to (4). The specific compound is a nonionic compound that is decomposed by irradiation (exposure) of actinic rays or radiation, and can function as a photoacid generator described later. Certain compounds preferably have substituents with a σp exceeding 0.5 in Hammet's law. The number of substituents X described later that the specific compound has is 1 or more. As the specific compound, the compound represented by any one of the chemical formulas (1) to (3) is preferable, and the compound represented by the chemical formula (2) is more preferable in terms of the effect of the present invention.

[chemical formula 2]

In the chemical formula (1), X ¹¹ represents a hydrogen atom or -L ¹¹ -(R ¹¹ )p ₁₁ . R ¹¹ to R ¹³ each independently represent a substituent. At least one of R ¹¹ to R ¹³ represents a substituent in which σp exceeds 0 in Hammet's law. R ¹¹ and R ¹³ may be bonded to each other to form a ring. L ¹¹ represents a single bond or a linking group having a valence of p ₁₁ +1. L ¹² represents a single bond or a linking group having a valence of p ₁₂ +1. L ¹³ represents a single bond or a linking group having a valence of p ₁₃ +1. p ₁₁ to _{p 13} each independently represent an integer of 1 or more. Wherein, when L ¹¹ represents a single bond, p ₁₁ represents 1, when L ¹² represents a single bond, p ₁₂ represents 1, and when L ¹³ represents a single bond, p ₁₃ represents 1.

X ¹¹ represents a hydrogen atom or -L ¹¹ -(R ¹¹ )p ₁₁ . X ¹¹ is preferably -L ¹¹ -(R ¹¹ )p ₁₁ . L ¹¹ , R ¹¹ and p ₁₁ are as described below.

R ¹¹ to R ¹³ each independently represent a substituent. At least one of R ¹¹ to R ¹³ represents a substituent in which σp exceeds 0 in Hammet's law. 1 to 3 of R ¹¹ to ^{R 13} preferably represent the substituent X described later, one or two of R ¹¹ to R ¹³ represent a further substituent X, and one or both of R ¹¹ and R ¹³ Indicates that the substituent X is more preferred, and one of R ¹³ indicates that the substituent X is particularly preferred. R ¹¹ that may exist in plural, R ¹² that may exist in plural, and R ¹³ that may exist in plural may be the same or different, respectively. When a plurality of R ¹¹ , a plurality of R ¹² and/or a plurality of R ¹³ exist, the aforementioned "at least one of R ¹¹ to ^{R 13} represents a substituent whose σp in Hammet's law exceeds 0." refers to a plurality of At least one of R ¹¹ , R ¹² and/or R ¹³ represents a substituent X described later. Specifically, when the compound represented by the aforementioned chemical formula (1) has one R ¹¹ , one R ¹² and two R ^13s , R ¹¹ represents a methyl group, R ¹² represents an ethyl group, and one of R ¹³ represents a propyl group, The other of R ¹³ represents a substituent X, and both R ¹³ may represent a substituent X. In other words, the compound represented by the chemical formula (1) means having at least one substituent X. In addition, description about the said substituent X is also the same for each compound mentioned later. As said substituent, for example, the group illustrated in the said substituent K is mentioned, More specifically, a hydroxyl group, an amino group, and an organic group are mentioned, Preferably it is an organic group. As an organic group, a hydrocarbon group is mentioned, for example. Examples of the hydrocarbon group include an alkyl group (linear or branched), an alkenyl group, a cycloalkyl group, and an aromatic ring group, and an alkyl group is preferred. The aforementioned substituent may also be a substituent in which σp exceeds 0 in Hammet's rule (hereinafter also referred to as "substituent X"). The aforementioned substituent X is a group corresponding to an electron-withdrawing group. Examples of the substituent X include a halogen atom, a nitro group (0.78), a thiol group (0.15), an alkyl group having a halogen atom, a cyano group (0.66), an aldehyde group (0.42), and a carboxyl group (0.45). , acyl, acyloxy, alkoxycarbonyl, aryloxycarbonyl, aminoformyl, sulfamoyl, benzotriazolyl, sulfo and sulfonyl groups. In addition, in the above and below, the numerical value in parentheses described together with each group shows σp of each substituent. That is, when expressed as "nitro (0.78)", it means that σp in Hammet's law of nitro is 0.78. Moreover, as said substituent X, the group whose σp exceeds 0 as described in Chem. Rev., 1991, 91, 165-195 is mentioned, for example, These content is taken in into this specification. In addition, the substituent constant σ of Hammet's rule is a numerical value representing the effect of the substituent in the acid dissociation equilibrium constant of the substituted benzoic acid, and is a parameter representing the strength of the electron-withdrawing and electron-donating properties of the substituent. In this specification, the σp value of Hammet's law means the substituent constant σ when the substituent is at the para position of benzoic acid. As mentioned above, the values described in Chem. Rev., 1991, 91, 2, 165-195 are used for the value of σp. As for substituents not described in the above-mentioned documents, those based on the documents "The Effect of Structure upon the Reactions of Organic Compounds. Benzene Derivatives" (J. Am. Chem. Soc. 1937, 59, 1, 96-103) can be used. The value calculated by the calculation method described.

As the halogen atom, Br(0.23), Cl(0.23), F(0.06) and I(0.18) are preferable. As the alkyl group having a halogen atom, a brominated alkyl group, a salinized alkyl group, a fluorinated alkyl group or an iodized alkyl group is preferable, a fluorinated alkyl group is further preferable, and trifluoromethyl (0.54) is more preferable. The acyl group is preferably acetyl (0.50), trifluoroacetyl (0.80), propionyl, trimethylacetyl, benzoyl or 4-methoxybenzoyl. The acyloxy group is preferably an acyloxymethyl group or an acyloxyethyl group. The alkoxycarbonyl group is preferably methoxycarbonyl (0.45), ethoxycarbonyl, 2-hydroxyethoxycarbonyl, 2-(3-trimethoxysilylpropylaminocarbonyloxy)ethoxycarbonyl, 2-(3 -triethoxysilylpropylaminocarbonyloxy)ethoxycarbonyl, 2-ethylhexylcarbonyloxy, trifluoromethoxycarbonyl or trifluoroethoxycarbonyl. As the aryloxycarbonyl group, phenoxycarbonyl or 4-methoxyphenoxycarbonyl is preferred. As the aminoformyl group, unsubstituted aminoformyl, N,N-dimethylaminoformyl, N,N-diethylaminoformyl, morpholineaminoformyl, and Acyl, N,N-Di-n-octylcarbamoyl or N-n-octylcarbamoyl. As a group having a sulfonyl group, a methanesulfonyl group (0.72), an ethanesulfonyl group, an octanesulfonyl group or a benzenesulfonyl group is preferable. As the sulfo group, methanesulfonate (0.36), ethanesulfonate or octanesulfonate is preferred. As the sulfamoyl group, unsubstituted sulfamoyl group (0.60) or N,N-dimethylsulfamoyl group (0.65) is preferred. Among them, as the substituent X, preferably selected from the group consisting of nitro, N,N-dimethylsulfamoyl, fluoroalkyl, cyano, acetyl, unsubstituted sulfamoyl, trifluoroethyl At least one group of the group consisting of an acyl group and a sulfonyl group.

The σp of the substituent X is more than 0, preferably 0.3 or more, further preferably more than 0.5, more preferably 0.6 or more. The upper limit is not particularly limited, but in most cases it is 1.0 or less, preferably 0.8 or less. In addition, σp of substituents other than substituent X is not particularly limited. The aforementioned substituents may be further substituted by substituents (any one of substituents X and other substituents may be used).

R ¹¹ and R ¹³ may be bonded to each other to form a ring. The ring formed above is preferably a ring represented by Y ⁵¹ in the chemical formula (5) described later.

L ¹¹ represents a single bond or a linking group having a valence of p ₁₁ +1. L ¹² represents a single bond or a linking group having a valence of p ₁₂ +1. L ¹³ represents a single bond or a linking group having a valence of p ₁₃ +1. When p ₁₁ +1 valence, p ₁₂ +1 valence, and p ₁₃ +1 valence are divalent, examples of L ¹¹ to ^{L 13} include -CO-, -O-, -S-, - SO-, -SO ₂ -, -NR ^N - (R ^N represents a substituent), hydrocarbon groups (such as alkylene, cycloalkylene, alkenylene and arylylene, etc.) and combinations thereof group. The aforementioned groups may further have substituents. As said substituent, the group illustrated by substituent K is mentioned.

p ₁₁ to _{p 13} each independently represent an integer of 1 or more. Wherein, when L ¹¹ represents a single bond, p ₁₁ represents 1, when L ¹² represents a single bond, p ₁₂ represents 1, and when L ¹³ represents a single bond, p ₁₃ represents 1. As p ₁₁ to _{p 13} , an integer of 1 to 5 is preferable, an integer of 1 to 3 is still more preferable, and 1 is more preferable.

In the chemical formula (2), X ²¹ represents a hydrogen atom or -L ²¹ -(R ²¹ )p ₂₁ . X ²² represents a hydrogen atom or -L ²² -(R ²² )p ₂₂ . R ²¹ to R ²⁴ each independently represent a substituent. At least one of R ²¹ to R ²⁴ represents a substituent in which σp exceeds 0 in Hammet's law. L ²¹ represents a single bond or a linking group having a valence of p ₂₁ +1. L ²² represents a single bond or a linking group having a valence of p ₂₂ +1. L ²³ represents a single bond or a linking group having a valence of p ₂₃ +1. L ²⁴ represents a single bond or a linking group having a valence of p ₂₄ +1. At least two of R ²¹ , R ²² and R ²⁴ may be bonded to each other to form a ring. p ₂₁ to _{p 24} each independently represent an integer of 1 or more. Wherein, when ^L21 represents a single bond, _p21 represents 1, when ^L22 represents a single bond, _p22 represents 1, when ^L23 represents a single bond, _p23 represents 1, and ^L24 represents a single bond In this case, p ₂₄ represents 1. n ₂₁ represents an integer of 1 or more.

At least one of X ²¹ and X ²² is preferably a hydrogen atom, and both X ²¹ and X ²² are more preferably a hydrogen atom. L ²¹ , R ²¹ and p ₂₁ , and L ²² , R ²² and p ₂₂ are described below.

Examples of substituents represented by R ²¹ to ^{R 24} include substituents represented by R ¹¹ to R ¹³ in the aforementioned chemical formula (1). 1 to 4 of R ²¹ to R ²⁴ are preferably substituents X, one or two of R ²¹ to R ²⁴ are more preferably substituents X, and one or both of R ²¹ and R ²⁴ are substituents The group X is more preferred, and one of ^R24 represents the substituent X is particularly preferred. R ²¹ that may exist in plural, R ²² that may exist in plural, R ²³ that may exist in plural _, and R ²⁴ that may exist in plural may be the same or different. In addition, at least two of R ²¹ , R ²² and R ²⁴ may be bonded to each other to form a ring. One of R ²¹ or R ²² and R ²⁴ are preferably bonded to each other to form a ring. The ring formed above may be either monocyclic or polycyclic.

When p ₂₁ +1 valence, p ₂₂ +1 valence, p ₂₃ +1 valence, and p ₂₄ +1 valence are divalent, examples of L ²¹ to ^{L 24} include -CO-, -O-, -S-, -SO-, -SO ₂ -, -NR ^N ( ^RN represents a substituent)-, hydrocarbon groups (such as alkylene, cycloalkylene, alkenyl and aryl, etc.) and the combined groups. The aforementioned groups may further have substituents. As said substituent, the group illustrated by substituent K is mentioned. As p ₂₁ to _{p 24} , an integer of 1 to 5 is preferable, an integer of 1 to 3 is still more preferable, and 1 is more preferable.

n ₂₁ represents an integer of 1 or more. As n ₂₁ , an integer of 1 to 5 is preferable, an integer of 1 to 3 is still more preferable, 1 or 2 is more preferable, and 1 is particularly preferable.

In the chemical formula (3), X ³¹ represents a hydrogen atom or -L ³¹ -(R ³¹ )p ₃₁ . R ³¹ and R ³² each independently represent a substituent. At least one of R ³¹ and R ³² represents a substituent in which σp exceeds 0 in Hammet's law. L ³¹ represents a single bond or a linking group having a valence of p ₃₁ +1. L ³² represents a single bond or a linking group having a valence of p ₃₂ +1. p ₃₁ and p ₃₂ each independently represent an integer of 1 or more. Wherein, when L ³¹ represents a single bond, p ₃₁ represents 1, and when L ³² represents a single bond, p ₃₂ represents 1. Ar ³¹ represents an aromatic ring group.

X ³¹ is preferably -L ³¹ -(R ³¹ )p ₃₁ . L ³¹ , R ³¹ and p ₃₁ are as described below.

As the substituents represented by R ³¹ and R ³² , for example, substituents represented by R ¹¹ to ^{R 13} in the aforementioned chemical formula (1) can be mentioned. One of R ³¹ and R ³² is preferably a substituent X, and one of R ³¹ is more preferably a substituent X. R ³¹ that may exist in plural and R ³² that may exist in plural may be the same or different. When p ₃₁ +1 valence and p ₃₂ +1 valence are divalent, examples of L ³¹ include -CO-, -O-, -S-, -SO-, -SO ₂ -, -NR ^N— (R ^N represents a substituent), a hydrocarbon group (such as an alkylene group, a cycloalkylene group, an alkenylene group, an arylylene group, etc.), and a group formed by combining them. The aforementioned groups may further have substituents. As said substituent, the group illustrated by substituent K is mentioned. As p ₃₁ and p ₃₂ , an integer of 1-5 is preferable, an integer of 1-3 is still more preferable, and 1 is more preferable.

Ar ³¹ represents an aromatic ring group. The aforementioned aromatic ring group may be either monocyclic or polycyclic. The number of ring atoms that are members of the aforementioned aromatic ring group is preferably from 5 to 15. The member ring atoms of the aforementioned aromatic ring group may have one or more (for example, 1 to 5) heteroatoms (for example, oxygen atom, sulfur atom, nitrogen atom, etc.). As the aromatic ring constituting the aforementioned aromatic ring group, for example, aromatic hydrocarbon rings such as benzene ring, naphthalene ring, and anthracene ring, and aromatic heterocyclic rings such as thiazole rings such as benzothiazole, the aromatic hydrocarbon ring is preferred, and benzene Ring is better.

In the chemical formula (4), X ⁴¹ represents a hydrogen atom or -L ⁴¹ -(R ⁴¹ )p ₄₁ . X ⁴² represents a hydrogen atom or -L ⁴² -(R ⁴² )p ₄₂ . R ⁴¹ to R ⁴³ each independently represent a substituent. At least one of R ⁴¹ to R ⁴³ represents a substituent in which σp exceeds 0 in Hammet's law. L ⁴¹ represents a single bond or a linking group having a valence of p ₄₁ +1. L ⁴² represents a single bond or a linking group having a valence of p ₄₂ +1. L ⁴³ represents a single bond or a linking group having a valence of p ₄₃ +1. R ⁴¹ and R ⁴² may be bonded to each other to form a ring. p ₄₁ to _{p 43} each independently represent an integer of 1 or more. Wherein, when L ⁴¹ represents a single bond, p ₄₁ represents 1, when L ⁴² represents a single bond, p ₄₂ represents 1, and when L ⁴³ represents a single bond, p ₄₃ represents 1.

X ⁴¹ represents a hydrogen atom or -L ⁴¹ -(R ⁴¹ )p ₄₁ . X ⁴² represents a hydrogen atom or -L ⁴² -(R ⁴² )p ₄₂ . As X ⁴¹ , -L ⁴¹ -(R ⁴¹ )p ₄₁ is preferable. X ⁴² is preferably -L ⁴² -(R ⁴² )p ₄₂ . L ⁴¹ , R ⁴¹ and p ₄₁ , and L ⁴² , R ⁴² and p ₄₂ are described below.

Examples of substituents represented by R ⁴¹ to ^{R 43} include substituents represented by R ¹¹ to ^{R 13} in the aforementioned chemical formula (1). 1 to 3 of R ⁴¹ to ^{R 43} are preferably substituent X, and one or two of R ⁴¹ and R ⁴² are more preferably substituent X. R ⁴¹ that may exist in plural, R ⁴² that may exist in plural, and R ⁴³ that may exist in plural may be the same or different from each other. When p ₄₁ +1 valence, p ₄₂ +1 valence and p ₄₃ +1 valence are divalent, examples of L ⁴¹ to ^{L 43} include -CO-, -O-, -S-, -SO -, -SO ₂ -, -NR ^N - ( ^RN represents a substituent), hydrocarbon groups (such as alkylene, cycloalkylene, alkenylene, arylylene, etc.) and groups formed by combining them . The aforementioned groups may further have substituents. As said substituent, the group illustrated by substituent K is mentioned. R ⁴¹ and R ⁴² may be bonded to each other to form a ring. The ring formed above may be either monocyclic or polycyclic. As p ₄₁ to _{p 43} , an integer of 1 to 5 is preferable, an integer of 1 to 3 is still more preferable, and 1 is more preferable.

As the compound represented by the chemical formula (1), a compound represented by the chemical formula (5) is preferable.

[chemical formula 3]

In the chemical formula (5), X ⁵¹ represents a hydrogen atom or -L ⁵¹ -(R ⁵¹ )p ₅₁ . R ⁵¹ and R ⁵² each independently represent a substituent. At least one of R ⁵¹ and R ⁵² represents a substituent in which σp exceeds 0 in Hammet's law. L ⁵¹ represents a single bond or a linking group having a valence of p ₅₁ +1. L ⁵² represents a single bond or a linking group having a valence of p ₅₂ +1. p ₅₁ and p ₅₂ each independently represent an integer of 1 or more. Wherein, when L ⁵¹ represents a single bond, p ₅₁ represents 1, and when L ⁵² represents a single bond, p ₅₂ represents 1. Y ⁵¹ represents a ring with -CO-N-CO-.

As X ⁵¹ , -L ⁵¹ -(R ⁵¹ )p ₅₁ is preferable. L ⁵¹ , R ⁵¹ and p ₅₁ are as described below.

As the substituents represented by R ⁵¹ and R ⁵² , for example, substituents represented by R ¹¹ to ^{R 13} in the aforementioned chemical formula (1) can be mentioned. One of R ⁵¹ and R ⁵² preferably represents the substituent X, and one of R ⁵¹ represents the substituent X is more preferable. R ⁵¹ that may exist in plural and R ⁵² that may exist in plural may be the same or different from each other. When p ₅₁ +1 valence and p ₅₂ +1 valence are divalent, examples of L ⁵¹ and L ⁵² include -CO-, -O-, -S-, -SO-, -SO ₂ - , -NR ^N - (R ^N represents a substituent), a hydrocarbon group (such as an alkylene group, a cycloalkylene group, an alkenylene group, an arylylene group, etc.) and a group formed by combining them. The aforementioned groups may further have substituents. As said substituent, the group illustrated by substituent K is mentioned. As p ₅₁ and p ₅₂ , an integer of 1-5 is preferable, an integer of 1-3 is still more preferable, and 1 is more preferable.

Y ⁵¹ represents a ring with -CO-N-CO-. Any of monocyclic and polycyclic rings may be used as the aforementioned ring. The number of ring members of the aforementioned ring is preferably 5-20. The member ring atoms of the aforementioned ring may have four or more (for example, 1 to 5) heteroatoms (for example, oxygen atom, sulfur atom, nitrogen atom, etc.). Examples of the aforementioned ring include an imide ring and a ring in which an imide ring is combined with a ring selected from the group consisting of an alicyclic ring and an aromatic ring. As the aforementioned ring, a polycyclic ring is preferable, and a polycyclic ring having at least one alicyclic ring and an aromatic ring is more preferable. The aforementioned polycyclic ring may also be a condensed ring. Examples of the imide ring include a maleimide ring, a succinimide ring, and a glutarimide ring. Examples of the alicyclic ring include monocyclic alicyclic rings such as cycloalkane and cycloalkene, and polycyclic alicyclic rings such as bicycloundecane, decalin, norbornene, norbornadiene, and adamantane. Examples of aromatic rings include aromatic homocyclic rings such as benzene rings, naphthalene rings, and anthracene rings, and aromatic heterocyclic rings such as thiazole rings such as benzothiazole, preferably aromatic homocyclic rings, and benzene rings or naphthalene rings. better.

As a specific compound, the following compounds are mentioned, for example.

[chemical formula 4]

One type of specific compound may be used alone, or two or more types may be used. When the photoresist composition contains a specific compound, the content of the specific compound is preferably at least 0.5% by mass, more preferably at least 1.0% by mass, more preferably at least 5.0% by mass, based on the total solid content of the photoresist composition. good. The upper limit is preferably 40.0% by mass or less, more preferably 30.0% by mass or less, based on the total solid content of the resist composition. In the case of using two or more, it is preferred that the total content is within the aforementioned preferred content range.

[Resin A] Resin A has a repeating unit A represented by the chemical formula (A). Resin A preferably has at least one selected from the group consisting of repeating unit a and repeating unit b. In addition, when the photoresist composition only satisfies condition A, resin A has acid-decomposable groups (preferably repeating unit b). In addition, when the photoresist composition only satisfies condition B, resin A has repeating unit a, and the content of repeating unit a in resin A is 10 mol% or more relative to all repeating units of resin A.

＜Repeating Unit A＞

[chemical formula 5]

In the chemical formula (A), R ^A1 to R ^A3 each independently represent a hydrogen atom, an alkyl group, a cycloalkyl group, a halogen atom, a cyano group or an alkoxycarbonyl group. L ^A represents a single bond or a divalent linking group. Ar ^A represents an aromatic ring group. R ^A2 and Ar ^A may be bonded to each other to form a ring. n _A represents an integer of 1-5.

R ^A1 to R ^A3 independently represent a hydrogen atom, an alkyl group, a cycloalkyl group, a halogen atom, a cyano group or an alkoxycarbonyl group. The aforementioned alkyl group may be either linear or branched. The carbon number of the aforementioned alkyl group is preferably 1-6, more preferably 1-3. The aforementioned cycloalkyl group may be either monocyclic or polycyclic. As carbon number of the said cycloalkyl group, 3-15 are preferable. Examples of the halogen atom include a fluorine atom, a chlorine atom, a bromine atom and an iodine atom. As carbon number of the said alkoxycarbonyl group, 1-10 are preferable. As an alkyl moiety in the said alkoxycarbonyl group, the thing similar to the said alkyl group is mentioned, for example. The aforementioned alkyl group, the aforementioned cycloalkyl group, and the aforementioned alkoxycarbonyl group may further have a substituent. Examples of the aforementioned substituent include an alkyl group, a cycloalkyl group, an aryl group, an amino group, an amido group, a urea group, a urethane group, a hydroxyl group, a carboxyl group, a halogen atom, an alkoxy group, and a thioether group. group, acyl group, acyloxy group, alkoxycarbonyl group, cyano group and nitro group. As R ^A1 and R ^A2 , a hydrogen atom or an alkyl group is preferable, and a hydrogen atom is more preferable. R ^A3 is preferably a hydrogen atom or an alkyl group, further preferably a hydrogen atom or an alkyl group, and more preferably a hydrogen atom or a methyl group.

L ^A represents a single bond or a divalent linking group. Examples of the divalent linking group include -CO-, -O-, -COO-, -S-, -SO-, -SO ₂ -, -NR ^N - (R ^N represents a substituent), hydrocarbon group ( For example, alkylene group, cycloalkylene group, alkenylene group, arylylene group, etc.) and groups formed by combining them. The aforementioned hydrocarbon group may further have a substituent. As said substituent, the group illustrated by substituent K is mentioned. As ^LA , a single bond, or -COO-, ^-CONRA - ( ^RA represents a hydrogen atom or an alkyl group), an alkylene group, or a combination thereof is preferred, and a single bond or -COO- is more preferred. good.

Ar ^A represents an aromatic ring group. The aforementioned aromatic ring group may be either monocyclic or polycyclic. The number of ring atoms of the aforementioned aromatic ring group is preferably from 5 to 15, more preferably from 6 to 12. As a member ring atom of the aforementioned aromatic ring group, one or more (for example, 1 to 5) heteroatoms (for example, oxygen atom, sulfur atom, nitrogen atom, etc.) may be included. The aforementioned aromatic ring group is preferably an aromatic hydrocarbon ring group having 6 to 18 carbon atoms such as a benzene ring group, a toluene ring group, a naphthalene ring group, and an anthracene ring group, or a thiophene ring group, a furan ring group, or a pyrrole ring group. , benzothiophene ring group, benzofuran ring group, benzopyrrole ring group, triazine ring group, imidazole ring group, benzimidazole ring group, triazole ring group, thiadiazole ring group and thiazole ring group and other aromatic Family heterocyclic group. The aforementioned aromatic ring may further have a substituent. As the aforementioned substituents, for example, the groups exemplified by the substituent K are mentioned, and an alkyl group or a halogen atom is preferable, and a fluorine atom, chlorine atom, iodine atom or bromine atom is more preferable. As the aforementioned aromatic ring group, divalent arylylene groups such as a phenylene group having a halogen atom and a naphthylene group that may have a halogen atom, or a trivalent arylylene group formed by removing one or two hydrogen atoms from the aforementioned divalent arylylene group. A valent or tetravalent group is preferable, and a phenylene group which may have a halogen atom, or a trivalent or tetravalent group formed by removing one or two hydrogen atoms from the aforementioned divalent phenylene group is more preferable.

R ^A2 and Ar ^A may be bonded to each other to form a ring. When R ^A2 and Ar ^A form a ring, R ^A2 preferably represents a single bond or an alkylene group. Examples of the ring formed by bonding R ^A2 and Ar ^A include polycyclic rings such as acenaphthylene rings and indene rings.

n _A represents an integer of 1-5. As n _A , an integer of 1-3 is preferable, and an integer of 1-2 is more preferable.

As repeating unit A, repeating unit A1 represented by chemical formula (A1) is preferable.

[chemical formula 6]

In the chemical formula (A1), R ^A11 represents a hydrogen atom, an alkyl group, a cycloalkyl group, a halogen atom or a cyano group. R ^A12 represents halogen, alkyl, cycloalkyl, aryl, alkenyl, aralkyl, alkoxy, alkylcarbonyloxy, alkylsulfonyloxy, alkoxycarbonyl or aryloxycarbonyl. n _A11 represents an integer of 1-5. n _A12 represents an integer of 0-4. n _A11 +n _A12 represents an integer of 1-5.

R ^A11 represents a hydrogen atom, an alkyl group, a cycloalkyl group, a halogen atom or a cyano group. R ^A11 has the same meaning as R ^A3 in the aforementioned chemical formula (A), and the preferred mode is also the same.

R ^A12 represents halogen, alkyl, cycloalkyl, aryl, alkenyl, aralkyl, alkoxy, alkylcarbonyloxy, alkylsulfonyloxy, alkoxycarbonyl or aryloxycarbonyl. As R ^A12 , a halogen atom is preferable, and a fluorine atom, chlorine atom, iodine atom or bromine atom is more preferable. When a plurality of R ^A12 exists, R ^A12 may be the same or different from each other.

n _A11 represents an integer of 1-5. n _A12 represents an integer of 0-4. n _A11 +n _A12 represents an integer of 1-5. As n _A11 , an integer of 1-3 is preferable, and an integer of 1-2 is more preferable. As n _A12 , an integer of 0-3 is preferable, and an integer of 0-2 is more preferable. As n _A11 +n _A12 , an integer of 1-3 is preferable.

As repeating unit A, the following repeating units are mentioned, for example. In the following description, a represents an integer from 1 to 3.

[chemical formula 7]

[chemical formula 8]

[chemical formula 9]

[chemical formula 10]

As the repeating unit A, one kind can be used alone or two or more kinds can be used. The content of the repeating unit A is preferably more than 0 mol%, further preferably 5 mol% or more, and more preferably 10 mol% or more, relative to all the repeating units in the resin A. The upper limit is preferably not more than 70 mol%, further preferably not more than 65 mol%, and more preferably not more than 60 mol%, based on the total repeating units of the resin A.

<Repeating unit a> Repeating unit a is a repeating unit with a specific base. The specific group can be directly bonded to the main chain of the repeating unit a, or form a part of the main chain of the repeating unit a. Specifically, when the main chain is an ethylene chain, a part of the ethylene chain may be composed of a specific group. The repeating unit derived from the specific compound M-40 and represented by the chemical formula (ae) is included in the repeating unit a. The repeating unit a is a repeating unit having a group that generates a polar group by decomposition by exposure. Resin A having a repeating unit a increases in polarity by exposure, increases solubility in an alkaline developing solution, and decreases solubility in an organic solvent.

(Specific group) A specific group is a residue formed by removing one or two hydrogen atoms from a specific compound. Specific groups are decomposed by irradiation with actinic rays or radiation to produce polar groups. The specific group has at least A preferred one, having at least one group selected from any one of the groups represented by any of the chemical formulas (1a) to (4a), further preferably having any of the groups selected from the chemical formulas (1a) to (3a) More preferably at least one of the groups represented by one, at least one selected from the group represented by the chemical formula (1a) and the group represented by (2a) is particularly preferred, It is most preferable to have a group represented by the chemical formula (2a).

[chemical formula 11]

In the chemical formula (1a), X ^11a represents a hydrogen atom or -L ^11a -(R ^11a )p _11a . R ^11a and R ^13a each independently represent a substituent. At least one of R ^11a and R ^13a represents a substituent in which σp exceeds 0 in Hammet's law. R ^11a and R ^13a may be bonded to each other to form a ring. L ^11a represents a single bond or a linking group having a valency of p _11a +1. L ^12a represents a single bond or a divalent linking group. L ^13a represents a single bond or a linking group having a valency of p _13a +1. p _11a and p _13a each independently represent an integer of 1 or more. However, when L ^11a represents a single bond, p _11a represents 1, and when L ^13a represents a single bond, p _13a represents 1. * Indicates bond position. X ^11a , L ^11a , L ^13a , R ^11a , R ^13a , p _11a and p _13a have the meanings of X ¹¹ , L ¹¹ , L ¹³ , R ¹¹ , R ¹³ , p ₁₁ and p ₁₃ in the aforementioned chemical formula (1) respectively The same, the preferred way is also the same. Examples of L ^12a include divalent linking groups that may be obtained by L ¹² in the aforementioned chemical formula (1).

The group represented by the chemical formula (1a) is preferably a group represented by the chemical formula (5a).

[chemical formula 12]

In the chemical formula (5a), X ^51a represents a hydrogen atom or -L ^51a -(R ^51a )p _51a . R ^51a each independently represent a substituent. At least one of R ^51a represents a substituent whose σp exceeds 0 in Hammet's law. L ^51a represents a single bond or a linking group having a valency of p _51a +1. L ^52a represents a single bond or a divalent linking group. p _{5 1a} represents an integer of 1 or more. Wherein, when L ^51a represents a single bond, p _51a represents 1. Y ^51a represents a ring having -CO-N-CO-. * Indicates bond position. X ^51a , L ^51a , R ^51a , Y ^51a and p _51a have the same meanings as X ⁵¹ , L ⁵¹ , R ⁵¹ , Y ⁵¹ and p ₅₁ in the aforementioned chemical formula (5), and the preferred modes are also the same. Examples of L ^52a include divalent linking groups that may be obtained by L ⁵² in the aforementioned chemical formula (5).

In the chemical formula (2a), X ^21a represents a hydrogen atom or -L ^21a -(R ^21a )p _21a . X ^22a represents a hydrogen atom or -L ^22a -(R ^22a )p _22a . R ^21a , R ^22a and R ^24a each independently represent a substituent. At least one of R ^21a , R ^22a and R ^24a represents a substituent in which σp exceeds 0 in Hammet's law. L ^21a represents a single bond or a linking group having a valency of p _21a +1. L ^22a represents a single bond or a linking group having a valence of p _22a +1. L ^23a represents a single bond or a divalent linking group. L ^24a represents a single bond or a linking group having a valency of p _24a +1. At least two of R ^21a , R ^22a and R ^24a may be bonded to each other to form a ring. p _21a , p _22a and p _24a each independently represent an integer of 1 or more. Wherein, when L ^21a represents a single bond, p _21a represents 1, when L ^22a represents a single bond, p _22a represents 1, and when L ^24a represents a single bond, p _24a represents 1. n _21a represents an integer of 1 or more. * Indicates bond position. X ^21a , X ^22a , L ^21a , L ^22a , L ^24a , R ^21a , R ^22a , R ^24a , p _21a , p _22a , p _24a and n _21a are respectively the same as X ²¹ , X ²² , L ²¹ , L ²² , L ²⁴ , R ²¹ , R ²² , R ²⁴ , p ₂₁ , p ₂₂ , p ₂₄ and n ₂₁ have the same meanings, and the preferred modes are also the same. Examples of L ^23a include divalent linking groups that may be obtained by L ²³ in the aforementioned chemical formula (2).

In the chemical formula (3a), X ^31a represents a hydrogen atom or -L ^31a -(R ^31a )p _31a . R ^31a each independently represent a substituent. At least one of R ^31a represents a substituent whose σp in Hammet's law exceeds 0. L ^31a represents a single bond or a linking group having a valency of p _31a +1. L ^32a represents a single bond or a divalent linking group. p _31a represents an integer of 1 or more. However, when L ^31a represents a single bond, p _31a represents 1. Ar ^31a represents an aromatic ring group. * Indicates bond position. X ^31a , L ^31a , R ^31a , p _31a and Ar ^31a have the same meanings as X ³¹ , L ³¹ , R ³¹ , p ₃₁ and Ar ³¹ in the aforementioned chemical formula (3), and the preferred modes are also the same. Examples of L ^32a include divalent linking groups that may be obtained by L ³² in the aforementioned chemical formula (3).

In the chemical formula (4a), X ^41a represents a hydrogen atom or -L ^41a -(R ^41a )p _41a . X ^42a represents a hydrogen atom or -L ^42a -(R ^42a )p _42a . R ^41a and R ^42a each independently represent a substituent. At least one of R ^41a and R ^42a represents a substituent in which σp exceeds 0 in Hammet's law. L ^41a represents a single bond or a linking group having a valency of p _41a +1. L ^42a represents a single bond or a linking group having a valence of p _42a +1. L ^43a represents a single bond or a divalent linking group. R ^41a and R ^42a may be bonded to each other to form a ring. p _41a and p _42a each independently represent an integer of 1 or more. However, when L ^41a represents a single bond, p _41a represents 1, and when L ^42a represents a single bond, p _42a represents 1. * Indicates bond position. X ^41a , X ^42a , L ^41a , L ^42a , R ^41a , R ^42a , p _41a and p _42a are respectively combined with X ⁴¹ , X ⁴² , L ⁴¹ , L ⁴² , R ⁴¹ , R ⁴² , p ₄₁ and p ₄₂ have the same meaning, and the preferred mode is also the same. Examples of L ^43a include divalent linking groups that may be obtained by L ⁴³ in the aforementioned chemical formula (4).

[chemical formula 13]

In the chemical formula (1b), X ^11b represents a hydrogen atom or -L ^11b -(R ^11b )p _11b . R ^11b and R ^12b each independently represent a substituent. At least one of R ^11b and R ^12b represents a substituent in which σp exceeds 0 in Hammet's law. L ^11b represents a single bond or a linking group having a valency of p _11b +1. L ^12b represents a single bond or a linking group having a valence of p _12b +1. L ^13b represents a single bond or a divalent linking group. p _11b and p _12b each independently represent an integer of 1 or more. However, when L ^11b represents a single bond, p _11b represents 1, and when L ^12b represents a single bond, p _12b represents 1. * Indicates bond position. X ^11b , L ^11b , L ^12b , R ^11b , R ^12b , p _11b and p _12b have the meanings of X ¹¹ , L ¹¹ , L ¹² , R ¹¹ , R ¹² , p ₁₁ and p ₁₂ in the aforementioned chemical formula (1) respectively The same, the preferred way is also the same. Examples of L ^13b include divalent linking groups that may be obtained by L ¹³ in the aforementioned chemical formula (1).

In the chemical formula (2b), X ^21b represents a hydrogen atom or -L ^21b -(R ^21b )p _21b . X ^22b represents a hydrogen atom or -L ^22b -(R ^22b )p _22b . R ^21b to ^{R 23b} each independently represent a substituent. At least one of R ^21b to ^{R 23b} represents a substituent in which σp exceeds 0 in Hammet's law. L ^21b represents a single bond or a linking group having a valence of p _12b +1. L ^22b represents a single bond or a linking group having a valence of p _22b +1. L ^23b represents a single bond or a linking group having a valence of p _23b +1. L ^24b represents a single bond or a divalent linking group. R ^21b and R ^22b may be bonded to each other to form a ring. p _21b to _{p 23b} each independently represent an integer of 1 or more. Wherein, when L ^21b represents a single bond, p _21b represents 1, when L ^22b represents a single bond, p _22b represents 1, and when L ^23b represents a single bond, p _23b represents 1. n _21b represents an integer of 1 or more. * Indicates bond position. X ^21b , X ^22b , L ^21b ~L ^23b , R ^21b ~R ^23b , p _21b ~p _23b and n _21b respectively correspond to X ²¹ , X ²² , L ²¹ ~L ²³ , R ²¹ ~ R ²³ , p ₂₁ to p ₂₃ and n ₂₁ have the same meanings, and the preferred modes are also the same. Examples of L ^24b include divalent linking groups that may be obtained by L ²⁴ in the aforementioned chemical formula (2).

In the chemical formula (3b), R ^32b each independently represent a substituent. At least one of R ^32b represents a substituent whose σp exceeds 0 in Hammet's law. L ^31b represents a single bond or a divalent linking group. L ^32b represents a bond or a linking group of p _32b +1 valency. p _32b represents an integer of 1 or more. Wherein, when L ^32b represents a single bond, p _32b represents 1. Ar ^31b represents an aromatic ring group. * Indicates bond position. R ^32b , L ^32b , p _32b and Ar ^31b have the same meanings as R ³² , L ³² , p ₃₂ and Ar ³¹ in the aforementioned chemical formula (3), respectively, and the preferred modes are also the same. As L ^31b , the aforementioned chemical formula (3) can be cited. L ³¹ in may obtain a divalent linking group.

In the chemical formula (4b), X ^41b represents a hydrogen atom, -L ^41b -(R ^41b )p _41b or -L ^4b -*. X ^42b represents a hydrogen atom, -L ^42b -(R ^42b )p _42b or -L ^4b -*. Either one of X ^41b and X ^42b represents -L ^4b -*. L ^4b represents a divalent linking group. R ^41b to ^{R 43b} each independently represent a substituent. At least one of R ^41b to R ^43b represents a substituent in which σp exceeds 0 in Hammet's law. L ^41b represents a single bond or a linking group having a valency of p _41b +1. L ^42b represents a single bond or a linking group with a valence of p _42b +1. L ^43b represents a single bond or a linking group having a valency of p _43b +1. R ^41b and R ^42b may be bonded to each other to form a ring. p _41b to _{p 43b} each independently represent an integer of 1 or more. Wherein, when L ^41b represents a single bond, p _41b represents 1, when L ^42b represents a single bond, p _42b represents 1, and when L ^43b represents a single bond, p _43b represents 1. * Indicates bond position. X ^41b , X ^42b , L ^41b ~ L ^43b , R ^41b ~ ^{R 43b} and p _41b ~ p _43b are respectively combined with X ⁴¹ , X ⁴² , L ⁴¹ ~ ^{L 43} , R ⁴¹ ~ ^{R 43} and p ₄₁ to _{p 43} have the same meaning, and the preferred mode is also the same. Examples of L ^4b include divalent linking groups that may be obtained by L ⁴¹ and L ⁴² in the aforementioned chemical formula (4).

In the chemical formula (5b), R ^52b each independently represent a substituent. At least one of R ^52b represents a substituent whose σp exceeds 0 in Hammet's law. L ^51b represents a single bond or a divalent linking group. L ^52b represents a single bond or a linking group having a valency of p _52b +1. p _52b represents an integer of 1 or more. Wherein, when L ^52b represents a single bond, p _52b represents 1. Y ^51b represents a ring with -CO-N-CO-. n _5b represents an integer of 1 or 2. * Indicates bond position. R ^52b , L ^52b , p _52b and Y ^51b have the same meanings as R ⁵² , L ⁵² , p ₅₂ and Y ⁵¹ in the aforementioned chemical formula (5), and the preferred modes are also the same. Examples of L ^51b include divalent linking groups that may be obtained by L ⁵¹ in the aforementioned chemical formula (5). When a plurality of L ^51b exists, L ^51b may be the same or different from each other.

The repeating unit a is preferably a repeating unit represented by the chemical formula (a).

[chemical formula 14]

In the chemical formula (a), R ^a1 to ^{R a3} each independently represent a hydrogen atom or a substituent. L ^a1 represents a single bond or a divalent linking group. T represents a specific group A.

R ^a1 to R ^a3 each independently represent a hydrogen atom or a substituent. As R ^a1 to ^{R a3} , each independently hydrogen atom, alkyl, cycloalkyl, halogen atom, cyano or alkoxycarbonyl is preferred, hydrogen atom, halogen atom or alkyl is further preferred, hydrogen atom or methyl better.

L ^a1 represents a single bond or a divalent linking group. Examples of the aforementioned divalent linking group include -CO-, -O-, -S-, -SO-, -SO ₂ -, -NR ^N -, hydrocarbon groups (e.g., alkylene, cycloalkylene, group, alkenyl group and aryl group, etc.), and a group formed by combining them. R ^N represents a substituent. The aforementioned hydrocarbon group may further have a substituent, and preferably has a halogen atom (preferably a fluorine atom) as the substituent.

The aforementioned alkylene group may be either linear or branched. The number of carbon atoms in the alkylene group is preferably 1-4. The aforementioned cycloalkylene group may be either monocyclic or polycyclic. The number of carbon atoms in the cycloalkylene group is preferably 3-15. One or more (for example, one or two) of -CH ₂ - constituting the ring structure of the aforementioned cycloalkylene group may be replaced by heteroatoms (such as -O- and -S-, etc.), -SO ₂ -, -SO ₃ - , alkoxycarbonyl or carbonyl substitution.

T represents a specific group A. The specific group A is a residue formed by removing a hydrogen atom from a specific compound. As the specific group A, for example, a monovalent group among the aforementioned specific groups can be mentioned.

The repeating unit a is preferably a repeating unit represented by any one of the chemical formulas (aa) to (ac).

[chemical formula 15]

In the chemical formula (aa), R ^1a to R ^3a each independently represent a hydrogen atom or a substituent. L ^1a represents a single bond, an alkylene group, -COO-, an aromatic ring group, or a combination thereof. Ar represents an aromatic ring group. Z represents a group represented by any one of the chemical formulas (Z1a) to (Z4a), or a group represented by any one of the chemical formulas (Z1b) to (Z4b).

R ^1a to R ^3a each independently represent a hydrogen atom or a substituent. As R ^1a to ^{R 3a} , each independently hydrogen atom, alkyl, cycloalkyl, halogen atom, cyano or alkoxycarbonyl is preferred, hydrogen atom, halogen atom or alkyl is further preferred, hydrogen atom or methyl better.

L ^1a represents a single bond, an alkylene group, -COO-, an aromatic ring group, or a combination thereof. The aforementioned alkylene group may be either linear or branched. The number of carbon atoms in the alkylene group is preferably 1-4. The aforementioned aromatic ring group may be either monocyclic or polycyclic. The number of ring atoms of the aforementioned aromatic ring group is preferably 5-15. The aforementioned aromatic ring group may have one or more (eg, 1 to 5) heteroatoms (eg, oxygen atom, sulfur atom, and/or nitrogen atom, etc.) as member ring atoms. As the aforementioned aromatic ring group, a benzene ring group is preferred. As the group of the aforementioned combination, for example, -COO-alkylene group and -COO-aromatic ring group are mentioned. The aforementioned alkylene group and the aforementioned aromatic ring group may further have a substituent. As the aforementioned substituents, possible substituents for R ¹¹ to ^{R 13} in the chemical formula (1) can be mentioned. As L ^1a , a single bond or an alkylene group is preferable, and a single bond is more preferable.

Ar represents an aromatic ring group. The aforementioned aromatic ring group may be either monocyclic or polycyclic. The number of ring atoms of the aforementioned aromatic ring group is preferably 5-15. As a member ring atom of the aforementioned aromatic ring group, one or more (for example, 1 to 5) heteroatoms (for example, oxygen atom, sulfur atom, nitrogen atom, etc.) may be included. The aforementioned aromatic ring group may further have a substituent. As the aforementioned substituents, possible substituents for R ¹¹ to ^{R 13} in the chemical formula (1) can be mentioned. As the aforementioned aromatic ring group, arylylene groups such as phenylene and naphthylene are preferable, and phenylene is more preferable.

Z represents a group represented by any one of the chemical formulas (Z1a) to (Z4a), or a group represented by any one of the chemical formulas (Z1b) to (Z4b). As Z, the group represented by any one of the chemical formulas (Z1a) to (Z4a) is preferred, the group represented by any one of the chemical formulas (Z1a) to (Z3a) is further preferred, and the group represented by the chemical formula (Z2a) The group is better.

[chemical formula 16]

The symbols in the chemical formulas (Z1a) to (Z4a) have the same meanings as the symbols in the aforementioned chemical formulas (1) to (4), and the preferred modes are also the same. * Indicates bond position.

As the group represented by the chemical formula (Z1a), a group represented by the chemical formula (Z5a) is preferable.

[chemical formula 17]

Each symbol in the chemical formula (Z5a) has the same meaning as each symbol in the aforementioned chemical formula (5), and the preferred mode is also the same. * Indicates bond position.

[chemical formula 18]

The symbols in the chemical formulas (Z1b) to (Z4b) have the same meanings as the symbols in the aforementioned chemical formulas (1) to (4), except for the following symbols, and the preferred forms are also the same. * Indicates bond position.

In the chemical formula (Z4b), X ^41zb represents a hydrogen atom, -L ⁴¹ -(R ⁴¹ )p ₄₁ or -*. X ^42zb represents a hydrogen atom, -L ⁴² -(R ⁴² )p ₄₂ or -*. Either one of X ^41zb and X ^42zb represents -*. * Indicates bond position. L ⁴¹ , R ⁴¹ , p ₄₁ , L ⁴² , R ⁴² and p ₄₂ are as described above.

In the chemical formula (ab), R ^1b to ^{R 3b} each independently represent a hydrogen atom or a substituent. L ^1b represents a single bond, an alkylene group, -COO-, or a combination thereof. L ^2b represents a single bond or an alkylene group. Z represents a group represented by any one of the chemical formulas (Z1a) to (Z4a), or a group represented by any one of the chemical formulas (Z1b) to (Z4b).

R ^1b to ^{R 3b} each independently represent a hydrogen atom or a substituent. As R ^1b to ^{R 3b} , each independently a hydrogen atom, an alkyl group, a cycloalkyl group, a halogen atom, a cyano group or an alkoxycarbonyl group is preferred, a hydrogen atom, a halogen atom or an alkyl group is further preferred, a hydrogen atom or a methyl group better.

L ^1b represents a single bond, an alkylene group, -COO-, or a combination thereof. The aforementioned alkylene group may be either linear or branched. The number of carbon atoms in the alkylene group is preferably 1-4. Examples of the combination group include -COO-alkylene. The aforementioned alkylene group may further have a substituent. As the aforementioned substituents, possible substituents for R ¹¹ to ^{R 13} in the chemical formula (1) can be mentioned. As L ^1b , a single bond or an alkylene group is preferable, and a single bond is more preferable.

L ^2b represents a single bond or an alkylene group. Examples of the aforementioned alkylene group include alkylene groups that may be obtained by L ^a1 in formula (a). L ^2b is preferably an alkylene group.

Z represents a group represented by any one of the chemical formulas (Z1a) to (Z4a), or a group represented by any one of the chemical formulas (Z1b) to (Z4b). Z has the same meaning as Z in the aforementioned chemical formula (aa), and the preferred mode is also the same.

In the chemical formula (ac), R ^1c to ^{R 3c} each independently represent a hydrogen atom or a substituent. L ^1c represents a single bond, an alkylene group, -COO-, an aromatic ring group, or a combination thereof. L ^2c represents a cycloalkylene group. L ^3c represents a single bond or a divalent linking group. Z represents a group represented by any one of the chemical formulas (Z1a) to (Z4a), or a group represented by any one of the chemical formulas (Z1b) to (Z4b).

R ^1c to ^{R 3c} each independently represent a hydrogen atom or a substituent. As R ^1c to R ^3c , each independently hydrogen atom, alkyl, cycloalkyl, halogen atom, cyano or alkoxycarbonyl is preferred, hydrogen atom, halogen atom or alkyl is further preferred, hydrogen atom or methyl better.

L ^1c represents a single bond, an alkylene group, -COO-, an aromatic ring group, or a combination thereof. Examples of L ^1c include L ^a1 in the chemical formula (a). As L ^1c , a single bond, an alkylene group, -COO- or a combination thereof is preferred, and -COO- is more preferred.

L ^2c represents a cycloalkylene group. The aforementioned cycloalkylene group may be either monocyclic or polycyclic. The number of carbon atoms in the cycloalkylene group is preferably 3-15. One or more (for example, one or two) of -CH ₂ - constituting the ring structure of the aforementioned cycloalkylene group may be replaced by heteroatoms (such as -O- and -S-, etc.), -SO ₂ -, -SO ₃ - , alkoxycarbonyl or carbonyl substitution. The aforementioned cycloalkylene group may further have a substituent. As the aforementioned substituents, possible substituents for R ¹¹ to ^{R 13} in the chemical formula (1) can be mentioned.

L ^3c represents a single bond or a divalent linking group. Examples of the aforementioned divalent linking group include -CO-, -O-, -S-, -SO-, -SO ₂ -, -NR ^N -, hydrocarbon groups (e.g., alkylene, cycloalkylene, group, alkenyl group and aryl group, etc.), and a group formed by combining them. R ^N represents a substituent (for example, the possible substituents of the aforementioned R ¹¹ to ^{R 13} ). The aforementioned hydrocarbon group may further have a substituent, and preferably has a halogen atom (preferably a fluorine atom) as the substituent. As L ^3c , an alkylene group which may have a fluorine atom or an alkoxycarbonyl group which may have a fluorine atom is preferable.

Z represents a group represented by any one of the chemical formulas (Z1a) to (Z4a), or a group represented by any one of the chemical formulas (Z1b) to (Z4b). Z has the same meaning as Z in the aforementioned chemical formula (aa), and the preferred mode is also the same.

As the repeating unit a, a repeating unit represented by the chemical formula (ad) or a repeating unit represented by the chemical formula (ae) is preferable.

[chemical formula 19]

The symbols of the repeating unit represented by the chemical formula (ad) and the repeating unit represented by the chemical formula (ae), except for the following symbols, have the same meanings as the symbols of the aforementioned chemical formula (5), and the preferred modes are also the same.

In the chemical formula (ad), R ^1b represents a hydrogen atom or a substituent. Y ^51d represents a ring having -CO-N-CO- and one carbon atom. R ^1d is preferably a hydrogen atom, an alkyl group, a cycloalkyl group, a halogen atom, a cyano group or an alkoxycarbonyl group, further preferably a hydrogen atom, a halogen atom or an alkyl group, and more preferably a hydrogen atom or a methyl group. Examples of Y ^51d include rings having one more carbon atom in Y ⁵¹ in the aforementioned chemical formula (5). The number of carbons contained in Y ^51d is not particularly limited if it is one, and may be two or more.

In the chemical formula (ae), Y ^51e represents -CO-N-CO- and a ring having two carbon atoms. Examples of Y ^51e include rings having two carbon atoms in Y ⁵¹ in the above chemical formula (5). The number of carbons contained in Y ^51e is not particularly limited if it is two, and may be three or more.

As repeating unit a, the repeating unit derived from the following monomer is mentioned, for example.

[chemical formula 20]

[chemical formula 21]

[chemical formula 22]

[chemical formula 23]

The content of the repeating unit a is preferably at least 1 mol %, more preferably at least 10 mol %, more preferably at least 30 mol %, particularly preferably at least 40 mol %, based on all the repeating units of resin A. The upper limit is preferably less than 100 mol%, further preferably 90 mol% or less, more preferably 70 mol% or less, based on the total repeating units. In addition, when the photoresist composition only satisfies the aforementioned condition B, the content of the repeating unit a relative to the total repeating units of the resin A is at least 10 mol%, preferably at least 30 mol%, and 40 mol% More than % is better. The upper limit is preferably less than 100 mol%, further preferably 90 mol% or less, more preferably 70 mol% or less, based on the total repeating units. When there are two or more resins A, the content of the repeating unit a is preferably 40 mol% or more of one or more resins A relative to all the repeating units. In this case, the content of the repeating unit a is preferably 30 to 100% by mass, and furthermore 60 to 100% by mass based on the total content of the resin A. Preferable, more preferably containing 80 to 100% by mass.

<A repeating unit having an acidic group> The resin A may contain a repeating unit having an acidic group. The repeating unit having an acid group is preferably different from the above-mentioned repeating unit. The acid dissociation constant (pKa) of the acid group is preferably 13 or less, more preferably 3-13, and more preferably 5-10. When the resin A has an acid group with a pKa of 13 or less, the content of the acid group in the resin A is at most 0.2~6.0mmol/g, preferably 0.8~6.0mmol/g, and 1.2~5.0mmol/g More preferably, 1.6~4.0mmol/g is more preferable. If the content of the acid group is within the above-mentioned range, image development will proceed favorably, the pattern shape to be formed will be excellent, and the resolution will also be excellent. The acid group is preferably a carboxyl group, a hydroxyl group, a phenolic hydroxyl group, a fluorinated alcohol group (hexafluoroisopropanol group), a sulfonic acid group, a sulfonamide group, or an isopropanol group. In the hexafluoroisopropanol group, one or more (preferably 1 to 2) fluorine atoms may be substituted by groups other than fluorine atoms (for example, alkoxycarbonyl, etc.). As the acid group, -C(CF ₃ )(OH)-CF ₂ - formed as described above is also preferable. In addition, one or more fluorine atoms may be substituted by groups other than fluorine atoms to form a ring containing -C(CF ₃ )(OH)-CF ₂ -. The repeating unit having an acid group may have a fluorine atom or an iodine atom.

As the repeating unit having an acid group, a repeating unit represented by the following chemical formula (B) is preferable.

[chemical formula 24]

R ₃ represents a hydrogen atom, or an organic group that may have a valence of a fluorine atom or an iodine atom. The organic group which may have a valence of a fluorine atom or an iodine atom is preferably a group represented by -L ₄ -R ₈ . L ₄ represents a single bond or -COO-. R ₈ represents 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 combination thereof.

R ₄ and R ₅ each independently represent a hydrogen atom, a fluorine atom, an iodine atom, or an alkyl group which may have a fluorine atom or an iodine atom.

L ₂ represents a single bond, preferably -COO- or -CO-, -O-, and an alkylene group (preferably having 1 to 6 carbon atoms. It may be linear or branched. In addition, - CH ₂ -a divalent group formed by a combination of heteroatoms).

L ₃ represents (n+m+1)-valent aromatic ring group or (n+m+1)-valent alicyclic group. The aromatic ring group may be either monocyclic or polycyclic. For example, a phenyl ring group and a naphthyl ring group are mentioned. The alicyclic group may be any of monocyclic and polycyclic. For example, cycloalkyl ring group, norbornene ring group and adamantane ring group are mentioned.

R ₆ represents a hydroxyl group or a fluorinated alcohol group. The fluorinated alcohol group is preferably a valent group represented by the chemical formula (3L). *-L _6X -R _6X (3L) L _6X represents a single bond or a divalent linking group. Examples of the divalent linking group include -CO-, -O-, -SO-, -SO ₂ -, -NR ^A - ( ^RA represents a hydrogen atom or an alkyl group having 1 to 6 carbons.) , an alkylene group (preferably having 1 to 6 carbon atoms. It may be a straight chain or a branched chain.), and a divalent linking group formed by combining a plurality of these. In addition, the aforementioned alkylene group may have a substituent. As a substituent, a halogen atom (preferably a fluorine atom) and a hydroxyl group are mentioned, for example. R _6X represents a hexafluoroisopropanol group. In addition, when R ₆ is a hydroxyl group, it is also preferable that L ₃ is an aromatic ring group with a valence of (n+m+1).

R ₇ represents a halogen atom. Examples of the halogen atom include a fluorine atom, a chlorine atom, a bromine atom and an iodine atom. m represents an integer of 1 or more. As m, the integer of 1-3 is preferable, and the integer of 1-2 is more preferable. n represents an integer of 0 or 1 or more. As n, an integer of 1-4 is preferable. As (n+m+1), an integer of 1-5 is preferable.

As a repeating unit which has an acid group, the following repeating unit is mentioned, for example.

[chemical formula 25]

[chemical formula 26]

[chemical formula 27]

The content of the repeating unit having an acid group is preferably 5 mol% or more, more preferably 10 mol% or more, based on the total repeating units of the resin A. The upper limit is preferably not more than 70 mol%, further preferably not more than 65 mol%, and more preferably not more than 60 mol%, based on the total repeating units of the resin A.

<Acid-decomposable group> Resin A preferably has an acid-decomposable group. The acid decomposition group does not include the above-mentioned specific groups. In addition, some acid-decomposable groups do not have specific groups. That is, the repeating unit b does not contain the repeating unit a. The so-called "acid decomposable group" refers to a group that is decomposed by the action of an acid to produce a polar group. The acid-decomposable group preferably has a structure in which a polar group is protected by a detachment group detached by the action of an acid. Regarding the acid decomposable group, it will be described below. Therefore, in the photoresist composition of the present invention, typically, when an alkaline developer is used as the developer, a positive pattern is preferably formed, and when an organic developer is used as the developer, it is preferably A negative pattern is formed. Hereinafter, the resin A having an acid-decomposable group may also be referred to as an acid-decomposable resin.

As a polar group, an alkali-soluble group is preferable. As the alkali-soluble group, for example, carboxyl group, phenolic hydroxyl group, fluorinated alcohol group, sulfonic acid group, phosphoric acid group, sulfonamide group, sulfonimide group, (alkylsulfonyl) (alkylcarbonyl group) ) methylene, (alkylsulfonyl)(alkylcarbonyl)imide, bis(alkylcarbonyl)methylene, bis(alkylcarbonyl)imide, bis(alkylsulfonyl) ) methylene, acidic groups such as bis(alkylsulfonyl)imide, tris(alkylcarbonyl)methylene and tris(alkylsulfonyl)methylene, and alcoholic hydroxyl groups. As described above, the acid-decomposable group preferably has a structure in which a polar group is protected by a detachment group detached by the action of an acid. Examples of the leaving group detached by the action of an acid include groups represented by chemical formulas (Y1) to (Y4). Chemical formula (Y1): -C(R _x1 )(R _x2 )(R _x3 ) Chemical formula (Y2): -C(=O)OC(R _x1 )(R _x2 )(R _x3 ) Chemical formula (Y3): -C (R ₃₆ )(R ₃₇ )(OR ₃₈ ) Chemical formula (Y4): -C(Rn)(H)(Ar)

In chemical formula (Y1) and chemical formula (Y2), Rx ₁ ～Rx ₃ independently represent alkyl (straight chain or branched, carbon number 1～6 is preferred), cycloalkyl (monocyclic or polycyclic, carbon 3 to 15 are preferred), alkenyl (straight chain or branched, preferably 2 to 6 carbons), aryl (monocyclic or polycyclic, preferably 6 to 15 carbons), or heteroaryl ( Monocyclic or polycyclic rings, preferably with 5 to 15 ring members). Two of Rx ₁ to Rx ₃ may be bonded to each other to form a ring. The aforementioned ring may be either monocyclic or polycyclic. As monocyclic and polycyclic rings, for example, cycloalkane rings can be mentioned. As the aforementioned cycloalkane ring, monocyclic cycloalkane rings such as cyclopentane ring and cyclohexane ring, or polycyclic rings such as norbornane ring, tetracyclodecane ring, tetracyclododecane ring and adamantane ring An alkane ring is preferred. In the aforementioned cycloalkane ring, for example, one or more methylene groups (for example, 1 to 3) constituting one ring may be replaced by a heteroatom (-O- or -S-, etc.), -SO ₂ -, -SO ₃ -, -COO-, carbonyl or vinylidene substitution. In addition, among the aforementioned cycloalkane rings, one or more ethylene groups (for example, 1 to 2) constituting one of the cycloalkane rings may be substituted with vinylene groups. In the chemical formula (Y1), two of Rx ₁ to _{Rx 3} are bonded to each other to form a cycloalkane ring, and for the C (carbon) atom in the chemical formula (Y1), the aforementioned cycloalkane ring forms a vinylene ring with the α carbon and the γ carbon. In the basic case, the remaining one of _Rx1 ~ _Rx3 can be a hydrogen atom.

In the chemical formula (Y3), R ₃₆ to R ₃₈ each independently represent a hydrogen atom or an organic group. As the aforementioned organic group, alkyl (straight chain or branched, preferably with 1 to 6 carbons), cycloalkyl (monocyclic or polycyclic, preferably with 3 to 15 carbons), aryl (monocyclic or polycyclic, preferably 3 to 15 carbons), ring, preferably with 6-15 carbons), aralkyl group (preferably with 7-18 carbons), or alkenyl (straight-chain or branched, preferably with 2-6 carbons). R ₃₇ and R ₃₈ may be bonded to each other to form a ring. As the ring formed above, for example, the same rings as monocyclic or polycyclic rings that can be formed by bonding two of Rx ₁ to Rx ₃ can be mentioned.

In the chemical formula (Y4), Ar represents an aromatic ring group. Rn represents an alkyl group (straight chain or branched chain, preferably 1 to 6 carbons), cycloalkyl (monocyclic or polycyclic, preferably 3 to 15 carbons), or aryl (monocyclic or polycyclic, preferably carbon Number 6-15 is better). Rn and Ar may be bonded to each other to form a non-aromatic ring. Rn is preferably an aryl group (monocyclic or polycyclic, preferably having 6 to 15 carbon atoms).

(Repeating Units Having Acid-Decomposable Groups) The resin A preferably contains repeating units having acid-decomposable groups (hereinafter also referred to as "repeating units b").

The repeating unit b preferably has at least one member selected from the group consisting of repeating units represented by any one of the chemical formulas (M1) to (M5), and preferably has a repeating unit selected from the chemical formula At least one of the group consisting of the repeating unit represented by (M4) and the repeating unit represented by the chemical formula (M5).

[chemical formula 28]

In the chemical formula (M1), R ^m11 to R ^m13 each independently represent a hydrogen atom, an alkyl group, a cycloalkyl group, a halogen atom, a cyano group or an alkoxycarbonyl group. L ^m11 represents a single bond or a divalent linking group. R ^m14 ~ R ^m16 independently represent an alkyl group, a cycloalkyl group, an aryl group, an aralkyl group or an alkenyl group. At least two of R ^m14 to R ^m16 may be bonded to each other to form a ring.

R ^m11 to R ^m13 each independently represent a hydrogen atom, an alkyl group, a cycloalkyl group, a halogen atom, a cyano group or an alkoxycarbonyl group. The aforementioned alkyl group may be either linear or branched. The carbon number of the alkyl group is preferably 1-6. The aforementioned cycloalkyl group may be either monocyclic or polycyclic. The carbon number of the aforementioned cycloalkyl group is preferably 3-15. Examples of the halogen atom include a fluorine atom, a chlorine atom, a bromine atom and an iodine atom. The number of carbon atoms in the alkoxycarbonyl group is preferably 1-10. As an alkyl moiety in the said alkoxycarbonyl group, the thing similar to the said alkyl group is mentioned, for example. R ^m11 is preferably a hydrogen atom or an alkyl group, further preferably an alkyl group, and more preferably a methyl group. R ^m12 and R ^m13 are preferably a hydrogen atom or an alkyl group, more preferably a hydrogen atom.

L ^m11 represents a single bond or a divalent linking group. Examples of the divalent linking group include -CO-, -O-, -S-, -SO-, -SO ₂ -, -NR ^N - (R ^N represents a substituent), hydrocarbon groups (for example, alkylene, cycloalkylene, alkenylene, arylylene, etc.), and groups formed by combining them. The aforementioned hydrocarbon group may further have a substituent, and preferably has a halogen atom as the substituent. L ^m11 is preferably a single bond or an alkylene group.

R ^m14 ~ R ^m16 independently represent an alkyl group, a cycloalkyl group, an aryl group, an aralkyl group or an alkenyl group. The aforementioned alkyl group may be either linear or branched. The carbon number of the aforementioned alkyl group is preferably 1-6, more preferably 1-3. The aforementioned cycloalkyl group may be either monocyclic or polycyclic. The number of carbon atoms in the cycloalkyl group is preferably 3-15. The aforementioned aryl group may be either monocyclic or polycyclic. The carbon number of the aforementioned aryl group is preferably 6-15. The carbon number of the aforementioned aralkyl group is preferably 7-18. The aforementioned alkenyl group may be either linear or branched. The carbon number of the aforementioned alkenyl group is preferably 2-6. The aforementioned alkyl group, the aforementioned cycloalkyl group, the aforementioned aryl group, the aforementioned aralkyl group, and the aforementioned alkenyl group may further have a substituent, and the substituent preferably has a halogen atom (preferably a fluorine atom). As R ^m14 to ^{R m16} , an alkyl group or an aryl group is preferable, and an alkyl group is more preferable.

In the chemical formula (M2), R ^m21 to R ^m24 each independently represent a hydrogen atom or an organic group. Wherein, at least one of R ^m21 and R ^m22 represents an organic group. X ^m21 represents -CO-, -SO- or -SO ₂ -. Y ^m21 represents -O-, -S-, -SO-, -SO ₂ - or -NR ³⁴ -. R ³⁴ represents a hydrogen atom or an organic group. L ^m21 represents a single bond or a divalent linking group. R ^m25 ～R ^m27 independently represent alkyl, cycloalkyl, aryl, aralkyl or alkenyl respectively. At least two of R ^m25 to R ^m27 may be bonded to each other to form a ring.

R ^m21 ~ ^{R m24} each independently represent a hydrogen atom or an organic group. Wherein, at least one of R ^m21 and R ^m22 represents an organic group. As the aforementioned organic group, alkyl (straight chain or branched, preferably with 1 to 6 carbons), cycloalkyl (monocyclic or polycyclic, preferably with 3 to 15 carbons), aryl (monocyclic or polycyclic, preferably 3 to 15 carbons), ring, preferably with 6-15 carbons), aralkyl group (preferably with 7-18 carbons), or alkenyl (straight-chain or branched, preferably with 2-6 carbons). As R ^m21 and R ^m22 , an alkyl group is preferable, and a hydrocarbon group having a fluorine atom is more preferable. As R ^m23 and R ^m24 , a hydrogen atom or an alkyl group is preferable, and a hydrogen atom is more preferable.

X ^m21 represents -CO-, -SO- or -SO ₂ -. X ^m21 is preferably -CO-. Y ^m21 represents -O-, -S-, -SO-, -SO ₂ - or -NR ³⁴ -. As Y ^m21 , -O- or -S- is preferable, and -O- is more preferable. R ³⁴ represents a hydrogen atom or an organic group. R ³⁴ is preferably an organic group. As the aforementioned organic group, for example, organic groups that can be obtained from R ^m21 to R ^m24 in the aforementioned chemical formula (M2) can be mentioned.

L ^m21 represents a single bond or a divalent linking group. Examples of the divalent linking group include -CO-, -O-, -S-, -SO-, -SO ₂ -, -NR ^N - (R ^N represents a substituent), hydrocarbon groups (for example, alkylene, cycloalkylene, alkenylene, arylylene, etc.), and groups formed by combining them. The aforementioned hydrocarbon group may further have a substituent, and preferably has a halogen atom as the substituent. As L ^m21 , a hydrocarbon group is preferable, and an alkylene group is more preferable.

R ^m25 ～R ^m27 independently represent alkyl, cycloalkyl, aryl, aralkyl or alkenyl respectively. The aforementioned alkyl group may be either linear or branched. The carbon number of the alkyl group is preferably 1-6. The aforementioned cycloalkyl group may be either monocyclic or polycyclic. The number of carbon atoms in the cycloalkyl group is preferably 3-15. The aforementioned aryl group may be either monocyclic or polycyclic. The carbon number of the aforementioned aryl group is preferably 6-15. The carbon number of the aforementioned aralkyl group is preferably 7-18. The aforementioned alkenyl group may be either linear or branched. The carbon number of the aforementioned alkenyl group is preferably 2-6. The aforementioned alkyl group, the aforementioned cycloalkyl group, the aforementioned aryl group, the aforementioned aralkyl group, and the aforementioned alkenyl group may further have a substituent, and the substituent preferably has a halogen atom (preferably a fluorine atom). R ^m25 to R ^m27 are preferably alkyl or aryl. At least two of R ^m25 to R ^m27 may be bonded to each other to form a ring.

In the chemical formula (M3), R ^m31 and R ^m32 each independently represent a hydrogen atom or an organic group. R ^m33 and R ^m34 each independently represent a hydrogen atom, an alkyl group, a cycloalkyl group, an aryl group, an aralkyl group, or an alkenyl group. At least two of R ^m31 to ^{R m34} may be bonded to each other to form a ring.

As the aforementioned organic group, for example, organic groups that can be obtained from R ^m21 to R ^m24 in the aforementioned chemical formula (M2) can be mentioned. As R ^m31 and R ^m32 , a hydrogen atom or an alkyl group is preferable, and a hydrogen atom is more preferable. Examples of R ^m33 and R ^m34 include groups that can be obtained from R ^m25 to R ^m27 in the aforementioned chemical formula (M2), and are preferably hydrogen atoms or alkyl groups. At least two of R ^m31 to ^{R m34} may be bonded to each other to form a ring. Among them, R ^m31 and R ^m32 , and R ^m33 and R ^m34 are preferably bonded to each other to form a ring.

In the chemical formula (M4), R ^m41 to R ^m43 each independently represent a hydrogen atom, an alkyl group, a cycloalkyl group, a halogen atom, a cyano group or an alkoxycarbonyl group. L ^m41 represents a single bond or a divalent linking group. ^Arm41 represents an aromatic ring group. R ^m44 ~R ^m46 each independently represent a hydrogen atom, an alkyl group, a cycloalkyl group, an aryl group, an aralkyl group or an alkenyl group. At least two of R ^m44 to R ^m46 may be bonded to each other to form a ring.

R ^m41 ~R ^m43 each independently represent a hydrogen atom, an alkyl group, a cycloalkyl group, a halogen atom, a cyano group or an alkoxycarbonyl group. The aforementioned alkyl group may be either linear or branched. The carbon number of the aforementioned alkyl group is preferably 1-6, more preferably 1-3. The aforementioned cycloalkyl group may be either monocyclic or polycyclic. The number of carbon atoms in the cycloalkyl group is preferably 3-15. As a halogen atom, a fluorine atom, a chlorine atom, a bromine atom, and an iodine atom are mentioned, for example. The number of carbon atoms in the alkoxycarbonyl group is preferably 1-10. As an alkyl moiety in the said alkoxycarbonyl group, the thing similar to the said alkyl group is mentioned, for example. As R ^m41 to ^{R m43} , a hydrogen atom or an alkyl group (preferably a methyl group) is preferable, and a hydrogen atom is more preferable.

L ^m41 represents a single bond or a divalent linking group. Examples of L ^m41 include groups that can be obtained by L ^m11 in the aforementioned chemical formula (M1), preferably a single bond.

^Arm41 represents an aromatic ring group. The aforementioned aromatic ring group may be either monocyclic or polycyclic. The number of ring atoms of the aforementioned aromatic ring group is preferably 5-15. The aforementioned aromatic ring group may have one or more (for example, 1 to 5) heteroatoms (for example, oxygen atom, sulfur atom, and/or nitrogen atom, etc.) as member ring atoms. As the aforementioned aromatic ring group, a benzene ring group or a naphthyl ring group is preferable, and a benzene ring is more preferable.

R ^m44 ~R ^m46 each independently represent a hydrogen atom, an alkyl group, a cycloalkyl group, an aryl group, an aralkyl group or an alkenyl group. Examples of R ^m44 to ^{R m46} include groups that can be obtained from R ^m25 to R ^m27 in the aforementioned chemical formula (M2). R ^m44 to ^{R m46} are preferably a hydrogen atom or an alkyl group (preferably a methyl group). At least two of R ^m44 to R ^m46 may be bonded to each other to form a ring. Among them, R ^m45 and R ^m47 are preferably bonded to each other to form a ring. In addition, Ar ^m41 may bond with R ^m43 or R ^m44 to form a ring.

In the chemical formula (M5), R ^m51 to R ^m53 each independently represent a hydrogen atom, an alkyl group, a cycloalkyl group, a halogen atom, a cyano group or an alkoxycarbonyl group. L ^m51 represents a single bond or a divalent linking group. R ^m54 and R ^m55 each independently represent a hydrogen atom, an alkyl group, a cycloalkyl group, an aryl group, an aralkyl group or an alkenyl group. R ^m56 represents an alkyl group, a cycloalkyl group, an aryl group, an aralkyl group or an alkenyl group. At least two of R ^m54 to R ^m56 may be bonded to each other to form a ring.

R ^m51 ~ ^{R m53} respectively have the same meaning as R ^m41 ~ ^{R m43} in the aforementioned chemical formula (M4), and the preferred mode is also the same. L ^m51 has the same meaning as L ^m41 in the aforementioned chemical formula (M4), and the preferred mode is also the same. R ^m54 ~ ^{R m56} have the same meanings as R ^m25 ~ R ^m27 in the aforementioned chemical formula (M2), and the preferred modes are also the same. At least two of R ^m54 to R ^m56 may be bonded to each other to form a ring. Among them, it is preferable that R ^m55 and R ^m56 are bonded to each other to form a ring.

The content of the repeating unit b is preferably at least 1 mol%, further preferably at least 10 mol%, and more preferably at least 15 mol%, based on all the repeating units in the resin A. The upper limit is preferably not more than 80 mol%, further preferably not more than 70 mol%, and more preferably not more than 60 mol%, based on the total repeating units of the resin A.

<Repeating unit having a lactone group> The resin A may contain a repeating unit having a lactone group. The repeating unit having a lactone group may or may not correspond to the aforementioned repeating unit. For example, a repeating unit having a lactone group may or may not correspond to repeating unit a, or may or may not correspond to a repeating unit having an acid-decomposable group as long as the repeating unit has a lactone group.

The lactone group is not particularly limited as long as it has a lactone structure or a sultone structure. The lactone structure is preferably a 5-7-membered cyclic lactone structure, and it is preferable to condense other ring structures with the 5-7-membered cyclic lactone structure in a manner of forming a bicyclic structure or a spiro ring structure. Resin A preferably contains a repeating unit with a lactone group, and the lactone group is removed from the lactone structure represented by any one of the chemical formulas (LC1-1) to (LC1-21) (for example, 1 ~2) hydrogen atoms. In addition, the lactone group can also be directly bonded to the main chain. For example, the member ring atoms of the lactone group may form part of the backbone of resin A.

[chemical formula 29]

The aforementioned lactone structure may have a substituent (Rb ₂ ) as the substituent (Rb ₂ ), for example, an alkyl group having 1 to 8 carbons, a cycloalkyl group having 4 to 7 carbons, a cycloalkyl group having 1 to 8 carbons, Alkoxyl group, alkoxycarbonyl group with 1 to 8 carbon atoms, carboxyl group, halogen atom, hydroxyl group, cyano group, group containing acid decomposable group (may be acid decomposable group itself), and combinations thereof group. n ₂ represents an integer of 0-4. When n ₂ is 2 or more, a plurality of Rb ₂ may be the same or different, and a plurality of Rb ₂ may be bonded to each other to form a ring. Among the member ring atoms of the aforementioned lactone structure, one or more methylene groups (for example, 1 to 2) that are not adjacent to -COO- or O- may be substituted by heteroatoms such as -O- or -S-.

As a repeating unit which has a lactone group, the repeating unit represented by chemical formula (AI) is mentioned, for example.

[chemical formula 30]

In the chemical formula (AI), Rb ₀ represents a hydrogen atom, a halogen atom, or an optionally substituted alkyl group having 1 to 4 carbon atoms. As the aforementioned substituent, a hydroxyl group or a halogen atom is preferred. As a halogen atom, a fluorine atom, a chlorine atom, a bromine atom, and an iodine atom are mentioned, for example. Rb 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, -COO-, a carbonyl group, a carboxyl group, or a combination thereof. Among them, a single bond or a linking group represented by -Ab ₁ -COO- is preferable. Ab ₁ represents a linear or branched alkylene group, or a monocyclic or polycyclic ring alkylene group. Among them, methylene group, ethylene group, cyclohexyl group, adamantyl group or norbornyl group are preferable. V represents a group formed by removing one hydrogen atom from a member ring atom of the lactone structure represented by any one of the chemical formulas (LC1-1) to (LC1-21).

The repeating unit having a lactone group is preferably a repeating unit represented by chemical formula (AII) or a repeating unit represented by (AIII).

[chemical formula 31]

In the chemical formulas (AII) and (AIII), RIII each independently represents a hydrogen atom or a substituent. RIII is preferably a hydrogen atom. ahd ₁ represents a group formed by removing one hydrogen atom from each of adjacent member ring atoms of the lactone structure represented by any one of the chemical formulas (LC1-1) to (LC1-21). ahd ₂ represents a group formed by removing two hydrogen atoms from one member ring atom of the lactone structure represented by any one of the chemical formulas (LC1-1) to (LC1-21).

As a repeating unit which has a lactone group, the following repeating unit is mentioned, for example.

[chemical formula 32]

[chemical formula 33]

When there is an optical isomer in the repeating unit having a lactone group, any optical isomer can be used. In addition, one kind of optical isomers may be used alone, or a plurality of optical isomers may be used in combination. When one optical isomer is used as the main body, the optical purity (ee) is preferably 90 or higher, more preferably 95 or higher. The upper limit is preferably 100 or less.

The content of the repeating unit having a lactone group is preferably 5 to 99 mol%, more preferably 10 to 80 mol%, more preferably 15 to 65 mol%, based on all the repeating units of resin A. Among the repeating units having a lactone group, the total of the repeating units having a lactone group corresponding to the repeating unit a and the repeating units having a lactone group not corresponding to the repeating unit a may satisfy the aforementioned preferred content; The repeating unit of the lactone group of the unit a alone may satisfy the aforementioned preferred content; the repeating unit having a lactone group not corresponding to the repeating unit a may independently satisfy the aforementioned preferred content.

<Repeating unit having sultone group or carbonate group> Resin A may contain a repeating unit having sultone group. There is no particular limitation on the sultone group as long as it has a sultone structure. The sultone structure is preferably a 5-7 membered ring sultone structure, and it is more preferable to condense other ring structures with the 5-7 membered ring sultone structure to form a bicyclic structure or a spiro ring structure. In addition, the sultone group can also be directly bonded to the main chain. For example, ring atoms that are members of the sultone group may form part of the backbone of resin A. Resin A preferably contains repeating units having a sultone group, and the sultone group is a member ring atom of the sultone structure represented by any one of the chemical formulas (SL1-1) to (SL1-3) It is formed by removing more than one (for example, 1 to 2) hydrogen atoms.

[chemical formula 34]

The aforementioned sultone structure may have a substituent (Rb ₂ ) _. Regarding the substituent (Rb ₂ ) in the chemical formulas (SL1-1) to (SL1-3), it can be combined with the substituent (Rb ₂ ) in the lactone structure represented by the aforementioned chemical formulas (LC1-1) to (LC1-21) ) for the same description. Among the member ring atoms of the aforementioned sultone structure, at least one (for example, 1 to 2) methylene groups not adjacent to -COO- or -O- may be substituted by a heteroatom such as -O- or -S-.

As the repeating unit having a sultone group, for example, in the repeating unit represented by the aforementioned chemical formula (AI), V is represented by any one of the chemical formulas (SL1-1) to (SL1-3). A repeating unit replaced by a group formed by removing a hydrogen atom from a member ring atom of the sultone structure; in the repeating unit represented by the aforementioned chemical formula (AII), ahd ₁ is changed from chemical formula (SL1-1) to (SL1 -3) in any one of the sultone structures represented by the adjacent ring members of the ring atoms each removed a hydrogen atom to form a group-substituted repeating unit; and, in the repeating unit represented by the aforementioned chemical formula (AIII) In the unit, ahd ₂ is a repeating unit replaced by a group formed by removing two hydrogen atoms from a member ring atom of the sultone structure represented by any one of the chemical formulas (SL1-1) to (SL1-3) .

As the carbonate group, a cyclic carbonate group is preferred. As the repeating unit having a cyclic carbonate group, it is preferably a repeating unit represented by chemical formula (A-1).

[chemical formula 35]

In the chemical formula (A-1), R _A ¹ represents a hydrogen atom, a halogen atom or a monovalent organic group (preferably a methyl group). n represents an integer of 0 or more. R _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. As the aforementioned divalent linking group, it is preferably an alkylene group, a divalent linking group with a monocyclic or polycyclic alicyclic hydrocarbon structure, -O-, -COO -, carbonyl, carboxyl, or a combination thereof. Z represents a ring having -O-CO-O-. The aforementioned ring may be either monocyclic or polycyclic.

As a repeating unit which has a sultone group or a carbonate group, the following repeating unit is mentioned, for example.

[chemical formula 36]

The content of the repeating unit having a sultone group or a carbonate group is preferably 1 mol % or more, more preferably 10 mol % or more, based on the total repeating units of the resin A. The upper limit is preferably not more than 85 mol%, further preferably not more than 80 mol%, more preferably not more than 70 mol%, and particularly preferably not more than 60 mol%, based on the total repeating units of resin A.

<Repeating unit having a fluorine atom or an iodine atom> The resin A may contain a repeating unit having a fluorine atom or an iodine atom. The repeating unit having a fluorine atom or an iodine atom is preferably different from the aforementioned repeating unit.

The repeating unit having a fluorine atom or an iodine atom is preferably a repeating unit represented by the chemical formula (C).

[chemical formula 37]

L ₅ represents a single bond or -COO-. R ₉ represents a hydrogen atom or an alkyl group which may have a fluorine atom or an iodine atom. R ₁₀ represents an alkyl group which may have a hydrogen atom, 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 combination thereof .

Examples of the repeating unit having a fluorine atom or an iodine atom include the following repeating units.

[chemical formula 38]

The content of the repeating unit having a fluorine atom or an iodine atom is preferably at least 1 mol%, further preferably at least 5 mol%, and more preferably at least 10 mol%, based on the total repeating units of resin A. The upper limit is preferably not more than 50 mol%, further preferably not more than 45 mol%, and more preferably not more than 40 mol%, based on the total repeating units of the resin A. In addition, it is also preferable not to contain repeating units having fluorine atoms or iodine atoms.

<The repeating unit represented by the chemical formula (V-1) or the repeating unit represented by the chemical formula (V-2)> Resin A may have the repeating unit represented by the chemical formula (V-1) or the repeating unit represented by the chemical formula (V-2) repeat unit. The repeating unit represented by chemical formula (V-1) and the repeating unit represented by chemical formula (V-2) are preferably different from the aforementioned repeating units.

[chemical formula 39]

In the chemical formulas (V-1) and (V-2), _R6 and _R7 each independently represent 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 , -OCOR or -COOR (R represents an alkyl group or fluorinated alkyl group having 1 to 6 carbon numbers), or a carboxyl group. The alkyl group is preferably a linear, branched or cyclic C 1-10 alkyl group. n ₃ represents an integer of 0-6. n ₄ represents an integer of 0-4. X ⁴ represents a methylene group, an oxygen atom or a sulfur atom. Examples of the repeating unit represented by the chemical formula (V-1) and the repeating unit represented by the chemical formula (V-2) include those described in paragraph [0100] of International Publication No. 2018/193954.

The content of the repeating unit represented by the chemical formula (V-1) or the repeating unit represented by the chemical formula (V-2), relative to all the repeating units of the resin A, is preferably 1-65 mol%, 5-45 mol% better.

<Repeating unit for reducing the mobility of the main chain> The resin A may have a repeating unit for reducing the mobility of the main chain. The repeating units used to reduce the mobility of the main chain are preferably different from the aforementioned repeating units. From the viewpoint of being able to suppress excessive diffusion of generated acid or pattern collapse during development, resin A with a higher glass transition temperature (Tg) is preferable. Tg is preferably over 90°C, more preferably over 100°C, more preferably over 110°C, and particularly preferably over 125°C. In addition, if the Tg temperature is too high, the dissolution rate in the developer will decrease, so the Tg is preferably below 400°C, more preferably below 350°C.

In addition, the glass transition temperature (Tg) of polymers, such as resin A, was computed by the following method. First, the Tg of a homopolymer composed only of each repeating unit contained in the polymer was calculated by the Bicerano method (hereinafter also referred to as "Tg of repeating unit"). Next, the mass ratio (%) of each repeating unit to all repeating units in the polymer was calculated. Next, Tg at each mass ratio was calculated using the Fox chemical formula (described in Materials Letters 62 (2008) 3152, etc.), and the total was taken as Tg (°C) of the polymer. The Bicerano method is described in Prediction of polymer properties, Marcel Dekker Inc, New York (1993) et al. In addition, calculation of Tg by the Bicerano method can be performed using MDL Polymer (MDL Information Systems, Inc.), a software for estimating physical properties of polymers.

In order to increase the Tg of the resin A (preferably to make the Tg exceed 90°C), it is preferable to reduce the mobility of the main chain of the resin A. As a method of reducing the mobility of the resin A main chain, for example, methods (a) to (e) are mentioned. (a) Introduce fluffy substituents into the main chain (b) Introduce multiple substituents into the main chain (c) Introduce substituents that cause interactions between resins A near the main chain (d) Formed in a ring structure Main chain (e) Linking the ring structure to the main chain In addition, the resin A preferably has a repeating unit whose homopolymer Tg is 130°C or higher. In addition, the type of the repeating unit whose Tg of the homopolymer is 130°C or higher may be any repeating unit whose Tg of the homopolymer calculated by the Bicerano method is 130°C or higher. Moreover, it corresponds to the repeating unit whose Tg of a homopolymer is 130 degreeC or more depending on the kind of the functional group in the repeating unit represented by following chemical formula (A)-(E).

(Repeating unit represented by chemical formula (Aa)) As a specific method of the aforementioned (a), for example, a method of introducing a repeating unit represented by chemical formula (Aa) into resin A can be mentioned.

[chemical formula 40]

In the chemical formula (Aa), R _A represents a group having a polycyclic structure. R _x represents a hydrogen atom, a methyl group or an ethyl group. The "group having a polycyclic structure" refers to a group having a plurality of ring structures, and the plurality of ring structures may or may not be condensed. Examples of the repeating unit represented by the chemical formula (Aa) include those described in paragraphs [0107] to [0119] of International Publication No. 2018/193954. The content of the repeating unit represented by the chemical formula (Aa) is preferably 1-65 mol %, more preferably 5-45 mol %, relative to all the repeating units of resin A.

(Repeating unit represented by chemical formula (B)) As a specific method of (b) above, for example, a method of introducing a repeating unit represented by chemical formula (B) into resin A can be mentioned.

[chemical formula 41]

In the chemical formula (B), R _b1 to _{R b4} each independently represent a hydrogen atom or an organic group. At least two or more of R _b1 to R _b4 represent organic groups. In addition, when at least one of the organic groups is a group in which the ring structure is directly linked to the main chain in the repeating unit, the type of other organic groups is not particularly limited. In addition, when none of the organic groups is a group in which the ring structure is directly linked to the main chain in the repeating unit, at least two or more of the organic groups are substituents having three or more constituent atoms other than hydrogen atoms. The repeating unit represented by the chemical formula (B) includes, for example, those described in paragraphs [0113] to [0115] of International Publication No. 2018/193954. The content of the repeating unit represented by the chemical formula (B) is preferably 1-65 mol%, more preferably 5-45 mol%, relative to all the repeating units of resin A.

(Repeating unit represented by chemical formula (C)) As a specific method of the aforementioned (c), for example, a method of introducing a repeating unit represented by chemical formula (C) into resin A can be mentioned.

[chemical formula 42]

In the chemical formula (C), R _c1 to _{R c4} each independently represent a hydrogen atom or an organic group. At least one of R _c1 to R _c4 represents a group having a hydrogen-bonding hydrogen atom within 3 atoms starting from a main chain carbon atom. Among them, from the viewpoint of causing interaction between the main chains of the resin A, hydrogen atoms having hydrogen bonding properties within 2 atoms (closer to the main chain side) are preferable. Examples of the repeating unit represented by the chemical formula (C) include those described in paragraphs [0119] to [0121] of International Publication No. 2018/193954. The content of the repeating unit represented by the chemical formula (C) is preferably 1-65 mol%, more preferably 5-45 mol%, relative to all the repeating units of resin A.

(Repeating unit represented by chemical formula (D)) As a specific method of (d) above, for example, a method of introducing a repeating unit represented by chemical formula (D) into resin A can be mentioned.

[chemical formula 43]

In the chemical formula (D), "cylic" represents a group that forms a main chain with a ring structure. The number of atoms constituting the ring is not particularly limited. As the repeating unit represented by the chemical formula (D), for example, those described in paragraphs [0126] to [0027] of International Publication No. 2018/193954 can be mentioned. The content of the repeating unit represented by the chemical formula (D) is preferably 1-65 mol%, more preferably 5-45 mol%, relative to all the repeating units of the resin A.

(Repeating unit represented by chemical formula (E)) As a specific method of (e) above, for example, a method of introducing a repeating unit represented by chemical formula (E) into resin A can be mentioned.

[chemical formula 44]

In the chemical formula (E), Re each independently represents a hydrogen atom or an organic group. As an organic group, an alkyl group, a cycloalkyl group, an aryl group, an aralkyl group, and an alkenyl group are mentioned, for example. The aforementioned organic group may further have a substituent. "cylic" is a cyclic group having carbon atoms in the main chain. There is no particular limitation on the number of atoms contained in the cyclic group. As the repeating unit represented by the chemical formula (E), for example, those described in paragraphs [0131] to [0133] of International Publication No. 2018/193954 can be mentioned. The content of the repeating unit represented by the chemical formula (E) is preferably 1-65 mol%, more preferably 5-45 mol%, relative to all the repeating units of resin A.

<Repeating unit having hydroxyl group or cyano group> The resin A may contain a repeating unit having hydroxyl group or cyano group. As a result, the adhesion to the substrate and/or the affinity of the developer can be improved. The repeating unit having a hydroxyl group or a cyano group is preferably a repeating unit having an alicyclic hydrocarbon structure substituted by a hydroxyl group or a cyano group. The repeating unit with hydroxyl or cyano group preferably does not have an acid decomposable group. The repeating unit having a hydroxyl group or a cyano group includes, for example, those described in paragraphs [0153] to [0158] of International Publication No. 2020/004306. The content of repeating units having hydroxyl or cyano groups is preferably 1-65 mol%, more preferably 5-45 mol%, relative to all repeating units of resin A.

<A repeating unit that has an alicyclic hydrocarbon structure and does not exhibit acid decomposability> Resin A may have an alicyclic hydrocarbon structure and have a repeating unit that does not exhibit acid decomposability. Thereby, during liquid immersion exposure, it is possible to reduce the elution of low molecular components from the resist film into the liquid immersion liquid. As the above-mentioned repeating unit, for example, 1-adamantyl (meth)acrylate, diadamantyl (meth)acrylate, tricyclodecanyl (meth)acrylate, or cyclohexyl ( Repeating unit of meth)acrylate. The content of repeating units having an alicyclic hydrocarbon structure and not exhibiting acid decomposability is preferably 1-65 mol%, more preferably 5-45 mol%, relative to all repeating units in resin A.

<Repeating unit having neither hydroxyl group nor cyano group represented by chemical formula (III)> Resin A may have a repeating unit represented by chemical formula (III) having neither hydroxyl group nor cyano group.

[chemical formula 45]

In the chemical formula (III), R ₅ represents a hydrocarbon group having at least one ring 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 group. Ra ₂ represents a hydrogen atom, an alkyl group or an acyl group.

The cyclic structure of R ₅ includes monocyclic hydrocarbon groups and polycyclic hydrocarbon groups. Examples of monocyclic hydrocarbon groups include cycloalkyl groups having 3 to 12 carbon atoms (preferably 3 to 7 carbon atoms) and cycloalkenyl groups having 3 to 12 carbon atoms. The definition of each group in the chemical formula (III) and the repeating unit include, for example, those described in paragraphs [0169] to [0173] of International Publication No. 2020/004306. The repeating unit having neither hydroxyl group nor cyano group represented by chemical formula (III) is preferably 1-65 mol %, more preferably 5-45 mol %, relative to all the repeating units of resin A.

<Other repeating units> The resin A may have other repeating units in addition to the above-mentioned repeating units. Other repeating units are not particularly limited as long as they are other than the aforementioned repeating units. As other repeating units, for example, repeating units having an oxathione ring group, repeating units having a oxazolone ring group, repeating units having a dioxane ring group, repeating units having a hydantoin ring group, and The repeating unit in the group consisting of a repeating unit having a cyclobutane ring group and a repeating unit having a cyclobutane ring group.

The content of other repeating units is preferably 1 to 65 mol%, more preferably 5 to 45 mol%, based on all the repeating units of resin A.

Examples of other repeating units include the following repeating units.

[chemical formula 46]

Resin A may have various repeating units for the purpose of adjusting dry etching resistance, standard developer compatibility, substrate adhesion, resist profile, resolution, heat resistance, and sensitivity in addition to the above-mentioned repeating units.

Resin A can be synthesized according to a conventional method (for example, radical polymerization). Using the GPC method, the weight average molecular weight of the resin A is preferably 1,000-200,000, more preferably 3,000-20,000, and more preferably 5,000-15,000 in terms of polystyrene conversion. When the weight-average molecular weight of the resin A is in the range of 1,000 to 200,000, the deterioration of heat resistance and dry etching resistance can be suppressed better. In addition, deterioration of developability and deterioration of film-forming property due to increase in viscosity can be further suppressed. The degree of dispersion (molecular weight distribution) of resin A is usually 1 to 5, preferably 1.00 to 3.00, more preferably 1.20 to 3.00, and more preferably 1.20 to 2.00. The smaller the dispersion, the better the resolution and shape of the photoresist, and the smoother the sidewall of the photoresist pattern, the smaller the surface roughness.

Resin A may be used individually by 1 type, and may use 2 or more types. When two or more kinds are used, it is preferable that the total content thereof is within the above-mentioned preferred content range. The content of the repeating units contained in the resin A, when two or more are used in each repeating unit, it is preferable that the total content is within the preferred range of the above-mentioned content of each repeating unit. The content of resin A is preferably 10.0 to 99.0% by mass, more preferably 20.0 to 98.0% by mass, more preferably 25.0 to 95.0% by mass relative to the total solid content of the photoresist composition.

[Photoacid Generator] The photoresist composition may contain at least one selected from the group consisting of compounds (I) and (II) (hereinafter also referred to as "specific photoacid generator") as Compounds that generate acid upon exposure to radiation or radiation (photoacid generators). In addition, as will be described later, the photoresist composition may have other photoacid generators than the specific photoacid generator (hereinafter also referred to as "other photoacid generators"). In addition, the photoresist composition may have compound (III). In addition, the aforementioned compound (1) is not included in the photoacid generator. In the following, first, specific photoacid generators (compounds (I) and (II)) will be described.

<Compound (I)> Compound (I) is a compound having one or more of the following structural parts X and one or more of the following structural parts Y, and is produced by irradiation with actinic rays or radiation, including A compound of an acid derived from the following first acidic site of site X and the following second acidic site of structural site Y described below. Structural site X: Consists of anion site A ₁ ^- and cationic site M ₁ ⁺ , and forms the structural site of the first acidic site represented by HA ₁ by irradiation with actinic rays or radiation Structural site Y: Consists of anion sites A site A ₂ ^- and a cationic site M ₂ ⁺ constitute a structural site that forms a second acidic site represented by HA ₂ by irradiation with actinic rays or radiation. Compound (I) satisfies the following condition I.

Condition I: In the aforementioned compound (I), the complex PI formed by substituting H ⁺ for the aforementioned cationic site M ₁ ⁺ in the aforementioned structural site X and the aforementioned cationic site M ₂ ⁺ in the aforementioned structural site Y has: ⁺ the acid dissociation constant a1 derived from the acidic site represented by _{HA 1} ^formed by substituting the aforementioned cationic site M ₁ in the aforementioned structural site X; and replacing the aforementioned cationic site M ₂ ⁺ in the aforementioned ^structural site Y with H + The acid dissociation constant a2 derived from the acid site represented by the formed HA ₂ , and the aforementioned acid dissociation constant a2 is greater than the aforementioned acid dissociation constant a1.

Hereinafter, condition I will be described more specifically. For example, when compound (I) is a compound that produces an acid having a first acidic moiety derived from the aforementioned moiety X and a second acidic moiety derived from the aforementioned moiety Y, compound PI is equivalent to "has HA ₁ and HA ₂ compound". More specifically, when the acid dissociation constant a1 and the acid dissociation constant a2 of the above-mentioned compound PI are obtained and the acid dissociation constant of the compound PI is obtained, when the compound PI is "a compound having A ₁ ^- and HA ₂ ", pKa is the acid dissociation constant a1, and when the aforementioned "compound having A ₁ ^- and HA ₂ " is "a compound having A ₁ ^- and A ₂ ^- ", pKa is the acid dissociation constant a2.

In addition, for example, when compound (I) is a compound that produces an acid having two first acidic moieties derived from the aforementioned structural moiety X and one acidic moiety derived from the aforementioned structural moiety Y, compound PI is equivalent to "Compound with two HA ₁ and one HA ₂ ". In the case where the acid dissociation constant of the above-mentioned compound PI is obtained, the acid dissociation constant of the compound PI being "a compound having one A ₁ ^- , one HA ₁ and one HA ₂ ", and "having one A ₁ ^- , one When the compound of HA ₁ and one HA ₂ " is "the compound having two A ₁ ^- and one HA ₂ ", the acid dissociation constant corresponds to the aforementioned acid dissociation constant a1. In addition, when the "compound having two A ₁ ^- and one HA ₂ " is "the compound having two A ₁ ^- and HA ₂ ^- ", the acid dissociation constant corresponds to the acid dissociation constant a2. That is, in the case of the above-mentioned compound PI, when having a plurality of acid dissociation constants derived from acidic sites represented by HA ₁ , which is obtained by substituting H ⁺ for the aforementioned cationic site M ₁ ⁺ in the aforementioned structural site X, compared with multiple The maximum value of the acid dissociation constant a1, the value of the acid dissociation constant a2 is larger. In addition, when the acid dissociation constant of the compound PI is "the compound having one A ₁ ^- , one HA ₁ and one HA ₂ " is set to aa, the "compound having one A ₁ ^- , one HA ₁ and one HA ₂ " When the acid dissociation constant for "a compound having two A ₁ ^- and one HA ₂ " is set to ab, the relationship between aa and ab satisfies aa<ab.

The acid dissociation constant a1 and the acid dissociation constant a2 can be obtained by the method for measuring the acid dissociation constant described above. The aforementioned compound PI corresponds to an acid generated when the compound (I) is irradiated with actinic rays or radiation. When the compound (I) has two or more structural sites X, the structural sites X may be the same or different. In addition, two or more aforementioned A ₁ ^−s and two or more aforementioned M ₁ ⁺ s may be the same or different from each other. In addition, in the compound (I), the aforementioned A ₁ ^- and the aforementioned A ₂ ^- , and the aforementioned M ₁ ⁺ and the aforementioned M ₂ ⁺ may be the same or different, respectively, preferably the aforementioned A ₁ ^- and the aforementioned A ₂ ^- are respectively different.

From the point of view that the LWR performance of the formed pattern is more excellent, in the aforementioned compound PI, the difference (a2-a1) between the acid dissociation constant a1 (the maximum value when there are multiple acid dissociation constants a1) and the acid dissociation constant a2, It is preferably at least 0.1, further preferably at least 0.5, and more preferably at least 1.0. In addition, the upper limit of the difference (a2-a1) between the acid dissociation constant a1 (the maximum value when there are a plurality of acid dissociation constants a1) and the acid dissociation constant a2 is preferably 16.0 or less.

In addition, in the compound PI, the acid dissociation constant a2 is preferably 20.0 or less, more preferably 15.0 or less, from the viewpoint of better LWR performance of the formed pattern. The lower limit thereof is preferably -4.0 or more.

In addition, in the above-mentioned compound PI, the acid dissociation constant a1 is preferably 2.0 or less, more preferably 0 or less, from the viewpoint of better LWR performance of the formed pattern. The lower limit thereof is preferably -20.0 or more.

The anion site A ₁ ^- and the anion site A ₂ ^- are structural sites having negatively charged atoms or atomic groups, for example, groups selected from the following chemical formulas (AA-1) to (AA-3) and Structural site in the group consisting of groups represented by chemical formulas (BB-1) to (BB-6). As the anion moiety A ₁ ^- , one capable of forming an acidic moiety with a smaller acid dissociation constant is preferable, and any one of groups represented by chemical formulas (AA-1) to (AA-3) is more preferable. In addition, as the anion site A ₂ ^- , those capable of forming an acidic site with a higher acid dissociation constant than the anion site A ₁ ^- are preferred, and any one of the groups represented by the chemical formulas (BB-1) to (BB-6) better. In addition, in the following chemical formulas (AA-1) to (AA-3) and chemical formulas (BB-1) to (BB-6), * represents a bonding position. In the chemical formula (AA-2), R ^A represents a monovalent organic group. Examples of the monovalent organic group represented by R ^A include a cyano group, a trifluoromethyl group, and a methylsulfonyl group.

[chemical formula 47]

In addition, the cationic site M ₁ ⁺ and the cationic site M ₂ ⁺ are structural sites having positively charged atoms or atomic groups, for example, the charge is a monovalent organic cation. In addition, examples of the organic cation include the same ones as those represented by M ₁₁ ⁺ and M ₁₂ ⁺ in the chemical formula (Ia-1) described later.

As a specific structure of compound (I), the compound represented by chemical formula (Ia-1) - chemical formula (Ia-5) mentioned later is mentioned, for example. In the following, first, the compound represented by the chemical formula (Ia-1) will be described. The compounds represented by the chemical formula (Ia-1) are as follows.

M ₁₁ ⁺ A ₁₁ ^- - L ₁ - A ₁₂ ^- M ₁₂ ⁺ (Ia-1)

When the compound (Ia-1) is irradiated with actinic rays or radiation, the compound represented by HA ₁₁ -L ₁ -A ₁₂ H generates an acid.

In the chemical formula (Ia-1), M ₁₁ ⁺ and M ₁₂ ⁺ each independently represent an organic cation. A ₁₁ ^- and A ₁₂ ^- each independently represent a monovalent anionic functional group. L ₁ represents a divalent linking group. M ₁₁ ⁺ and M ₁₂ ⁺ may be the same or different. A ₁₁ ^- and A ₁₂ ^- may be the same or different, but are preferably different from each other. Among them, in the above chemical formula (Ia-1), the compound PIa (HA ₁₁ -L ₁ -A ₁₂ H), which ^is formed by replacing the organic cations represented by M ₁₁ ⁺ and M ₁₂ ⁺ with H +, is derived from A ₁₂ The acid dissociation constant a2 of the acid site represented by H is larger than the acid dissociation constant a1 derived from the acid site represented by _HA11 . In addition, preferable values of the acid dissociation constant a1 and the acid dissociation constant a2 are as described above. In addition, compound PIa is the same as the acid generated from the compound represented by the chemical formula (Ia-1) by irradiation with actinic rays or radiation. Furthermore, at least one of M ₁₁ ⁺ , M ₁₂ ⁺ , A ₁₁ ⁻ , A ₁₂ ⁻ and L ₁ may have an acid decomposable group as a substituent.

In the chemical formula (Ia-1), the organic cations represented by M ₁ ⁺ and M ₂ ⁺ will be described later.

The monovalent anionic functional group represented by A ₁₁ ^- refers to a valent group having the aforementioned anion site A ₁ ^- . In addition, the monovalent anionic functional group represented by A ₁₂ ^- refers to a valent group having the aforementioned anion site A ₂ ^- . The monovalent anionic functional groups represented by A ₁₁ ^- and A ₁₂ ^- have any one of the anions represented by the aforementioned chemical formulas (AA-1) to (AA-3) and chemical formulas (BB-1) to (BB-6) The one-valent anionic functional group of the site is preferably selected from the one-valent anionic functional group of the anionic site represented by chemical formulas (AX-1) to (AX-3) and chemical formulas (BX-1) to (BX-7) A monovalent anionic functional group in the group consisting of groups is more preferable. The monovalent anionic functional group represented by A ₁₁ ^- is preferably any one of the monovalent anionic functional groups represented by the chemical formulas (AX-1) to (AX-3). In addition, as the monovalent anionic functional group represented by A ₁₂ ^- , any one of the monovalent anionic functional groups represented by the chemical formulas (BX-1) to (BX-7) is preferable, and the chemical formulas (BX-1) to ( Any one of monovalent anionic functional groups represented by BX-6) is more preferable.

[chemical formula 48]

In the chemical formulas (AX-1) to (AX-3), R ^A1 and R ^A2 each independently represent a monovalent organic group. * Indicates bond position.

Examples of the monovalent organic group represented by R ^A1 include a cyano group, a trifluoromethyl group and a methylsulfonyl group.

The monovalent organic group represented by R ^A2 is preferably a linear, branched or cyclic alkyl or aromatic group. The carbon number of the aforementioned alkyl group is preferably 1-15, more preferably 1-10, and more preferably 1-6. The aforementioned alkyl group may have a substituent. As the substituent, a fluorine atom or a cyano group is preferable, and a fluorine atom is more preferable. When the aforementioned alkyl group has a fluorine atom as a substituent, it may be a perfluoroalkyl group.

As the aryl group, phenyl or naphthyl is preferable, and phenyl is more preferable. The aforementioned aryl group may have a substituent. As a substituent, a fluorine atom, an iodine atom, a perfluoroalkyl group (for example, preferably having 1 to 10 carbon atoms, and more preferably a carbon number of 1 to 6), or a cyano group, preferably a fluorine atom, an iodine atom or a perfluoroalkyl group better.

In the chemical formulas (BX-1) to (BX-4) and the chemical formula (BX-6), R ^B represents a monovalent organic group. * Indicates bond position. The monovalent organic group represented by ^RB is preferably a linear, branched or cyclic alkyl group or aromatic group. The carbon number of the aforementioned alkyl group is preferably 1-15, more preferably 1-10, and more preferably 1-6. The aforementioned alkyl group may have a substituent. As the substituent, a fluorine atom or a cyano group is preferable, and a fluorine atom is more preferable. When the aforementioned alkyl group has a fluorine atom as a substituent, it may be a perfluoroalkyl group. Moreover, when the carbon atom which becomes a bonding position has a substituent in an alkyl group, what is a substituent other than a fluorine atom or a cyano group is also preferable. (For example, in the case of chemical formulas (BX-1) and (BX-4), it corresponds to the carbon atom directly bonded to -CO- in the chemical formula in the alkyl group; chemical formulas (BX-2) and (BX In the case of -3), it corresponds to the carbon atom directly bonded to -SO ₂ - shown in the chemical formula in the alkyl group; in the case of chemical formula (BX-6), it corresponds to the carbon atom shown in the chemical formula in the alkyl group carbon atom directly bonded to ^N- ) In addition, the carbon atom of the aforementioned alkyl group may also be substituted by carbonyl carbon.

As the aryl group, phenyl or naphthyl is preferable, and phenyl is more preferable. The aforementioned aryl group may have a substituent. As a substituent, a fluorine atom, an iodine atom, a perfluoroalkyl group (for example, preferably having 1 to 10 carbon atoms, more preferably having 1 to 6 carbon atoms), a cyano group, an alkyl group (for example, preferably having 1 to 10 carbon atoms, carbon number 1-6 is more preferable), alkoxy group (for example, carbon number 1-10 is preferable, carbon number 1-6 is more preferable), or alkoxycarbonyl group (for example, carbon number 2-10 is preferable, carbon number 2 ~6 is more preferred), fluorine atom, iodine atom, perfluoroalkyl group, alkyl group, alkoxy group or alkoxycarbonyl group are more preferred.

Examples of the divalent linking group represented by L in the chemical formula (Ia- ₁ ) include -CO-, -NR-, -CO-, -O-, -S-, -SO-, - SO ₂ -, alkylene group (preferably with 1 to 6 carbons. It can be any one of straight chain and branched chain), ring alkylene (preferably with 3 to 15 carbons), alkenyl(carbon number 2 to 6 are preferred), divalent aliphatic heterocyclic groups (5 to 10 membered rings having at least one nitrogen atom, oxygen atom, sulfur atom or Se atom in the ring structure are preferred, and 5 to 7 membered rings are further preferred preferably, 5-6 membered ring is more preferred), divalent aromatic heterocyclic group (5-10 membered ring having at least one nitrogen atom, oxygen atom, sulfur atom or Se atom in the ring structure is preferred, 5-7 membered ring ring is further preferred, 5-6 membered ring is more preferable), divalent aromatic ring group (6-10 membered ring is preferable, 6-membered ring is more preferable), and a divalent linking group formed by combining these . The aforementioned R includes a hydrogen atom or a monovalent organic group. As the monovalent organic group, for example, an alkyl group (preferably having 1 to 6 carbon atoms) is preferable. In addition, the aforementioned alkylene group, the aforementioned cycloalkylene group, the aforementioned alkenylene group, the aforementioned divalent aliphatic heterocyclic group, the aforementioned monovalent aromatic heterocyclic group, and the aforementioned divalent aromatic ring group may have a substituent. As a substituent, a halogen atom (preferably a fluorine atom) is mentioned, for example.

The divalent linking group represented by _L1 is preferably a divalent linking group represented by chemical formula (L1).

[chemical formula 49]

In the chemical formula (L1), L ₁₁₁ represents a single bond or a divalent linking group. Examples of the divalent linking group represented by L ₁₁₁ include -CO-, -NH-, -O-, -SO-, -SO ₂ -, alkylene groups having substituents (carbon number 1 to 6 is preferred. Any one of linear and branched.), ring alkylene with substituents (preferably 3 to 15 carbons), aryl groups that may have substituents (preferably 6 to 10 carbons) Excellent), and a divalent linking group formed by combining these multiples. As a substituent, a halogen atom is mentioned, for example. p represents an integer of 0 to 3, preferably an integer of 1 to 3. v represents an integer of 0 or 1. Xf ₁ each independently represent a fluorine atom or an alkyl group substituted with at least one fluorine atom. The carbon number of the alkyl group is preferably 1-10, more preferably 1-4. In addition, the alkyl group substituted with at least one fluorine atom is preferably a perfluoroalkyl group. Xf ₂ each independently represent a hydrogen atom, a fluorine atom, or an alkyl group which may have a fluorine atom as a substituent. The carbon number of the alkyl group is preferably 1-10, more preferably 1-4. Xf ₂ is preferably a fluorine atom or a hydrocarbon group substituted by at least one fluorine atom, more preferably a fluorine atom or a perfluoroalkyl group. Among them, Xf ₁ and Xf ₂ are each independently preferably a fluorine atom or a perfluoroalkyl group having 1 to 4 carbons, more preferably a fluorine atom or CF ₃ , and particularly preferably both Xf ₁ and Xf ₂ are a fluorine atom. * Indicates bond position. When L ₁₁ in the chemical formula (Ia-1) represents a divalent linking group represented by the chemical formula (L1), it is preferable that the bonding bond (*) on the side of the L ₁₁₁ in the chemical formula (L1) is the same as that of the chemical formula (Ia- A ₁₂ ^-bonding in 1).

In (Ia-1), preferred forms of the organic cations represented by M ₁₁ ⁺ and M ₁₂ ⁺ will be described in detail. The organic cations represented by M ₁₁ ⁺ and M ₁₂ ⁺ are preferably organic cations (cations (ZaI)) represented by chemical formula (ZaI) or organic cations represented by chemical formula (ZaII) (cations ( ZaII)).

[chemical formula 50]

In the chemical formula (ZaI), R ²⁰¹ , R ²⁰² and R ²⁰³ each independently represent an organic group. The carbon number of the organic groups of R ²⁰¹ , R ²⁰² and R ²⁰³ is usually 1-30, preferably 1-20. In addition, two of R ²⁰¹ to R ²⁰³ may be bonded to form a ring structure, and the ring may have an oxygen atom, a sulfur atom, -COO-, an amido group, or a carbonyl group. Examples of groups formed by bonding two of R ²⁰¹ to R ²⁰³ include alkylene groups (for example, butylene groups and pentylene groups), and -CH ₂ -CH ₂ -O-CH ₂ -CH ₂ -.

As a preferred aspect of the organic cation in the chemical formula (ZaI), organic cations (cations (ZaI- 3b)), and the organic cation represented by the chemical formula (ZaI-4b) (cation (ZaI-4b)).

First, the cation (ZaI-1) will be described. The cation (ZaI-1) is an aryl alumium cation in which at least one of R ²⁰¹ to R ²⁰³ of the aforementioned chemical formula (ZaI) is an aryl group. As the aryl cobaltium cation, all of R ²⁰¹ to R ²⁰³ may be aryl groups, or a part of R ²⁰¹ to R ²⁰³ may be aryl groups, and the rest may be alkyl or cycloalkyl. In addition, one of R ²⁰¹ to R ²⁰³ may be an aryl group, and the remaining two of R ²⁰¹ to R ²⁰³ may be bonded to form a ring structure, and the ring may also have an oxygen atom, a sulfur atom, -COO-, acyl Amino or carbonyl. As the group formed by two bonds among R ²⁰¹ to R ²⁰³ , for example, an alkylene group (for example, a butylene group, a pentylene group, or -CH ₂ -CH ₂ -O-CH ₂ -CH ₂ -), wherein more than one methylene group may be substituted by an oxygen atom, a sulfur atom, -COO-, an amido group and/or a carbonyl group. As the aryl columium cation, for example, a triaryl cobalium cation, a diaryl alkyl columium cation, an aryl dialkyl columium cation, a diarylcycloalkyl columium cation, and an aryl bicycloalkyl columium cation .

As the aryl group contained in the arylconium cation, phenyl or naphthyl is preferable, and phenyl is more preferable. The aryl group may be an aryl group having a heterocyclic structure including an oxygen atom, a nitrogen atom, or a sulfur atom. Examples of the heterocyclic structure include pyrrole residues, furan residues, thiophene residues, indole residues, benzofuran residues, and benzothiophene residues. When the aryl perium 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 that the aryl group cation may have as needed, the linear alkyl group with 1 to 15 carbons, the branched chain alkyl group with 3 to 15 carbons or the cycloalkyl group with 3 to 15 carbons Preferably, methyl, ethyl, propyl, n-butyl, secondary butyl, tertiary butyl, cyclopropyl, cyclobutyl, and cyclohexyl are more preferred.

As the aryl group, alkyl group and cycloalkyl group of R ²⁰¹ to R ²⁰³ , it is preferable to independently have an alkyl group (for example, having 1 to 15 carbon atoms), a cycloalkyl group (for example, having 3 to 15 carbon atoms), Aryl group (for example, carbon number 6-14), alkoxy group (for example, carbon number 1-15), cycloalkylalkoxy group (for example, carbon number 1-15), halogen atom (for example, fluorine and iodine) , hydroxyl, carboxyl, -COO-, sulfinyl, sulfonyl, alkylthio or phenylthio as substituents. If the situation permits, the above-mentioned substituents may further have substituents. For example, the above-mentioned alkyl groups have halogen atoms as substituents, and it is also preferable to change them into halogenated alkyl groups such as trifluoromethyl. In addition, it is also preferable that the aforementioned substituents form an acid-decomposable group by arbitrary combinations. In addition, the acid-decomposable group refers to a group that is decomposed by the action of an acid to generate an acid group, and is preferably a structure in which the acid group is protected by a detachment group detached by the action of an acid. The aforementioned acid group and leaving group are as described above.

Next, the cation (ZaI-2) will be described. The cation (ZaI-2) is a cation in which R ²⁰¹ to R ²⁰³ in the chemical formula (ZaI) each independently represent an organic group not having an aromatic ring. Moreover, the aromatic ring which has a heteroatom is also contained as an aromatic ring. The organic group without an aromatic ring as R ²⁰¹ to ^{R 203} usually has 1 to 30 carbons, preferably 1 to 20 carbons. R ²⁰¹ to R ²⁰³ are each independently alkyl, cycloalkyl, allyl or vinyl, preferably linear or branched 2-oxyalkyl, 2-oxycycloalkyl or alkoxycarbonylmethyl A group is further preferred, and a linear or branched 2-oxyalkyl group is more preferred.

As the alkyl and cycloalkyl groups of R ²⁰¹ to R ²⁰³ , for example, linear alkyl groups having 1 to 10 carbons or branched alkyl groups having 3 to 10 carbons (for example, methyl, ethyl, etc.) , propyl, butyl, and pentyl), and cycloalkyl groups with 3 to 10 carbon atoms (for example, cyclopentyl, cyclohexyl, and norbornyl). R ²⁰¹ to R ²⁰³ may be further substituted by a halogen atom, an alkoxy group (for example, having 1 to 5 carbon atoms), a hydroxyl group, a cyano group or a nitro group. In addition, it is preferable that the substituents of R ²⁰¹ to R ²⁰³ each independently form an acid-decomposable group through any combination of substituents.

Next, the cation (ZaI-3b) will be described. The cation (ZaI-3b) is the cation represented by the chemical formula (ZaI-3b).

[chemical formula 51]

In the chemical formula (ZaI-3b), R _1c to R _5c each independently represent a hydrogen atom, alkyl, cycloalkyl, aryl, alkoxy, aryloxy, alkoxycarbonyl, alkylcarbonyloxy, cycloalkane an ylcarbonyloxy group, a halogen atom, a hydroxyl group, a nitro group, an alkylthio group or an arylthio group. R _6c and R _7c each independently represent a hydrogen atom, an alkyl group (such as a tertiary butyl group), a cycloalkyl group, a halogen atom, a cyano group or an aryl group. R _x and R _y each independently represent an alkyl group, a cycloalkyl group, a 2-oxyalkyl group, a 2-oxycycloalkyl group, an alkoxycarbonylalkyl group, an allyl group or a vinyl group. In addition, the substituents of R _1c to R _7c , and R _x and R _y are preferably each independently formed an acid-decomposable group by any combination of substituents.

Any two or more of R _1c to R _5c , 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 the rings may be independently Contains oxygen atom, sulfur atom, keto group, ester bond or amide bond. Examples of the aforementioned rings include aromatic or non-aromatic hydrocarbon rings, aromatic or non-aromatic heterocycles, and polycyclic condensed rings in which two or more of these rings are combined. Examples of the ring include rings with 3 to 10 members, preferably rings with 4 to 8 members, and more preferably rings with 5 or 6 members.

Examples of groups formed by bonding any two or more of R _1c to R _5c , R _6C and R _7C , and R _x and R _y include alkylene groups such as butylene and pentylene. The methylene group in the alkylene group may be substituted by a heteroatom such as an oxygen atom. The group formed by bonding R _5c and R _6c , and R _5c and R _x is preferably a single bond or an alkylene group. As an alkylene group, a methylene group, an ethylene group, etc. are mentioned, for example.

R _1c to R _5c , R _6c , R _7c , R _x , R _y , and any two or more of R 1c to R _5c , _{R 5c} and R _6c , R _6c and R _7c , R _5c and R _x , and The ring formed by R _x and R _y being bonded to each other may have a substituent.

Next, the cation (ZaI-4b) will be described. The cation (ZaI-4b) is the cation represented by the chemical formula (ZaI-4b).

[chemical formula 52]

In the chemical formula (ZaI-4b), l represents an integer of 0-2, and r represents an integer of 0-8. R ₁₃ represents a hydrogen atom, a halogen atom (for example, a fluorine atom, an iodine atom, etc.), a hydroxyl group, an alkyl group, a halogenated alkyl group, an alkoxy group, a carboxyl group, an alkoxycarbonyl group, or a group having a cycloalkyl group (which may be a ring An alkyl group itself may also be a group containing a part of a cycloalkyl group). These groups may further have substituents. _R represents a hydroxyl group, a halogen atom (for example, a fluorine atom, an iodine atom, etc.), 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 (it may be a cycloalkyl group itself, or a group containing part of a cycloalkyl group). These groups may have substituents. When R ₁₄ exists in plural, each independently represents the aforementioned groups such as hydroxyl. R ₁₅ each independently represent an alkyl group, a cycloalkyl group or a naphthyl group. Two R ₁₅ may be bonded to each other to form a ring. When two R ₁₅ are bonded to each other to form a ring, heteroatoms such as oxygen atoms or nitrogen atoms may be included in the ring skeleton. In one aspect, it is preferable that two R ₁₅ are alkylene groups and are bonded to each other to form a ring structure. In addition, the aforementioned alkyl group, the aforementioned cycloalkyl group, the aforementioned naphthyl group, and a ring formed by bonding two R ₁₅ to each other may have a substituent.

The hydrocarbon groups of R ₁₃ , R ₁₄ and R ₁₅ may be linear or branched. The carbon number of the alkyl group is preferably 1-10. As the alkyl group, methyl, ethyl, n-butyl or tert-butyl is more preferable. In addition, each substituent of R ₁₃ to R ₁₅ , and R _x and R _y is preferably one that independently forms an acid-decomposable group through any combination of substituents.

Next, chemical formula (ZaII) will be described. In the chemical formula (ZaII), R ²⁰⁴ and R ²⁰⁵ each independently represent an aryl group, an alkyl group or a cycloalkyl group. As the aryl group of ^R204 and ^R205 , phenyl or naphthyl is preferred, and phenyl is more preferred. The aryl group of R ²⁰⁴ and R ²⁰⁵ may be an aryl group having a heterocyclic ring having an oxygen atom, a nitrogen atom or 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. The alkyl and cycloalkyl groups for ^R204 and ^R205 are preferably linear alkyl groups with 1 to 10 carbons or branched chain alkyl groups with 3 to 10 carbons (for example, methyl, ethyl, propyl, etc.) group, butyl or pentyl), or a cycloalkyl group with 3 to 10 carbon atoms (for example, cyclopentyl, cyclohexyl or norbornyl).

The aryl group, alkyl group, and cycloalkyl group of R ²⁰⁴ and R ²⁰⁵ may each independently have a substituent. As substituents that the aryl group, alkyl group and cycloalkyl group of R ²⁰⁴ and R ²⁰⁵ may have, for example, an alkyl group (for example, having 1 to 15 carbon atoms), a cycloalkyl group (for example, having 3 to 15 carbon atoms), ), aryl group (for example, carbon number 6-15), alkoxy group (for example, carbon number 1-15), halogen atom, hydroxyl group, phenylthio group and the like. In addition, the substituents of R ²⁰⁴ and R ²⁰⁵ are preferably those that independently form an acid-decomposable group through any combination of substituents.

Next, formulas (Ia-2) to (Ia-4) will be described.

[chemical formula 53]

In the chemical formula (Ia-2), A _21a ^- and A _21b ^- each independently represent a monovalent anionic functional group. Here, the monovalent anionic functional group represented by A _21a ^- and A _21b ^- refers to a valent group having the aforementioned anion site A ₁ ^- . Examples of the monovalent anionic functional groups represented by A _21a ^- and A _21b ^- include monovalent anionic functional groups selected from the group consisting of the aforementioned chemical formulas (AX-1) to (AX-3). . A ₂₂ ^- represents a dianionic functional group. Here, the divalent anionic functional group represented by A ₂₂ ^- refers to a divalent group having the aforementioned anion site A ₂ ^- . Examples of the dianionic functional group represented by A ₂₂ ^- include dianionic functional groups represented by the following chemical formulas (BX-8) to (BX-11).

[chemical formula 54]

M _21a ⁺ , M _21b ⁺ and M ₂₂ ⁺ each independently represent an organic cation. The organic cations represented by M _21a ⁺ , M _21b ⁺ and M ₂₂ ⁺ have the same meaning as M ₁ ⁺ above, and their preferred modes are also the same. L ₂₁ and L ₂₂ each independently represent a divalent organic group.

In addition, in the aforementioned chemical formula (Ia-2), the compound PIa-2, which is obtained by substituting H ⁺ for the organic cations represented by M _21a ⁺ , M _21b ⁺ and M ₂₂ ⁺ , is derived from the acidity represented by A ₂₂ H The acid dissociation constant a2 of the site is greater than the acid dissociation constant a1-1 derived from A _21a H and the acid dissociation constant a1-2 derived from the acidic site represented by A _21b H. In addition, the acid dissociation constant a1-1 and the acid dissociation constant a1-2 correspond to the aforementioned acid dissociation constant a1. In addition, A _21a ^- and A _21b ^- may be the same as or different from each other. In addition, M _21a ⁺ , M _21b ⁺ and M ₂₂ ⁺ may be the same as or different from each other. In addition, at least one of M _21a ⁺ , M _21b ⁺ , M ₂₂ ⁺ , A _21a ⁻ , A _21b ⁻ , L ₂₁ and L ₂₂ may have an acid-decomposable group as a substituent.

In the chemical formula (Ia-3), A _31a ^- and A ₃₂ ^- each independently represent a monovalent anionic functional group. In addition, the definition of the monovalent anionic functional group represented by A _31a ^- is the same as that of A _21a ^- and A _21b ^- in the aforementioned chemical formula (Ia-2), and the preferred mode is also the same. The monovalent anionic functional group represented by A ₃₂ ^- refers to a valent group including the aforementioned anionic portion A ₂ ^- . Examples of the monovalent anionic functional group represented by A ₃₂ ^- include monovalent anionic functional groups selected from the group consisting of the aforementioned chemical formulas (BX-1) to (BX-7). A _31b ^- represents a dianionic functional group. Here, the divalent anionic functional group represented by A _31b ^- refers to a divalent group including the aforementioned anion site A ₁ ^- . Examples of the dianionic functional group represented by A _31b ^- include, for example, dianionic functional groups represented by the following chemical formula (AX-4).

[chemical formula 55]

M _31a ⁺ , M _31b ⁺ and M ₃₂ ⁺ each independently represent a monovalent organic cation. M _31a ⁺ , M _31b ⁺ , and M ₃₂ ⁺ organic cations have the same meaning as M ₁ ⁺ above, and their preferred modes are also the same. L ₃₁ and L ₃₂ each independently represent a divalent organic group.

In addition, in the aforementioned chemical formula (Ia-3), the compound PIa-3, which is obtained by substituting H ⁺ for organic cations represented by M _31a ⁺ , M _31b ⁺ and M ₃₂ ⁺ , is derived from the acidity represented by A ₃₂ H The acid dissociation constant a2 of the site is greater than the acid dissociation constant a1-3 derived from the acid site represented by A _31a H and the acid dissociation constant a1-4 derived from the acid site represented by A _31b H. In addition, the acid dissociation constant a1-3 and the acid dissociation constant a1-4 correspond to the aforementioned acid dissociation constant a1. In addition, A _31a ^- and A ₃₂ ^- may be the same as or different from each other. In addition, M _31a ⁺ , M _31b ⁺ and M ₃₂ ⁺ may be the same as or different from each other. In addition, at least one of M _31a ⁺ , M _31b ⁺ , M ₃₂ ⁺ , A _31a ^- , A ₃₂ ^- , L ₃₁ and L ₃₂ may have an acid decomposable group as a substituent.

In the chemical formula (Ia-4), A _41a ^- , A _41b ^- and A ₄₂ ^- each independently represent a monovalent anionic functional group. In addition, the definition of the monovalent anionic functional group represented by A _41a ^- and A _41b ^- is the same as that of A _21a ^- and A _21b ^- in the aforementioned chemical formula (Ia-2). In addition, the definition of the monovalent anionic functional group represented by A ₄₂ ^- is the same as that of A ₃₂ ^- in the aforementioned chemical formula (Ia-3), and the preferred mode is also the same. M _41a ⁺ , M _41b ⁺ and M ₄₂ ⁺ each independently represent an organic cation. L ₄₁ represents a trivalent organic group.

In addition, in the aforementioned chemical formula (Ia-4), the compound PIa-4, which is obtained by substituting H ⁺ for the organic cations represented by M _41a ⁺ , M _41b ⁺ and M ₄₂ ⁺ , is derived from the acidity represented by A ₄₂ H The acid dissociation constant a2 of the site is greater than the acid dissociation constant a1-5 derived from the acidic site represented by A _41a H and the acid dissociation constant a1-6 derived from the acidic site represented by A _41b H. In addition, the acid dissociation constant a1-5 and the acid dissociation constant a1-6 correspond to the aforementioned acid dissociation constant a1. In addition, A _41a ^- , A _41b ^- and A ₄₂ ^- may be the same as or different from each other. In addition, M _41a ⁺ , M _41b ⁺ and M ₄₂ ⁺ may be the same as or different from each other. In addition, at least one of M _41a ⁺ , M _41b ⁺ , M ₄₂ ⁺ , A _41a ^- , A _41b ^- , A ₄₂ ^- and L ₄₁ may have an acid decomposable group as a substituent.

Examples of divalent organic groups represented by L ₂₁ and L ₂₂ in the chemical formula (Ia-2) and L ₃₁ and L ₃₂ in the chemical formula (Ia-3) include -CO-, -NR- _. 3 to 15 are preferred), alkenyl groups (2 to 6 carbons are preferred), divalent aliphatic heterocyclic groups (5 to 5 with at least one nitrogen atom, oxygen atom, sulfur atom or Se atom in the ring structure) A 10-membered ring is preferred, a 5-7 membered ring is further preferred, and a 5-6-membered ring is more preferred.), a divalent aromatic heterocyclic group (having at least one nitrogen atom, oxygen atom, sulfur atom or Se in the ring structure 5-10-membered ring is preferred, 5-7-membered ring is further preferred, and 5-6-membered ring is more preferred.), divalent aromatic ring group (6-10-membered ring is preferred, 6-membered ring is more preferred) , and a divalent organic group formed by combining these multiple groups. The aforementioned R includes a hydrogen atom or a monovalent organic group. As the monovalent organic group, for example, an alkyl group (preferably having 1 to 6 carbon atoms) is preferable. In addition, the aforementioned alkylene group, the aforementioned cycloalkylene group, the aforementioned alkenylene group, the aforementioned divalent aliphatic heterocyclic group, the aforementioned divalent aromatic heterocyclic group, and the aforementioned divalent aromatic ring group may have substituents. As a substituent, a halogen atom (preferably a fluorine atom) is mentioned, for example.

As the divalent organic groups represented by L ₂₁ and L ₂₂ in the chemical formula (Ia-2) and L ₃₁ and L ₃₂ in the chemical formula (Ia-3), for example, divalent organic groups represented by the chemical formula (L2) The organic base is also good.

[chemical formula 56]

In chemical formula (L2), q represents the integer of 1-3. * Indicates bond position. Xf each independently represent a fluorine atom or an alkyl group substituted with at least one fluorine atom. The carbon number of the alkyl group is preferably 1-10, more preferably 1-4. Furthermore, as the alkyl group substituted with at least one fluorine atom, a perfluoroalkyl group is preferred. Xf is preferably a fluorine atom or a perfluoroalkyl group having 1 to 4 carbons, more preferably a fluorine atom or CF ₃ . Xf of both is more preferably a fluorine atom.

L _A represents a single bond or a divalent linking group. Examples of the monovalent linking group represented by L _A include -CO-, -O-, -SO-, -SO ₂ - and alkylene groups (preferably having 1 to 6 carbon atoms. Linear and branched) chain), ring alkylene (3-15 carbons), divalent aromatic ring group (6-10 membered ring is better, 6-membered ring is more preferable), and combinations of these A linking group with two valences. In addition, the aforementioned alkylene group, the aforementioned cycloalkylene group, and the divalent aromatic ring group may have a substituent. As a substituent, a halogen atom (preferably a fluorine atom) is mentioned, for example.

Examples of the divalent organic group represented by the chemical formula (L2) include *-CF ₂ -*, *-CF ₂ -CF ₂ -*, *-CF ₂ -CF ₂ -CF ₂ -*, * -Ph-O-SO ₂ -CF ₂ -*, *-Ph-O-SO ₂ -CF ₂ -CF ₂ -*, *-Ph-O-SO ₂ -CF ₂ -CF ₂ -CF ₂ -* and *-Ph-OCO-CF ₂ -*. In addition, Ph means a phenylene group which may have a substituent, preferably a 1,4-phenylene group. As a substituent, it is preferably an alkyl group (preferably having 1 to 10 carbon atoms, more preferably having 1 to 6 carbon atoms), an alkoxy group (preferably having 1 to 10 carbon atoms, more preferably having 1 to 6 carbon atoms), or an alkane group. Oxycarbonyl (preferably having 2 to 10 carbons, more preferably 2 to 6 carbons). In the case where L ₂₁ and L ₂₂ in the chemical formula (Ia-2) represent a divalent organic group represented by the chemical formula (L2), it is preferable that the bonding bond (*) on _{the LA} side in the chemical formula (L2) and the chemical formula A ₂₁ ^- and ^A _21b -bonding in (Ia-2). In addition, when L ₃₁ and L ₃₂ in the chemical formula (Ia-3) represent a divalent organic group represented by the chemical formula (L2), it is preferably a bond (*) on _{the LA} side in the chemical formula (L2) It is bonded to A _31a ^- and A ₃₂ ^- in the chemical formula (Ia-3).

Examples of the trivalent organic group represented by L ₄₁ in the chemical formula (Ia-4) include trivalent organic groups represented by the chemical formula (L3).

[chemical formula 57]

In the chemical formula (L3), L _B represents a trivalent hydrocarbon ring group or a trivalent heterocyclic group. * Indicates bond position.

The aforementioned hydrocarbon ring group may be any one of an aromatic ring group and an aliphatic hydrocarbon ring group. The number of carbons contained in the aforementioned hydrocarbon ring group is preferably 6-18, more preferably 6-14. The aforementioned heterocyclic group may be any one of an aromatic ring group and an aliphatic hydrocarbon ring group. As the aforementioned heterocyclic ring, a 5-10-membered ring having at least one nitrogen atom, oxygen atom, sulfur atom or Se atom in the ring structure is preferred, a 5-7-membered ring is further preferred, and a 5-6-membered ring is more preferred. As L _B , a trivalent hydrocarbon ring group is preferable, and a phenyl ring group or an adamantane ring group is more preferable. The phenyl ring group or adamantane ring group may have a substituent. As a substituent, a halogen atom (preferably a fluorine atom) is mentioned, for example.

In addition, in the chemical formula (L3), L _B1 to _{L B3} each independently represent a single bond or a divalent linking group. Examples of divalent linking groups represented by L _B1 to L _B3 include -CO-, -NR-, -O-, -S-, -SO-, -SO ₂ -, alkylene (carbon The number is preferably 1 to 6. Any one of straight chain and branched chain), ring alkylene (preferably 3 to 15 carbons), alkenyl (preferably 2 to 6 carbons), divalent Aliphatic heterocyclic group (preferably a 5-10-membered ring having at least one nitrogen atom, oxygen atom, sulfur atom or Se atom in the ring structure, more preferably a 5-7-membered ring, more preferably a 5-6-membered ring), A divalent aromatic heterocyclic group (a 5-10-membered ring with at least one nitrogen atom, oxygen atom, sulfur atom or Se atom in the ring structure is preferred, a 5-7-membered ring is further preferred, a 5-6-membered ring is more preferred) preferably), a divalent aromatic ring group (preferably a 6-10-membered ring, more preferably a 6-membered ring), and a divalent linking group formed by combining these. The aforementioned R includes a hydrogen atom or a monovalent organic group. As the monovalent organic group, for example, an alkyl group (preferably having 1 to 6 carbon atoms) is preferable. In addition, the aforementioned alkylene group, the aforementioned cycloalkylene group, the aforementioned alkenylene group, the aforementioned divalent aliphatic heterocyclic group, the aforementioned divalent aromatic heterocyclic group, and the aforementioned divalent aromatic ring group may have substituents. As a substituent, a halogen atom (preferably a fluorine atom) is mentioned, for example. The divalent linking group represented by L _B1 to L _B3 is preferably -CO-, -NR-, -O-, -S-, -SO-, -SO ₂ -, an alkane which may have a substituent group, or a divalent linking group combining these.

As the divalent linking group represented by L _B1 to L _B3 , the divalent linking group represented by the chemical formula (L3-1) is more preferable.

[chemical formula 58]

In the chemical formula (L3-1), L _B11 represents a single bond or a divalent linking group. The monovalent linking group represented by the chemical formula L _B11 , for example, includes -CO-, -O-, -SO-, -SO ₂ -, an alkylene group that may have a substituent (preferably having 1 to 6 carbon atoms) .A straight chain and a branched chain), and a divalent linking group formed by combining these. As a substituent, a halogen atom is mentioned, for example. r represents the integer of 1-3. Xf has the same meaning as Xf in the aforementioned chemical formula (L2), and the preferred mode is also the same. * Indicates bond position.

Examples of divalent linking groups represented by L _B1 to _{L B3} include *-O-*, *-O-SO ₂ -CF ₂ -*, *-O-SO ₂ -CF ₂ -CF ₂ -*, *-O- _SO2 - _CF2 - _CF2 - _CF2- * and *-COO- _CH2 - _CH2- *. When L ₄₁ in the chemical formula (Ia-4) has a divalent organic group represented by the chemical formula (L3-1), and the divalent organic group represented by the chemical formula (L3-1) is bonded to A ₄₂ ^- , preferably the bond (*) on the side of the carbon atom clearly indicated in the chemical formula (L3-1) is bonded to A ₄₂ ^- in the chemical formula (Ia-4).

Next, Chemical Formula (Ia-5) will be described.

[chemical formula 59]

In the chemical formula (Ia-5), A _51a ^- , A _51b ^- and A _51c ^- each independently represent a monovalent anionic functional group. Here, the monovalent anionic functional group represented by A _51a ^- , A _51b ^- and A _51c ^- refers to a valent group including the aforementioned anion site A ₁ ^- . Examples of monovalent anionic functional groups represented by A _51a ^- , A _51b ^- and A _51c ^- include monovalent anionic functional groups selected from the group consisting of the aforementioned chemical formulas (AX-1) to (AX-3). Anionic functional groups. A _52a ^- and A _52b ^- represent a divalent anionic functional group. Here, the divalent anionic functional group represented by A _52a ^- and A _52b ^- refers to a divalent group including the aforementioned anion site A ₂ ^- . Examples of the dianionic functional group represented by A ₂₂ ^- include dianionic functional groups selected from the group consisting of the aforementioned chemical formulas (BX-8) to (BX-11).

M _51a ⁺ , M _51b ⁺ , M _51c ⁺ , M _52a ⁺ and M _52b ⁺ each independently represent an organic cation. The organic cations represented by M _51a ⁺ , M _51b ⁺ , M _51c ⁺ , M _52a ⁺ and M _52b ⁺ have the same meanings and preferred modes as M ₁ ⁺ above. L ₅₁ and L ₅₃ each independently represent a divalent organic group. The divalent organic groups represented by L ₅₁ and L ₅₃ have the same meaning as L ₂₁ and L ₂₂ in the aforementioned chemical formula (Ia-2), and the preferred modes are also the same. L ₅₂ represents a trivalent organic group. The trivalent organic group represented by L ₅₂ has the same meaning as that of L ₄₁ in the aforementioned chemical formula (Ia-4), and the preferred mode is also the same.

In addition, in the aforementioned chemical formula (Ia-5), the compound PIa-5, which is formed by replacing the organic cations represented by M _51a ⁺ , M _51b ⁺ , M _51c ⁺ , M _52a ⁺ and M _52b ⁺ with H ⁺ , is derived from The acid dissociation constant a2-1 of the acid site represented by A _52a H and the acid dissociation constant a2-2 derived from the acid site represented by A _52b H are greater than the acid dissociation constant a1-1 derived from A _51a H, The acid dissociation constant a1-2 derived from the acid site represented by A _51b H and the acid dissociation constant a1-3 derived from the acid site represented by A _51c H. In addition, the acid dissociation constants a1-1 to a1-3 correspond to the aforementioned acid dissociation constant a1, and the acid dissociation constants a2-1 and 2-2 correspond to the aforementioned acid dissociation constant a2. In addition, A _51a ^- , A _51b ^- and A _51c ^- may be the same as or different from each other. In addition, A _52a ^- and A _52b ^- may be the same as or different from each other. In addition, M _51a ⁺ , M _51b ⁺ , M _51c ⁺ , M _52a ⁺ and M _52b ⁺ may be the same as or different from each other. In addition, at least one of M _51b ⁺ , M _51c ⁺ , M _52a ⁺ , M _52b ⁺ , A _51a ⁻ , A _51b ⁻ , A _51c ⁻ , L ₅₁ , L ₅₂ and L ₅₃ may have an acid decomposable group as a substitute base.

<Compound (II)> Compound (II) has two or more of the above-mentioned structural parts X and one or more of the following structural parts Z, and is produced by irradiation with actinic rays or radiation, and contains two or more of the aforementioned structures. A compound of the aforementioned first acidic site of site X and the acid of the aforementioned structural site Z. Structural part Z: non-ionic part capable of neutralizing acid

In compound (II), the definition of structural site X and the definitions of A ₁ ^- and M ₁ ⁺ are the same as the definitions of structural site X and A ₁ ^- and M ₁ ⁺ in the aforementioned compound (I), and the preferred mode is also same.

In the aforementioned chemical formula (II), the source of chemical formula PII formed by replacing ^the aforementioned cationic site M ₁ ⁺ in the aforementioned structural site X with H ⁺ is used to replace the aforementioned cationic site M ₁ ⁺ in the aforementioned structural site X The preferred range of the acid dissociation constant a1 derived from the acid site represented by HA ₁ is the same as the acid dissociation constant a1 in the aforementioned chemical substance PI. In addition, for example, when compound (II) is a compound having two acids derived from the aforementioned first acidic site of the aforementioned structural site X and the aforementioned structural site Z, compound PII is equivalent to "having two HA ₁ compound of". In the case of obtaining the acid dissociation constant of the compound PII, the acid dissociation constant when the compound PII is "the compound with one A ₁ ^- and one HA ₁ ", and "the compound with one A ₁ ^- and one HA ₁ " is the acid dissociation constant when "a compound having two A ₁ ^- " is equivalent to the acid dissociation constant a1.

The acid dissociation constant a1 can be obtained by the above-mentioned determination method of the acid dissociation constant. The aforementioned compound PII corresponds to an acid generated when the compound (II) is irradiated with actinic rays or radiation. In addition, the aforementioned two or more structural sites X may be the same or different. In addition, two or more of the aforementioned A ₁ ^- and two or more of the aforementioned M ₁ ⁺ may be the same or different.

As the nonionic site capable of neutralizing acid in the structural site Z, for example, a site having a group capable of electrostatically interacting with protons or a functional group having electrons is preferable. As a group capable of electrostatically interacting with protons or a functional group having electrons, for example, a functional group having a macrocyclic structure such as cyclic polyether or a functional group having a non-shared electron that does not contribute to π-conjugation can be mentioned. Functional group for the nitrogen atom. As a nitrogen atom having an unshared electron pair not contributing to π conjugation, for example, a nitrogen atom having a partial structure shown in the chemical formula.

[chemical formula 60]

As partial structures having groups capable of electrostatically interacting with protons or functional groups having electrons, for example, crown ether structures, azacrown ether structures, primary to tertiary amine structures, pyridine structures, imidazole structures, and Pyrazine structure, preferably 1-3 amine structure.

As the compound (II), for example, compounds represented by the chemical formulas (IIa-1) and (IIa-2) are mentioned.

[chemical formula 61]

In the aforementioned chemical formula (IIa-1), A _61a ^- and A _61b ^- have the same meanings as A ₁₁ ^- in the aforementioned chemical formula (Ia-1), and the preferred modes are also the same. In addition, M _61a ⁺ and M _61b ⁺ have the same meanings as M ₁₁ ⁺ in the aforementioned chemical formula (Ia-1), respectively, and preferred modes are also the same. In the chemical formula (IIa-1), L ₆₁ and L ₆₂ have the same meanings as L ₁ in the aforementioned chemical formula (Ia-1), and the preferred modes are also the same.

In the chemical formula (IIa-1), R _2X represents a monovalent organic group. As the monovalent organic group represented by R _2X , for example, -CH ₂ - can be selected from -CO-, -NH-, -O-, -S-, -SO- and -SO ₂ - One or more combinations of substituted hydrocarbon groups (preferably with 1 to 10 carbons. Any one of straight chain and branched chain), cycloalkyl (preferably with 3 to 15 carbons), Or alkenyl (preferably having 2 to 6 carbon atoms). In addition, the aforementioned alkylene group, the aforementioned cycloalkylene group, and the aforementioned alkenylene group may have a substituent. As a substituent, a halogen atom (preferably a fluorine atom) is mentioned, for example.

In addition, in the aforementioned chemical formula (IIa-1), in the compound PIIa-1 obtained by replacing the organic cations represented by M _61a ⁺ and M _61b ⁺ with H ⁺ , the acid dissociation originating from the acidic site represented by A _61a H The constant a1-7 and the acid dissociation constant a1-8 derived from the acid site represented by A _61b H correspond to the aforementioned acid dissociation constant a1. In addition, in the aforementioned compound (IIa-1), the compound PIIa-1 obtained by substituting H ⁺ for the aforementioned cationic sites M _61a ⁺ and M _61b ⁺ in the aforementioned structural site X corresponds to HA _61a -L ₆₁ -N(R _2X )-L ₆₂ -A _61b H. In addition, compound PIIa-1 is the same as the acid generated from the compound represented by formula (IIa-1) by irradiation with actinic rays or radiation. In addition, at least one of M _61a ⁺ , M _61b ⁺ , A _61a ⁻ , A _61b ⁻ , L ₆₁ , L ₆₂ and R _2X may have an acid decomposable group as a substituent.

In the aforementioned chemical formula (IIa-2), A _71a ^- , A _71b ^- and A _71c ^- have the same meanings as A ₁₁ ^- in the aforementioned chemical formula (Ia-1), and the preferred modes are also the same. In addition, M _71a ⁺ , M _71b ⁺ and M _71c ⁺ have the same meanings as M ₁₁ ⁺ in the aforementioned chemical formula (Ia-1), and the preferred modes are also the same. In the aforementioned chemical formula (IIa-2), L ₇₁ , L ₇₂ and L ₇₃ have the same meanings as L ₁ in the aforementioned chemical formula (Ia-1), and the preferred modes are also the same.

In addition, in the aforementioned chemical formula (IIa-2), the compound PIIa-2, which is obtained by substituting H ⁺ for the organic cations represented by M _71a ⁺ , M _71b ⁺ and M _71c ⁺ , is derived from the acidity represented by A _71a H The acid dissociation constant a1-9 of the site, the acid dissociation constant a1-10 derived from the acid site represented by A _71b H, and the acid dissociation constant a1-11 derived from the acid site represented by A _71c H are equivalent to The aforementioned acid dissociation constant a1. In addition, in the aforementioned compound (IIa-1), the compound PIIa-2 obtained by substituting the aforementioned cationic sites M _71a ⁺ , M _71b ⁺ and M _71c ⁺ in the aforementioned structural site X corresponds to HA _71a -L ₇₁ -N( L ₇₃ -A _71c H) - L ₇₂ -A _71b H. In addition, compound PIIa-2 is the same as the acid generated from the compound represented by formula (IIa-2) by irradiation with actinic rays or radiation. In addition, at least one of M _71a ⁺ , M _71b ⁺ , M _71c ⁺ , A _71a ⁻ , A _71b ⁻ , A _71c ⁻ , L _{71 ,} L ₇₂ and L ₇₃ may have an acid decomposable group as a substituent.

Hereinafter, the organic cation which a specific photoacid generator may have, and the site other than it are illustrated. The aforementioned organic cations, for example, can be used as M ₁₁ ⁺ , M ₁₂ ⁺ , M _21a ⁺ , M _21b ⁺ , M ₂₂ ⁺ , M _31a ⁺ in the compounds represented by chemical formula (Ia-1) to chemical formula (Ia-5). , M _31b ⁺ , M ₃₂ ⁺ , M _41a + , M _41b ⁺ , M ₄₂ ^{+ ,} M _51a ⁺ , M _51b ⁺ , M _51c ⁺ , M _52a ⁺ or M _52b ⁺ use. Parts other than the above, for example, can be used as M ₁₁ ⁺ , M ₁₂ ⁺ , M _21a ⁺ , M _21b ⁺ , M ₂₂ ⁺ , M _31a in the compounds represented by chemical formula (Ia-1) to chemical formula (Ia-5). ⁺ , M _31b ⁺ , M ₃₂ ⁺ , M _41a ⁺ , M _41b ⁺ , M ₄₂ ⁺ , M _51a ⁺ , M _51b ⁺ , M _51c ⁺ , M _52a ⁺ or M _52b ⁺ are used. An appropriate combination of the organic cations shown below and other parts can be used as a specific photoacid generator.

First, examples of organic cations that a specific photoacid generator may have are shown.

[chemical formula 62]

[chemical formula 63]

[chemical formula 64]

Next, sites other than organic cations that a specific photoacid generator may have are exemplified.

[chemical formula 65]

[chemical formula 66]

The molecular weight of the specific photoacid generator is preferably from 100 to 10,000, more preferably from 100 to 2,500, and more preferably from 100 to 1,500.

The content of the specific photoacid generator (total content of compounds (I) and (II)) is preferably 10% by mass or more, preferably 15% by mass or more, and 20% by mass relative to the total solid content of the photoresist composition The above is more preferable, and 40 mass % or more are more preferable. The upper limit is preferably 80% by mass or less, further preferably 70% by mass or less, and more preferably 60% by mass or less, with respect to the total solid content of the photoresist composition. One or two or more specific photoacid generators can be used alone. When two or more kinds are used, it is preferable that the total content thereof is within the above-mentioned preferred content range.

<Compound (III)> Compound (III) is a compound (onium salt) represented by "M ⁺ X ^- ", and is preferably a compound that generates an organic acid by exposure. Examples of the aforementioned organic acid include sulfonic acids (aliphatic sulfonic acids such as fluorinated aliphatic sulfonic acids, aromatic sulfonic acids, and camphorsulfonic acids), bis(alkylsulfonyl)imidic acids, and (Alkylsulfonyl)methylating acid.

M ⁺ represents an organic cation. The aforementioned organic cation is preferably an organic cation (cation (ZaI)) represented by the chemical formula (ZaI), or an organic cation (cation (ZaII)) represented by the chemical formula (ZaII). In the compound represented by "M ⁺ X ^- ", X ^- represents an organic anion. As the aforementioned organic anion, a non-nucleophilic anion (an anion having a particularly low ability to cause a nucleophilic reaction) is preferred.

Examples of non-nucleophilic anions include sulfonic acid anions (aliphatic sulfonic acid anions, aromatic sulfonic acid anions, camphor sulfonic acid anions, etc.), sulfonimide anions, bis(alkylsulfonyl)acyl iminium anion and tris(alkylsulfonyl)methide anion.

The aliphatic part in the aliphatic sulfonic acid anion can be an alkyl group or a cycloalkyl group, preferably a linear or branched alkyl group with 1 to 30 carbons, or a ring with 3 to 30 carbons alkyl. The aforementioned alkyl group may be, for example, a fluoroalkyl group (it may or may not have a substituent other than a fluorine atom. It may also be a perfluoroalkyl group).

The aryl group in the aromatic sulfonic acid anion and the aromatic carboxylic acid anion is preferably an aryl group having 6 to 14 carbon atoms, and examples thereof include phenyl, tolyl, and naphthyl.

The alkyl group, cycloalkyl group and aryl group mentioned above may have a substituent. Specifically, examples of substituents include nitro groups, halogen atoms such as fluorine atoms and chlorine atoms, carboxyl groups, hydroxyl groups, amino groups, cyano groups, alkoxy groups (preferably having 1 to 15 carbon atoms), alkyl groups (carbon preferably 1-10), cycloalkyl (preferably 3-15 carbon), aryl (preferably 6-14 carbon), alkoxycarbonyl (preferably 2-12 carbon), acyl (preferably carbon preferably 2-12), alkoxycarbonyloxy (preferably 2-18 carbon), alkylthio (preferably 1-15 carbon), alkylsulfonyl (preferably 1-15 carbon) , alkyliminosulfonyl (preferably 1-15 carbons), alkylaminosulfonyl (preferably 1-15 carbons), and aryloxysulfonyl (preferably 6-20 carbons) good).

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. Examples of substituents of these alkyl groups include halogen atoms, alkyl groups substituted by halogen atoms, alkoxy groups, alkylthio groups, alkoxysulfonyl groups, aryloxysulfonyl groups, and cycloalkylaryl groups. The oxysulfonyl group is preferably a fluorine atom or an alkyl group substituted by a fluorine atom. In addition, the alkyl groups in the bis(alkylsulfonyl)imide anion can also bond with each other to form a ring structure. Thereby, acid strength can be increased.

As the non-nucleophilic anion, preferred are aliphatic sulfonic acid anions in which at least the alpha position of sulfonic acid is substituted by fluorine atoms, aromatic sulfonic acid anions in which fluorine atoms or groups having fluorine atoms are substituted, and alkyl groups substituted by fluorine atoms. A substituted bis(alkylsulfonyl)imide anion, or a tris(alkylsulfonyl)methide anion in which the alkyl group is substituted with a fluorine atom.

As the non-nucleophilic anion, an anion represented by the chemical formula (AN1) is also preferable.

[chemical formula 67]

In chemical formula (AN1), o represents the integer of 1-3. p represents an integer of 0-10. q represents an integer of 0-10.

Xf represents a fluorine atom or an alkyl group substituted by at least one fluorine atom. The carbon number of the aforementioned alkyl group is preferably 1-10, more preferably 1-4. Furthermore, as the alkyl group substituted with at least one fluorine atom, a perfluoroalkyl group is preferred. Xf is preferably a fluorine atom or a perfluoroalkyl group having 1 to 4 carbon atoms, more preferably a fluorine atom or CF ₃ , more preferably Xf of both is a fluorine atom.

R ₄ and R ₅ each independently represent a hydrogen atom, a fluorine atom, an alkyl group, or an alkyl group substituted by at least one fluorine atom. When there are multiple R ₄ and R ₅ , R ₄ and R ₅ may be the same or different from the alkyl group represented by R ₄ and R ₅ , preferably having 1 to 4 carbon atoms. The aforementioned alkyl group may have a substituent. R ₄ and R ₅ are preferably hydrogen atoms. The specific examples and preferred aspects of the alkyl group substituted by at least one fluorine atom are the same as the specific examples and preferred aspects of Xf in the chemical formula (AN1).

L represents a divalent linking group. When a plurality of L exists, L may be respectively the same or different. Examples of divalent linking groups include -O-CO-O-, -COO-, -CONH-, -CO-, -O-, -S-, -SO-, -SO ₂ -, extended Alkyl (preferably 1 to 6 carbons), cycloalkylene (preferably 3 to 15 carbons), alkenylene (preferably 2 to 6 carbons), and a divalent combination of these link base. Among them, as the divalent linking group, -O-CO-O-, -COO-, -CONH-, -CO-, -O-, -SO ₂ -, -O-CO-O-alkylene-, -COO-alkylene-, or -CONH-alkylene-preferably, -O-CO-O-, -O-CO-O-alkylene-, -COO-, -CONH-, -SO ₂ -, or -COO-alkylene is more preferred.

W represents an organic group including a ring structure. Among them, a cyclic organic group is preferable. As the cyclic organic group, for example, an alicyclic group, an aryl group and a heterocyclic group are mentioned. The alicyclic group can be monocyclic or polycyclic. Examples of the monocyclic alicyclic group include monocyclic cycloalkyl groups such as cyclopentyl, cyclohexyl, and cyclooctyl. Examples of the polycyclic alicyclic group include polycyclic cycloalkyl groups such as norbornyl, tricyclodecanyl, tetracyclodecanyl, tetracyclododecyl, and adamantyl. Among them, alicyclic groups having a bulky structure having 7 or more carbon atoms such as norbornyl, tricyclodecanyl, tetracyclodecanyl, tetracyclododecyl, and adamantyl are preferable.

Aryl groups can be monocyclic or polycyclic. Examples of the aforementioned aryl group include phenyl, naphthyl, phenanthrenyl and anthracenyl. A heterocyclic group can be monocyclic or polycyclic. Among them, in the case of a polycyclic heterocyclic group, the diffusion of acid can be more suppressed. In addition, a heterocyclic group may or may not have aromaticity. As an aromatic heterocycle, a furan ring, a thiophene ring, a benzofuran ring, a benzothiophene ring, a dibenzofuran ring, a dibenzothiophene ring, and a pyridine ring are mentioned, for example. Examples of the non-aromatic heterocycle 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.

The aforementioned cyclic organic group may have a substituent. As the aforementioned cyclic organic group, for example, an alkyl group (which may be any of straight chain and branched chain, preferably having 1 to 12 carbon atoms), cycloalkyl group (which may be monocyclic, polycyclic and Any of the spiro rings, preferably with 3 to 20 carbons), aryl (preferably with 6 to 14 carbons), hydroxyl, alkoxy, ester, amido, carbamate, ureido , sulfide group, sulfonamide group and sulfonate group. In addition, carbon constituting the cyclic organic group (carbon contributing to ring formation) may be carbonyl carbon.

As the anion represented by the chemical formula (AN1), SO ₃ ^- -CF ₂ -CH ₂ -OCO-(L) _q' -W, SO ₃ ^- -CF ₂ -CHF-CH ₂ -OCO-(L) are preferable. _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 ^- - CF2 _- CH( _CF3 )-OCO-(L) _q' -W. Here, the definitions of L, q, and W are the same as in chemical formula (AN1). q' represents the integer of 0-10.

As the non-nucleophilic anion, an anion represented by the following chemical formula (AN2) is also preferable.

[chemical formula 68]

In the chemical formula (AN2), X ^B1 and X ^B2 each independently represent a hydrogen atom or an organic group having no valency of a fluorine atom. X ^B1 and X ^B2 are preferably hydrogen atoms. X ^B3 and X ^B4 each independently represent a hydrogen atom or a monovalent organic group. It is preferable that at least one of X ^B3 and X ^B4 is a fluorine atom or an organic group having a valence of a fluorine atom, and it is more preferable that both of X ^B3 and X ^B4 are a fluorine atom or an organic group having a valency of a fluorine atom. Both X ^B3 and X ^B4 are more preferably hydrocarbon groups substituted with fluorine. Here, the definitions of L, q, and W are the same as in chemical formula (AN1).

As the non-nucleophilic anion, an anion represented by the chemical formula (AN3) is preferable.

[chemical formula 69]

In the chemical formula (AN3), Xa each independently represents a fluorine atom or an alkyl group substituted with at least one fluorine atom. Xb each independently represents a hydrogen atom or an organic group not having a fluorine atom. The definitions and preferred forms of o, p, q, R ₄ , R ₅ , L and W are the same as those in formula (AN1).

As the non-nucleophilic anion, an anion represented by the chemical formula (AN4) is also preferable.

[chemical formula 70]

In the chemical formula (AN4), R ¹ and R ² each independently represent a non-electron-attracting group or a hydrogen atom. Examples of the aforementioned non-electron-attracting groups include hydrocarbon groups, hydroxyl groups, oxyhydrocarbyl groups, oxycarbonylhydrocarbyl groups, amine groups, hydrocarbon-substituted amino groups, and hydrocarbon-substituted amido groups. In addition, each of the non-electron-attracting groups is preferably -R', -OH, -OR', -OCOR', -NH ₂ , -NR' ₂ , -NHR', or -NHCOR' independently. . R' is a monovalent hydrocarbon group.

Examples of the monovalent hydrocarbon group represented by R' include alkyl groups such as methyl, ethyl, propyl, and butyl; alkenyl groups such as vinyl, propenyl, and butenyl; ethynyl, propynyl, etc. Monovalent linear or branched hydrocarbon groups such as alkynyl such as butynyl; cycloalkyl such as cyclopropyl, cyclobutyl, cyclopentyl, cyclohexyl, norbornyl and adamantyl; cyclopropenyl , cyclobutenyl, cyclopentenyl and norbornenyl and other monovalent alicyclic hydrocarbon groups such as cycloalkenyl; phenyl, tolyl, xylyl, tricresyl, naphthyl, methylnaphthyl, anthracenyl , and aryl groups such as methyl anthracenyl; monovalent aromatic ring groups such as aralkyl groups such as methyl, phenethyl, phenylpropyl, naphthalene methyl anthracenyl, etc. Wherein, R ¹ and R ² are each independently a hydrocarbon group (preferably a cycloalkyl group) or a hydrogen atom.

In the chemical formula (AN4), L represents a divalent linking group composed of more than one linking group S and an alkylene group that may have more than one substituent, or a divalent linking group consisting of more than one linking group S base. Linking group S is selected from * ^A -O-CO-O-* ^B , * ^A -CO-* ^B , * ^A -CO-O-* ^B , * ^A -O-CO-* ^B , * ^A -O A group in the group consisting of -* ^B , * ^A -S-* ^B and * ^A -SO ₂ -* ^B. Among them, L is a form of "a divalent linking group formed by combining more than one linking group S and an alkylene group that may have more than one substituent", that is, "comprising more than one linking group S and not having one In the case of a divalent linking group formed by a combination of alkylene groups of the above substituents, the linking group S is preferably selected from * ^A -O-CO-O-* ^B , * ^A -CO-* ^B , Groups in the group consisting of * ^A -O-CO-* ^B , * ^A -O-* ^B , * ^A -S-* ^B and * ^A -SO ₂ -* ^B . In other words, when all the alkylene groups in the "divalent linking group formed by combining one or more linking groups S and alkylene groups that may have one or more substituents" are unsubstituted alkylene groups, the linking group The group S is preferably selected from * ^A -O-CO-O-* ^B , * ^A -CO-* ^B , * ^A -O-CO-* ^B , * ^A -O-* ^B , * ^A -S- A group in the group consisting of * ^B and * ^A -SO ₂ -* ^B . * ^A represents the bonding position of the R ³ side in the chemical formula (AN4), and * ^B represents the bonding position of the -SO ₃ ^- side in the chemical formula (AN4).

In a divalent linking group composed of one or more linking groups S and an alkylene group which may have one or more substituents, only one linking group S may exist, or two or more linking groups may exist. Similarly, the alkylene group which may have a substituent may exist only one, or may exist two or more. When there are a plurality of the aforementioned linking groups S, the linking groups S present in the plurality may be the same as or different from each other. When the aforementioned alkylene group exists in plural, the plural alkylene groups may be the same or different. In addition, the linking groups S may be bonded continuously. Among them, the groups selected from the group consisting of * ^A -CO-* ^B , * ^A -O-CO-* ^B and * ^A -O-* ^B are bonded continuously without forming "* ^A -O-CO -O-* ^B " is preferred. In addition, the groups selected from the group consisting of * ^A -CO-* ^B and * ^A -O-* ^B are bonded continuously without forming "* ^A -O-CO-* ^B " and "* ^A -CO Any one of -O-* ^B is preferred.

In the bivalent linking group composed of one or more linking groups S, only one linking group S may exist, or two or more linking groups S may exist. When there are a plurality of linking groups S, the linking groups S when there are a plurality of them may be the same or different. At this time, the groups selected from the group consisting of * ^A -CO-* ^B , * ^A -O-CO-* ^B and * ^A -O-* ^B are bonded continuously without forming "* ^A -O- CO-O-* ^B " is preferred. In addition, the groups selected from the group consisting of * ^A -CO-* ^B and * ^A -O-* ^B are bonded continuously without forming "* ^A -O-CO-* ^B " and "* ^A -CO Any one of -O-* ^B is preferred.

However, in either case, in L, the atom at the β-position with respect to -SO ₃ ^- is not a carbon atom having a fluorine atom as a substituent. In addition, when the atom at the β position is a carbon atom, it is sufficient that the carbon atom is not directly substituted by a fluorine atom, and the carbon atom may have a substituent containing a fluorine atom (for example, a fluorinated alkyl group such as trifluoromethyl) ). In addition, in other words, the aforementioned β-position is the atom in L that is directly bonded to -C(R ¹ )(R ² )- in the chemical formula (AN4).

Among them, it is preferable that L has only one linking group S. That is, it is preferable that L represents a divalent linking group consisting of one linking group S and an alkylene group which may have one or more substituents, or a divalent linking group consisting of one linking group S.

For example, it is preferable that L is a group represented by chemical formula (AN4-2). * ^a -(CR ^2a ₂ ) _X -Q-(CR ^2b ₂ ) _Y -* ^b (AN4-2)

In the chemical formula (AN4-2), * ^a represents the bonding position with ^R in the chemical formula (AN4). * ^b represents the bonding position with -C(R ¹ )(R ² )- in the chemical formula (AN4). X and Y each independently represent the integer of 0-10, Preferably it is the integer of 0-3. R ^2a and R ^2b each independently represent a hydrogen atom or a substituent. When a plurality of R ^2a and R ^2b respectively exist, the plurality of R ^2a and R ^2b present may be the same or different. However, when Y is 1 or more, R ^2b in CR ^2b ₂ directly bonded to -C(R ¹ )(R ² )- in the chemical formula (AN4) is other than a fluorine atom. Q means * ^A -O-CO-O-* ^B , * ^A -CO-* ^B , * ^A -CO-O-* ^B , * ^A -O-CO-* ^B , * ^A -O-* ^B , * ^A -S-* ^B , or * ^A - _SO2- * ^B . Wherein, when X+Y in the chemical formula (AN4-2) is 1 or more and either R ^2a and R ^2b in the chemical formula (AN4-2) is a hydrogen atom, Q represents * ^A -O-CO-O -* ^B , * ^A -CO-* ^B , * ^A -O-CO-* ^B , * ^A -O-* ^B , * ^A -S-* ^B , or * ^A - _SO2- * ^B . * ^A represents the bonding position on the R ³ side in the chemical formula (AN4), and * ^B represents the bonding position on the -SO ₃ ^- side in the chemical formula (AN4).

In the chemical formula (AN4), R ³ represents an organic group. The aforementioned organic group is not limited as long as it has more than one carbon atom, and may be a straight-chain group (for example, a straight-chain alkyl group), a branched-chain group (for example, a branched-chain group such as a tert-butyl group) Alkyl group), can also be a cyclic group. The aforementioned organic group may or may not have a substituent. The aforementioned organic group may or may not have a heteroatom (oxygen atom, sulfur atom, and/or nitrogen atom, etc.).

Among them, R ³ is preferably an organic group with a ring structure. The aforementioned cyclic structure may be monocyclic or polycyclic, and may have a substituent. The ring in the organic group having a ring structure is preferably directly bonded to L in the chemical formula (AN4). The organic group having the aforementioned cyclic structure, for example, may or may not have a heteroatom (oxygen atom, sulfur atom, and/or nitrogen atom, etc.). A heteroatom may be substituted with one or more of the carbon atoms forming the ring structure. The organic group having the aforementioned cyclic structure, for example, is preferably a hydrocarbon group having a cyclic structure, a lactone cyclic group, and a sultone cyclic group. Among them, the organic group having the aforementioned cyclic structure is preferably a hydrocarbon group having a cyclic structure. The hydrocarbon group having the aforementioned cyclic structure is preferably a monocyclic or polycyclic cycloalkyl group. These groups may have substituents. The aforementioned cycloalkyl group can be monocyclic (cyclohexyl, etc.) or polycyclic (adamantyl, etc.), preferably with 5-12 carbon atoms. As the aforementioned lactone group and sultone group, for example, any of the structures represented by the aforementioned chemical formulas (LC1-1) to (LC1-21) and the structures represented by the aforementioned chemical formulas (SL1-1) to (SL1-3) Among them, a group obtained by removing one hydrogen atom from the member ring atoms constituting the lactone structure or the sultone structure is preferable.

The non-nucleophilic anion may be benzenesulfonate anion, preferably benzenesulfonate anion substituted with a branched alkyl or cycloalkyl group.

As the non-nucleophilic anion, an aromatic sulfonic acid anion represented by the chemical formula (AN5) is also preferable.

[chemical formula 71]

In the chemical formula (AN5), Ar represents an aryl group (phenyl, etc.), and may further have a substituent other than a sulfonic acid anion and a -(D-B) group. As a substituent which may have further, a fluorine atom and a hydroxyl group are mentioned, for example.

n represents an integer of 0 or more. As n, 1-4 are preferable, 2-3 are still more preferable, and 3 is still more preferable.

D represents a single bond or a divalent linking group. Examples of the divalent linking group include -O-, thioether group, carbonyl group, arylene group, arboryl group, sulfonic acid -COO-, -COO-, and groups consisting of two or more of them. .

B represents a hydrocarbon group.

B is preferably an aliphatic hydrocarbon structure. B is more preferably an isopropyl group, a cyclohexyl group, or an aryl group which may have a substituent (tricyclohexylphenyl group, etc.).

As the non-nucleophilic anion, disulfonamide anion is also preferred. For example, the disulfonamide anion is an anion represented by N ^- (SO ₂ -R ^q ) ₂ . Here, R ^q represents an alkyl group which may have a substituent, preferably a fluoroalkyl group, more preferably a perfluoroalkyl group. Two R ^q may be bonded to each other to form a ring. As a group formed by bonding two R ^q to each other, an alkylene group which may have a substituent is preferable, a fluoroalkylene group is further preferable, and a perfluoroalkylene group is more preferable. The number of carbon atoms in the aforementioned alkylene group is preferably 2-4.

Compound (III) may be in the form of a low-molecular compound or embedded in a part of a polymer. In addition, the form of a low-molecular compound and the form embedded in a part of a polymer may be used together. The molecular weight of the compound (III) in the form of a low-molecular compound is preferably at most 3,000, further preferably at most 2,000, and more preferably at most 1,000. The lower limit is preferably 100 or more. When the compound (III) is embedded in a part of the polymer, it may be embedded in a part of the resin A, or may be embedded in a resin different from the resin A. Compound (III) is preferably in the form of a low molecular weight compound.

As (III), for example, paragraphs [0135] to [0171] of International Publication No. 2018/193954, paragraphs [0077] to [0116] of International Publication No. 2020/066824, paragraphs [0077] to [0116] of International Publication No. 2017/154345 [ The photoacid generators disclosed in paragraphs [0018] to [0075] and paragraphs [0334] to [0335] are also preferable.

When the photoresist composition contains the compound (III), its content is preferably 0.5% by mass or more, more preferably 1% by mass or more, based on the total solid content of the photoresist composition. The upper limit is preferably 40% by mass or less, more preferably 30% by mass or less, based on the total solid content of the photoresist composition. Other photoacid generators can be used alone or two or more. When two or more kinds are used, it is preferable that the total content thereof is within the aforementioned preferred content range.

[Acid diffusion control agent (C)] The photoresist composition may contain an acid diffusion control agent. The acid diffusion control agent is a quencher that captures the acid generated from the photoacid generator, etc. during exposure, and suppresses the reaction of the acid-degradable resin in the unexposed part caused by the excess generated acid. The kind of the acid diffusion control agent is not particularly limited, for example, a basic compound (CA), a low-molecular compound (CB) having a nitrogen atom and a group detached by the action of an acid, and a Compounds (CC) whose ability to control acid diffusion decreases or disappears due to exposure to chemical rays or radiation. Examples of the compound (CC) include an onium salt compound (CD) that becomes a relatively weak acid relative to a photoacid generator, and a basic compound (CE) that reduces or disappears basicity by irradiation with actinic rays or radiation. In addition, for example, as a specific example of the basic compound (CA), those described in paragraphs [0132] to [0136] of International Publication No. 2020/066824 can be cited. Specific examples of basic compounds (CE) that have reduced or disappeared properties include those described in paragraphs [0137] to [0155] of International Publication No. 2020/066824, which have a nitrogen atom and have Specific examples of the low-molecular-weight compound (CB) of the detached group include those described in paragraphs [0156] to [0163] of International Publication No. 2020/066824, as an onium salt compound having a nitrogen atom in the cationic portion ( Specific examples of CE) include those described in paragraph [0164] of International Publication No. 2020/066824. In addition, specific examples of onium salt compounds (CD) that are relatively weak acids relative to photoacid generators include those described in paragraphs [0305] to [0314] of International Publication No. 2020/158337.

In addition to the foregoing, for example, 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, U.S. Patent Application Publication No. 2016/ No. 0237190A1 No. [0403] ~ [0423] paragraphs, and U.S. Patent Application Publication No. 2016/0274458A1 No. [0259] ~ [0328] paragraphs disclosed known compounds as acid diffusion control agent.

When the photoresist composition contains an acid diffusion control agent, the content of the acid diffusion control agent (if there are multiple types, the total) is preferably 0.1 to 15.0% by mass relative to the total solid content of the photoresist composition , 1.0~15.0% by mass is more preferable. In the photoresist composition, one kind of acid diffusion control agent can be used alone, or two or more kinds can be used in combination.

[Hydrophobic resin (D)] The photoresist composition may further contain a hydrophobic resin different from the resin A. The hydrophobic resin is preferably designed to be partial to the surface of the resist film, but unlike surfactants, it does not necessarily have to have a hydrophilic group in the molecule, and it does not help the uniform mixing of polar substances and non-polar substances . As effects brought about by adding a hydrophobic resin, control of the static and dynamic contact angles of the surface of the resist film with respect to water, and suppression of outgassing can be mentioned.

From the viewpoint of localization on the surface of the film, the hydrophobic resin preferably has any one or more of fluorine atoms, silicon atoms, and _CH3 moiety structures included in the side chain portion of the resin, more preferably two or more. In addition, the aforementioned hydrophobic resin preferably has a hydrocarbon group having 5 or more carbon atoms. These groups may exist in the main chain of the resin, or may be substituted by side chains. Examples of the hydrophobic resin include compounds described in paragraphs [0275] to [0279] of International Publication No. 2020/004306.

When the photoresist composition contains a hydrophobic resin, the content of the hydrophobic resin is preferably 0.01 to 20.0% by mass, more preferably 0.1 to 15.0% by mass based on the total solid content of the photoresist composition.

[Surfactant (E)] The photoresist composition may contain a surfactant. When a surfactant is contained, it is possible to form a pattern with more excellent adhesion and fewer image development defects. The surfactant is preferably a fluorine-based and/or silicon-based surfactant. In addition, from the viewpoint of environmental control, silicon-based surfactants and/or fluorine-based surfactants having 7 or less carbon atoms can also be used. As the fluorine-based and/or silicon-based surfactants, the surfactants disclosed in paragraphs [0218] and [0219] of International Publication No. 2018/019395 can be mentioned.

Surfactants may be used alone or in combination of two or more.

When the photoresist composition 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, more preferably 0.1 to 1.0% with respect to the total solid content of the photoresist composition. Quality % is better.

[Solvent (F)] The photoresist composition preferably contains a solvent. The solvent is preferably (M1) propylene glycol monoalkyl ether carboxylate, and (M2) is selected from the group consisting of propylene glycol monoalkyl ether, lactate, acetate, alkoxy propionate, chain ketone, cyclic ketone, internal At least one of at least one of the group consisting of esters and alkylene carbonates. In addition, the aforementioned solvent may further contain components other than components (M1) and (M2).

The inventors of the present invention found that when these solvents are used in combination with the above-mentioned resin, the coatability of the photoresist composition is improved, and a pattern with few development defects can be formed. The reason for this is not clear, but the present inventors believe that the cause is as follows: These solvents can suppress the uneven thickness of the resist film and the generation of precipitates during spin coating due to the good balance of the solubility, boiling point, and viscosity of the above-mentioned resins. wait. Component (M1) and component (M2) are described in detail in paragraphs [0218] to [0226] of International Publication No. 2020/004306, and these contents are incorporated into this specification.

When the solvent further contains components other than components (M1) and (M2), the content of components other than components (M1) and (M2) is preferably 5 to 30% by mass based on the total amount of the solvent.

The content of the solvent in the photoresist composition is preferably set at a solid content concentration of 0.5 to 30% by mass, more preferably 1 to 20% by mass. Thereby, the applicability of the photoresist composition can be further improved.

[Other additives] The photoresist composition may further contain dissolution inhibiting compounds, dyes, plasticizers, photosensitizers, light absorbers, and/or compounds that promote solubility with respect to the developer (for example, molecular weight below 1000 phenolic compounds, or alicyclic or aliphatic compounds with carboxyl groups).

The photoresist composition may further contain a dissolution inhibiting compound. Here, the term "dissolution inhibiting compound" refers to a compound having a molecular weight of 3000 or less that is decomposed by the action of an acid to lower its solubility in an organic developer.

The photoresist composition of the present invention is suitable as a photosensitive composition for EUV light. The wavelength of EUV light is 13.5nm, which is shorter than that of ArF (wavelength 193nm) light, etc., so the number of incident photons is less when exposed with the same sensitivity. Therefore, the "photon shot noise" in which the number of photons varies in probability has a large influence, leading to LER deterioration and bridge defects. In order to reduce photon shot noise, there is a method to increase the number of incident photons by increasing the exposure, but it often needs to be traded off with the requirement of high sensitivity.

When the A value obtained from the following chemical formula (1) is high, the EUV and electron beam absorption efficiency of the resist film formed of the photoresist composition becomes high, and photon shot noise can be effectively reduced. The A value represents the absorption efficiency of EUV light and electron beams in the mass ratio of the resist film. Chemical formula (1): A=([H]×0.04+[C]×1.0+[N]×2.1+[O]×3.6+[F]×5.6+[S]×1.5+[I]×39.5) /([H]×1+[C]×12+[N]×14+[O]×16+[F]×19+[S]×32+[I]×127) A value is preferably 0.120 above. The upper limit is not particularly limited, but when the A value is too large, the EUV light and electron beam transmittance of the resist film will decrease, the optical image profile in the resist film will deteriorate, and as a result, it will be difficult to obtain a good pattern shape, so it is 0.240 It is preferably not more than 0.220, and more preferably not more than 0.220.

In addition, in the chemical formula (1), [H] represents the molar ratio of hydrogen atoms derived from the total solid content to all atoms in the total solid content of the actinic radiation-sensitive or radiation-sensitive resin composition, and [C] represents The molar ratio of carbon atoms derived from the total solid content relative to the total atoms of the total solid content in the actinic radiation-sensitive or radiation-sensitive resin composition, [N] represents the nitrogen atom derived from the total solid content relative to the photosensitized The molar ratio of the total atoms of the total solid content in the radioactive or radiation-sensitive resin composition, [O] represents the oxygen atoms derived from the total solid content relative to the total oxygen atoms in the actinic radiation-sensitive or radiation-sensitive resin composition. The molar ratio of all atoms in the solid content, [F] represents the molar ratio of fluorine atoms derived from the total solid content to the total atoms in the total solid content of the actinic radiation-sensitive or radiation-sensitive resin composition, [S ] represents the molar ratio of sulfur atoms derived from the total solid content relative to the total atoms of the total solid content in the actinic radiation-sensitive or radiation-sensitive resin composition, and [I] represents the ratio of iodine atoms derived from the total solid content to The molar ratio of all atoms in the total solid content of the actinic radiation-sensitive or radiation-sensitive resin composition. For example, when a photoresist composition has a resin A, a photoacid generator, an acid diffusion controller, and a solvent, the resin A, the photoacid generator, and the acid diffusion controller correspond to solid components. That is, all atoms in the total solid content correspond to the total of all atoms derived from the resin A, all atoms derived from the photoacid generator, and all atoms derived from the acid diffusion control agent. For example, [H] represents the molar ratio of hydrogen atoms derived from the total solid content to all atoms in the total solid content, and [H] represents the hydrogen atoms derived from the aforementioned resin A, The total of the hydrogen atoms of the aforementioned photoacid generator and the hydrogen atoms derived from the aforementioned acid diffusion controller relative to the total atoms derived from the aforementioned resin A, the total atoms derived from the aforementioned photoacid generator, and the aforementioned acid diffusion controller The total molar ratio of all atoms in .

When the structure and content of the constituent components of the total solid content in the photoresist composition are known, the A value can be calculated by calculating the contained atomic ratio. In addition, even when the constituent components are unknown, the constituent atomic ratio can be calculated by an analytical method such as elemental analysis for a resist film obtained by evaporating the solvent component of the photoresist composition.

[Resist Film, Pattern Formation Method] The steps of the pattern formation method using the aforementioned photoresist composition preferably have the following processes. Process 1: The process of forming a resist film on a substrate using a photoresist composition Process 2: The process of exposing the resist film Process 3: The process of developing the exposed resist film using a developer as follows , the steps of each of the aforementioned processes will be described in detail.

<Process 1: Resist film formation process> Process 1 is a process for forming a resist film on a substrate using a photoresist composition. The definition of photoresist composition is as above.

As a method of forming a resist film on a substrate using a photoresist composition, for example, a method of coating a photoresist composition on a substrate is mentioned. Before coating, it is better to filter the photoresist composition according to the need. The pore diameter of the filter is preferably at most 0.1 μm, further preferably at most 0.05 μm, and more preferably at most 0.03 μm. The lower limit is often 0.01 μm or more. In addition, the filter is preferably made of polytetrafluoroethylene, polyethylene, or nylon.

The photoresist composition can be coated on substrates such as those used in the manufacture of integrated circuit devices (eg, silicon and silicon dioxide coatings, etc.) by a suitable coating method such as a spin coater or a coater. The coating method is preferably spin coating using a spin coater. When performing spin coating using a spin coater, the rotation speed is preferably 1000 to 3000 rpm. After coating the photoresist composition, the substrate can be dried to form a resist film. In addition, various undercoat films (for example, inorganic films, organic films, antireflection films, etc.) may be formed under the resist film as needed.

As a drying method, the method of heating and drying is mentioned, for example. Heating may be performed by a device provided in a general exposure machine and/or developing machine, or may be performed using a hot plate or the like. The heating temperature is preferably 80 to 150°C, more preferably 80 to 140°C, more preferably 80 to 130°C. The heating time is preferably from 30 to 1000 seconds, more preferably from 60 to 800 seconds, and more preferably from 60 to 600 seconds.

The thickness of the resist film is preferably from 10 to 120 nm from the viewpoint of being able to form a finer pattern with higher precision. Among them, in the case of EUV exposure, the thickness of the resist film is preferably from 10 to 65 nm, more preferably from 15 to 50 nm.

In addition, a top coat composition may be used to form a top coat layer on a resist film. The composition of the top coat layer is preferably not mixed with the resist film, and thus can be evenly coated on the upper layer of the resist film. The top coat is not particularly limited, and a previously known top coat can be formed by a previously known method. For example, the top coat can be formed according to paragraphs [0072] to [0082] of JP-A-2014-059543 . For example, it is preferable to form a top coat layer containing a basic compound such as described in JP-A-2013-61648 on a resist film. As a basic compound which a top coat layer may have, the basic compound which a photoresist composition may contain is mentioned, for example. In addition, it is also preferable that the top coat layer contains a compound having at least one group or bond selected from the group consisting of ether bond, thioether bond, hydroxyl group, thiol group, carbonyl bond, and ester bond.

<Process 2: Exposure process> Process 2 is a process of exposing the resist film. As the exposure method, a method of irradiating the formed resist film with actinic rays or radiation through a predetermined mask is mentioned. Examples of actinic rays or radiation include infrared light, visible light, ultraviolet light, deep ultraviolet light, extreme ultraviolet light, X-rays and electron beams. The wavelength of actinic rays or radiation is preferably deep ultraviolet light. The wavelength of the far ultraviolet light is preferably 250 nm or less, more preferably 220 nm or less, and more preferably 1 to 200 nm. Specifically, KrF excimer laser (248nm), ArF excimer laser (193nm), F ₂ excimer laser (157nm), EUV light (13nm), X-rays and electron beams are mentioned.

After exposure, it is preferable to perform baking (heating) before image development. The reaction of the exposed part is accelerated by baking, and the sensitivity and pattern shape are further improved. The heating temperature is preferably 80 to 150°C, more preferably 80 to 140°C, and more preferably 80 to 130°C. The heating time is preferably 10 to 1000 seconds, more preferably 10 to 180 seconds, and more preferably 30 to 120 seconds. Heating can be carried out by means of a device equipped with a normal exposure machine and/or developing machine, or using a heating plate or the like. This process is also called Post Exposure Bake (PEB: Post Exposure Bake).

<Process 3: Developing process> Process 3 is a process of using a developer to develop the exposed resist film and 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).

As the developing method, for example, a method in which the substrate is immersed in a tank filled with a developer solution for a certain period of time (dipping method); a method in which the developer solution is deposited on the surface of the substrate by surface tension and left to stand for a certain period of time for development method (immersion method); method of spraying developer on the surface of the substrate (spray method); and method of spraying the developer out of the nozzle at a certain speed on the substrate rotating at a certain speed for scanning and continuously spraying the developer (dynamic distribution method). In addition, after the development process is performed, the development process can be stopped while being replaced with another solvent. The development time is not particularly limited as long as it is the time for the resin in the unexposed part to fully dissolve, and is preferably 10 to 300 seconds, and more preferably 20 to 120 seconds. As the temperature of the developer, 0-50°C is better, and 15-35°C is more preferable.

As an alkaline developing solution, it is preferable to use an alkaline aqueous solution containing an alkali. Types of alkaline aqueous solutions include, for example, alkaline aqueous solutions containing quaternary ammonium salts represented by tetramethylammonium hydroxide, inorganic bases, primary amines, secondary amines, tertiary amines, alcohol amines, or cyclic amines. . Among them, the alkaline developer is preferably a quaternary ammonium salt solution represented by tetramethylammonium hydroxide (TMAH). Appropriate amount of alcohols, surfactants, etc. can be added to the alkaline developer. The alkali concentration of an alkaline developing solution is 0.1-20 mass % normally. In addition, the pH value of the alkaline developer is usually 10.0-15.0. The content of water in the alkaline developer is preferably from 51 to 99.95% by mass.

The organic developer is preferably a developer containing at least one organic solvent selected from the group consisting of ketone solvents, ester solvents, alcohol solvents, amide solvents, ether solvents, and hydrocarbon solvents.

The aforementioned solvents may be mixed in plural kinds, and may be mixed with solvents other than the aforementioned or water. The water content of the entire developer is preferably less than 50% by mass, more preferably less than 20% by mass, more preferably less than 10% by mass, and particularly preferably substantially free of water, relative to the entire mass of the developer. The content of the organic solvent relative to the organic developer is preferably 50 to 100% by mass, more preferably 80 to 100% by mass, more preferably 90 to 100% by mass, and particularly preferably 95 to 100% by mass, based on the entire mass of the developer. good.

<Other processes> The pattern forming method described above preferably includes a process of washing with a cleaning solution after process 3.

As a washing|cleaning liquid used in the washing|cleaning process after the image development process using alkaline developing solution, pure water is mentioned, for example. In addition, an appropriate amount of surfactant can be added to pure water. It is also possible to add an appropriate amount of surfactant to the washing liquid.

The washing liquid used in the washing process after the developing process 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 washing liquid is preferably a washing 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.

The method of the cleaning process is not particularly limited, for example, the following methods can be mentioned: on the substrate rotating at a certain speed, the method of continuously spraying the cleaning solution (spin coating method); dipping the substrate in a tank filled with cleaning solution for a certain period of time The method of time (dipping method); and the method of spraying the cleaning solution on the surface of the substrate (spray method). In addition, the pattern forming method of the present invention may include a heating process (Post Bake) after the washing process. Through this process, the developer and cleaning solution remaining between the patterns and inside the patterns can be removed. In addition, this process also has the effect of smoothing the resist pattern and improving the surface roughness of the pattern. The heating process after the washing process is usually performed at 40-250°C (preferably 90-200°C) for 10 seconds-3 minutes (preferably 30 seconds-2 minutes).

In addition, substrate etching can be performed using the formed pattern as a mask. That is, the pattern formed in process 3 can be used as a mask to process the substrate (or the underlying film and substrate) to form a pattern on the substrate. The processing method of the substrate (or the lower film and the substrate) is not particularly limited, and it is preferable to use the pattern formed in process 3 as a mask to form the pattern by dry etching the substrate (or the lower film and the substrate). method. Dry etching is preferably oxygen plasma etching.

Various materials used in the photoresist composition and the pattern forming method of the present invention (for example, solvent, developer, cleaning solution, composition for forming an antireflection film, composition for forming a top coat layer, etc.) are preferably not Contains impurities such as metals. The content of impurities contained in these materials is preferably not more than 1 mass ppm, more preferably not more than 10 mass ppb, and not more than 100 mass ppt (parts per trillion) relative to the total solid content of the photoresist composition or various materials Better, special offer below 10 quality ppt, best below 1 quality ppt. The lower limit thereof is preferably 0 mass ppt or more. 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.

As a method of removing impurities such as metals from various materials, for example, filtration using a filter is mentioned. The details of using the filter are described in paragraph [0321] of International Publication No. 2020/004306.

In addition, as a method of reducing impurities such as metals contained in various materials, for example, a method of selecting a raw material with a low metal content as a raw material constituting various materials; a method of filtering raw materials constituting various materials with a filter ; and the method of carrying out distillation under the conditions of suppressing pollution as much as possible by using Teflon (registered trademark) to form a lining in the device, etc.

In addition to filter filtration, adsorption materials can also be used to remove impurities, and filter filtration and adsorption materials can also be used in combination. As the adsorbent, known adsorbents can be used, for example, inorganic adsorbents such as silica gel and zeolite, and organic adsorbents such as activated carbon can be used. In order to reduce impurities such as metals contained in the aforementioned various materials, it is necessary to prevent mixing 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 liquid used to clean the manufacturing equipment. The content of the metal component contained in the used cleaning solution is preferably not more than 100 ppt by mass (parts per trillion), further preferably not more than 10 ppt by mass, and more preferably not more than 1 ppt by mass. The lower limit thereof is preferably 0 mass ppt or more.

Conductive compounds can be added to organic treatment liquids such as washing liquids to prevent malfunctions in chemical piping and various components (filters, O-rings, tubes, etc.) that accompany electrostatic charging and subsequent electrostatic discharge. As a conductive compound, methanol is mentioned, for example. From the viewpoint of maintaining good developing properties or washing properties, the amount added is preferably 10% by mass or less, more preferably 5% by mass or less. The lower limit thereof is preferably 0% by mass or more. As the chemical piping, for example, SUS (stainless steel), or various piping coated with antistatic-treated polyethylene, polypropylene, or fluororesin (polytetrafluoroethylene or perfluoroalkoxy resin, etc.) can be used. Likewise, antistatic-treated polyethylene, polypropylene, or fluororesin (polytetrafluoroethylene, perfluoroalkoxy resin, etc.) can be used for filters and O-rings.

[Manufacturing method of electronic components] In addition, the present invention also relates to a method of manufacturing electronic components including the aforementioned pattern forming method, and an electronic device manufactured according to the manufacturing method. The electronic components of the present invention are preferably electronic components mounted on electrical and electronic equipment (home appliances, OA (Office Automation), media-related equipment, optical equipment, and communication equipment, etc.). [Example]

Hereinafter, the present invention is described in more detail based on examples. As long as the materials, usage amounts, ratios, processing contents, and processing steps shown in the following examples do not depart from the purpose of the present invention, they can be appropriately changed. Therefore, the scope of the present invention should not be limitedly interpreted by the examples shown below.

[Components of Photoresist Composition] The components contained in the photoresist compositions used in Examples and Comparative Examples are as follows.

[Resin] <Synthesis of Resin A-1> Cyclohexanone (62 g) was heated to 85° C. under a nitrogen stream. Stir the liquid, and add dropwise the monomer (25 g) represented by the chemical formula (M-1), the monomer (8.6 g) represented by the chemical formula (M-23), and the monomer represented by the chemical formula (M-31) over 3 hours. Monomer (46g), monomer represented by chemical formula (M-8) (21g), cyclohexanone (248g) and dimethyl 2,2'-azobisisobutyrate (V-601, Fujifilm and A mixed solution (100.7 g) of a cyclohexanone solution (10% by weight) produced by Ko Pure Chemical Industry Co., Ltd.) was used to obtain a reaction solution. After completion of the dropwise addition, the reaction liquid was further stirred at 85° C. for 3 hours. After cooling the obtained reaction solution, reprecipitate with a large amount of ethyl acetate/heptane=1/9 (mass ratio) mixed solution, filter, and vacuum-dry the obtained solid to obtain resin A-1 (83g) . In addition, all the synthesis|combination of the said resin A-1 was performed under the yellow light. In addition, resins other than resin A-1 were synthesized according to the synthesis method of resin A-1.

[chemical formula 72]

The resins (A-1 to A-42 (corresponding to resin A), a-1) used to prepare the photoresist composition are as follows. In Table 1, the "mole ratio" column indicates the content (mole %) of each repeating unit relative to all repeating units. The "Mw" column indicates the weight average molecular weight. The "Mw/Mn" column shows the degree of dispersion. Mn represents a number average molecular weight.

[Table 1]

The structure of the monomer corresponding to each repeating unit in the resin is shown below. M-31～M-65 correspond to specific compounds.

[chemical formula 73]

[chemical formula 74]

[chemical formula 75]

[chemical formula 76]

[chemical formula 77]

[chemical formula 78]

[chemical formula 79]

[chemical formula 80]

[Photoacid Generators] The structures of the photoacid generators (B-1 to B-16 (corresponding to specific compounds), b-1 to b-10) used to prepare the photoresist composition are shown below.

[chemical formula 81]

[chemical formula 82]

[Acid diffusion control agent] The structure of the acid diffusion control agent used to prepare the photoresist composition is shown below.

[chemical formula 83]

[Hydrophobic Resin] The structure of the hydrophobic resin used to prepare the photoresist composition is shown below.

[chemical formula 84]

The compositional ratio (mass ratio, corresponding to the left side), weight average molecular weight (Mw) and degree of dispersion (Mw/Mn) of each repeating unit of the aforementioned hydrophobic resin are shown below. Mn represents a number average molecular weight. Hydrophobic resin was synthesized according to the synthesis method of resin A-1 (synthesis example 1).

[Table 2]

[Surfactant] Surfactants used to prepare the photoresist composition are as follows. W-1: MEGAFAC R08 (manufactured by DIC, fluorine and silicon-based surfactant) W-2: MEGAFAC F176 (manufactured by DIC, fluorine-based surfactant) W-3: Troysol S-366 (manufactured by TROY CHEMICAL, Fluorinated surfactant) W-4: PF656 (manufactured by OMNOVA, fluorinated surfactant)

[Solvent] The solvents used for preparing the photoresist composition are as follows. S-1: Propylene glycol monomethyl ether acetate (PGMEA) S-2: Propylene glycol monomethyl ether (PGME) S-3: Propylene glycol monoethyl ether (PGEE) S-4: Cyclohexanone S-5: Cyclopentanone S -6: 2-heptanone S-7: Ethyl lactate S-8: γ-butyrolactone S-9: Propylene carbonate

[Preparation of photoresist composition] The components shown in the table below were mixed so that the solid content concentration was 1.4% by mass. Next, the obtained liquid mixture was filtered using a filter made of polyethylene with a pore diameter of 0.02 μm to prepare each photoresist composition. In addition, "solid content" means all components except a solvent. In the table, the "Amount" column indicates the content (mass %) of each solid component relative to the total solid component. The "mixing ratio" column of "solvent" indicates the mixing ratio (mass ratio) of each solvent.

[table 3]

[Test] [Pattern formation (1): EB exposure, alkaline development] The 6-inch silicon wafer (or chromium wafer) was treated with hexamethyldisilazane (HMDS). Each photoresist composition shown in the table below was coated on the obtained surface-treated silicon wafer using a spin coater Mark8 (manufactured by Tokyo Electron Co., Ltd.), and dried on a hot plate at a temperature of 130°C for 300 seconds to obtain a film Resist films each having a thickness of 100 nm. In addition, in the aforementioned method of producing the resist film, a chromium substrate may also be used instead of a silicon wafer. The obtained resist film was subjected to pattern exposure through an exposure mask (line:space=1:1) using an electron beam drawing device (manufactured by Advantest, F7000S, acceleration voltage 50KeV). Next, it was heated on a hot plate at a temperature of 100° C. for 60 seconds, immersed in a 2.38% by mass tetramethylammonium hydroxide (TMAH) aqueous solution for 60 seconds, and then washed with water for 30 seconds. Finally, after the silicon wafer was rotated at 4000 rpm for 30 seconds, it was baked at a temperature of 95° C. for 60 seconds to dry it to obtain a silicon wafer with a predetermined pattern.

<Defects in development> Using a defect inspection device KLA2360 (trade name) manufactured by KLA-Tencor Corporation, the pixel size of the defect inspection device was set to 0.16 μm, and the threshold value was set to 20, and the sensitivity (Eop) described later was formed. A pattern with a line width of 50nm (line: space = 1:1), detect defects (number/cm ² ) extracted from the difference between the image for comparison and the overlap of the pixel unit, and calculate the defect per unit area Number (pcs/cm ² ). Then, review the defects, classify and extract the development defects from all the defects, and calculate the number of development defects per unit area (pieces/cm ² ). A: The number of development defects is less than 0.5/ ^{cm 2} B: The number of development defects is 0.5 or more and less than 1.0/cm ² C: The number of development defects is 1.0 or more/cm ² and less than 5.0/cm ² D : The number of developing defects is 5.0 pieces/cm ² or more

<Sensitivity> The line width of the line and space pattern formed while changing the exposure amount (electron beam irradiation amount) was measured, and the exposure amount when the line width was 50nm was obtained as the sensitivity (Eop, μC/cm ² ) . The smaller the value of sensitivity, the better the sensitivity.

<Result>

The evaluation results are shown in the table below. In the table, each record is expressed as follows. The column "Substituent X (σp)" indicates the type of substituent X and its σp. Specifically, "Br(0.23)" in Example 1a means that it has Br (bromine atom) as the substituent X, and σp in Hammet's law of Br is 0.23.

[Table 4]

It was confirmed that the photoresist composition of the present invention is excellent in development defect suppression. In the compound represented by any one of chemical formulas (1) to (4), it was confirmed that the effect of the present invention is more excellent when the σp in Hammet's law has a substituent exceeding 0.5 (Example 2a and Example 1a compare, etc.). Satisfy the following conditions: the compound represented by the chemical formula (2) is more contained, and the resin A further has a group whose polarity is increased by decomposition by the action of an acid; or, the resin further has a repeating unit a, and the repeating unit a has a chemical formula (2) In the case of at least one of the residues formed by removing one or two hydrogen atoms in the indicated compound, the content of the repeating unit a is 10 mol% or more relative to all the repeating units of the resin, it was confirmed that the sensitivity is more excellent ( Example 5a compared with Example 2a, and Example 8a compared with Example 7a, etc.). Resin A further includes a repeating unit b, and when the repeating unit b has a group whose polarity is increased by decomposition by the action of an acid, it is confirmed that the sensitivity is more excellent (Examples 13a, 16a, 39a and Examples 9a, 10a, 22a, 23a comparison, etc.). Resin A further includes a repeating unit b, the repeating unit b has a group whose polarity is increased by decomposition by the action of an acid, and the repeating unit b includes a group selected from repeating units represented by any one of the chemical formulas (M1) to (M5). In the case of at least one of them, it was confirmed that the sensitivity was more excellent (comparison of Examples 5a, 8a, and 11a with Examples 13a, 16a, and 39a, etc.). When the repeating unit b contains at least one of the repeating unit represented by the chemical formula (M4) and the repeating unit represented by the chemical formula (M5), it was confirmed that the sensitivity is more excellent (Examples 12a, 14a, 15a and Example 5a, 8a, 11a comparison, etc.).

[Pattern formation (2): EUV exposure, alkaline development] A 6-inch silicon wafer (or chrome wafer) was treated with hexamethyldisilazane (HMDS). Each photoresist composition shown in the table below was coated on the obtained surface-treated silicon wafer using a spin coater Mark8 (manufactured by Tokyo Electron Co., Ltd.), and dried on a hot plate at a temperature of 130°C for 300 seconds to obtain a film Resist films each having a thickness of 100 nm. In addition, in the aforementioned method of producing the resist film, a chromium substrate may also be used instead of a silicon wafer. For the obtained resist film, using an EUV exposure device (Micro Exposure Tool manufactured by Exitech Corporation, NA (numerical aperture) 0.3, Quadrupole, outer σ0.68, inner σ0.36), an exposure mask (line: space=1 : 1) Pattern exposure was performed. Next, it was heated on a hot plate at a temperature of 100° C. for 90 seconds, immersed in a 2.38% by mass tetramethylammonium hydroxide (TMAH) aqueous solution for 60 seconds, and washed with water for 30 seconds. Finally, after the silicon wafer was rotated at 4000 rpm for 30 seconds, it was baked at a temperature of 95° C. for 60 seconds to dry it to obtain a silicon wafer with a predetermined pattern. Similar to the development defect and sensitivity in the aforementioned [pattern formation (1): EB exposure, alkaline development], each item of the obtained pattern was evaluated.

<Results> In the table, each description is the same as in Table 4.

[table 5]

It was confirmed that the photoresist composition of the present invention is excellent in development defect suppression. Resin A further has repeating unit a, and when the content of repeating unit a is 40 mol% or more relative to all repeating units of the resin, it is confirmed that the effect of the present invention is more excellent (Examples 19b, 20b and Examples 5b, 8b , 11b comparison, etc.). Satisfy the following conditions: the compound represented by the chemical formula (2) is more contained, and the resin A further has a group whose polarity is increased by decomposition by the action of an acid; or, the resin further has a repeating unit a, and the repeating unit a has a chemical formula (2) In the case of at least one of the residues formed by removing one or two hydrogen atoms in the indicated compound, the content of the repeating unit a is 10 mol% or more relative to all the repeating units of the resin, it was confirmed that the sensitivity is more excellent ( Comparison of Examples 9b, 10b with Examples 34b, 35b, etc.). Resin A further includes a repeating unit b, and when the repeating unit b has a group whose polarity is increased by decomposition by the action of an acid, it is confirmed that the sensitivity is more excellent (comparison of Example 16b with Examples 9b, 10b, 22b, 23b, etc. ). Resin A further includes a repeating unit b, the repeating unit b has a group whose polarity is increased by decomposition by the action of an acid, and the repeating unit b includes a group selected from repeating units represented by any one of the chemical formulas (M1) to (M5). In the case of at least one of them, it was confirmed that the sensitivity was more excellent (comparison of Examples 19b and 20b with Example 16b, etc.). When the repeating unit b includes at least one of the group consisting of the repeating unit represented by the chemical formula (M4) and the repeating unit represented by the chemical formula (M5), it was confirmed that the sensitivity is more excellent (Example 12b, 15b, 21b and Example 19b, 20b comparison, etc.).

none

none.

none.

Claims (11)

An actinic radiation-sensitive or radiation-sensitive resin composition comprising a resin having a repeating unit A represented by chemical formula (A), the actinic radiation-sensitive or radiation-sensitive resin composition satisfying at least one of the following conditions : further comprising a compound represented by any one of the chemical formulas (1) to (4), the resin further has a group whose polarity is increased by decomposition by the action of an acid; and, the resin further has a repeating unit a, The repeating unit a has a residue formed by removing one or two hydrogen atoms from the compound represented by any one of the chemical formulas (1) to (4), and the content of the repeating unit a is relative to the resin All repeating units of are more than 10 mol%, [chemical formula 1]

In the chemical formula (A), R ^A1 ~ R ^A3 independently represent a hydrogen atom, an alkyl group, a cycloalkyl group, a halogen atom, a cyano group or an alkoxycarbonyl group; ^LA represents a single bond or a divalent linking group; Ar ^A represents Aromatic ring group; R ^A2 and Ar ^A can be bonded to each other to form a ring; n _A represents an integer of 1 to 5, [chemical formula 2]

In the chemical formula (1), X ¹¹ represents a hydrogen atom or -L ¹¹ -(R ¹¹ )p ₁₁ ; R ¹¹ ~ ^{R 13} independently represent substituents; at least one of R ¹¹ ~ ^{R 13} represents σp in Hammet's law More than 0 substituents; R ¹¹ and R ¹³ can be bonded to each other to form a ring; L ¹¹ represents a single bond or a linking group with a valence of p ₁₁ +1; L ¹² represents a single bond or a linking group with a valence of p ₁₂ +1; L ¹³ represents a single bond or a linking group of p ₁₃ +1 valence; p ₁₁ ~ _{p 13} each independently represent an integer greater than 1, wherein, when L ¹¹ represents a single bond, p ₁₁ represents 1; when L ¹² represents a single In the case of a bond, p ₁₂ represents 1; when L ¹³ represents a single bond, p ₁₃ represents 1, and in chemical formula (2), X ²¹ represents a hydrogen atom or -L ²¹ -(R ²¹ )p ₂₁ ; X ²² Represents a hydrogen atom or -L ²² -(R ²² )p ₂₂ ; R ²¹ ~ ^{R 24} independently represent a substituent; at least one of R ²¹ ~ ^{R 24} represents a substituent whose σp exceeds 0 in Hammet's law; L ²¹ Indicates a single bond or a linking group of p ₂₁ +1 valence; L ²² expresses a single bond or a p ₂₂ +1 valence linking group; L ²³ expresses a single bond or a p ₂₃ +1 valence linking group; L ²⁴ expresses a single bond or p ₂₄ +1-valent linking group; at least two of R ²¹ , R ²² and R ²⁴ may be bonded to each other to form a ring; p ₂₁ ~ _{p 24} each independently represent an integer of 1 or more, wherein, when L ²¹ represents a single In the case of a bond, p ₂₁ represents 1; when L ²² represents a single bond, p ₂₂ represents 1; when L ²³ represents a single bond, p ₂₃ represents 1; when L ²⁴ represents a single bond, p ₂₄ represents 1, n ₂₁ represents an integer greater than 1, in chemical formula (3), X ³¹ represents a hydrogen atom or -L ³¹ -(R ³¹ )p ₃₁ ; R ³¹ and R ³² each independently represent a substituent; R ³¹ And at least one of R ³² represents a substituent whose σp exceeds 0 in Hammet's law; L ³¹ represents a single bond or a linking group of p ₃₁ +1 valence; L ³² represents a single bond or a linking group of p ₃₂ +1 valence; p ₃₁ and _p32 each independently represent an integer of 1 or more, wherein, when ^L31 represents a single bond, _p31 represents 1; when ^L32 represents a single bond, _p32 represents 1, and ^Ar31 represents an aromatic ring In the chemical formula (4), X ⁴¹ represents a hydrogen atom or -L ⁴¹ -(R ⁴¹ )p ₄₁ ; X ⁴² represents a hydrogen atom or -L ⁴² -(R ⁴² )p ₄₂ ; R ⁴¹ ~ ^{R 43} are independently Represents a substituent; at least one of R ⁴¹ ~ ^{R 43} represents a substituent whose σp exceeds 0 in Hammet's law; L ⁴¹ represents a single bond or a linking group of p ₄₁ +1 valence; L ⁴² represents a single bond or p ₄₂ +1 valence linking group; L ⁴³ represents a single bond or p ₄₃ +1 valence linking group; R ⁴¹ and R ⁴² can be bonded to each other to form a ring; p ₄₁ ~ p ₄₃ each independently represent an integer of 1 or more, wherein, when When L ⁴¹ represents a single bond, p ₄₁ represents 1; when L ⁴² represents a single bond, p ₄₂ represents 1; when L ⁴³ represents a single bond, p ₄₃ represents 1. The actinic radiation-sensitive or radiation-sensitive resin composition as described in claim 1, the resin further has a repeating unit a, and the repeating unit a has any one of chemical formulas (1) to (4) A residue formed by removing one or two hydrogen atoms in the represented compound, the residue includes at least one selected from the group consisting of groups represented by any one of the chemical formulas (1a) to (4a), [chemical formula 3]

In chemical formula (1a), X ^11a represents a hydrogen atom or -L ^11a -(R ^11a )p _11a ; R ^11a and R ^13a each independently represent a substituent; at least one of R ^11a and R ^13a represents σp in Hammet's law Substituents exceeding 0; R ^11a and R ^13a can be bonded to each other to form a ring; L ^11a represents a single bond or p _11a + 1-valent linking group; L ^12a represents a single bond or a divalent linking group; L ^13a represents a single bond or p _13a + 1 valence linking group; p _11a and p _13a each independently represent an integer of 1 or more, wherein, when L ^11a represents a single bond, p _11a represents 1; when L ^13a represents a single bond Below, p _13a represents 1; * represents the bonding position, in chemical formula (2a), X ^21a represents a hydrogen atom or -L ^21a -(R ^21a )p _21a ; X ^22a represents a hydrogen atom or -L ^22a -(R ^22a ) p _22a ; R ^21a , R ^22a and R ^24a each independently represent a substituent; at least one of R ^21a , R ^22a and R ^24a represents a substituent in which σp exceeds 0 in Hammet's law; L ^21a represents a single bond or p _21a +1-valent linking group; L ^22a represents a single bond or p _22a +1-valent linking group; L ^23a represents a single bond or a divalent linking group; L ^24a represents a single bond or p _24a +1-valent linking group; R At least two of ^21a , R ^22a , and R ^24a may be bonded to each other to form a ring; p _21a , p _22a , and p _24a each independently represent an integer of 1 or more, wherein, when L ^21a represents a single bond, p _21a represents 1; when L ^22a represents a single bond, p _22a represents 1; when L ^24a represents a single bond, p _24a represents 1; n _21a represents an integer greater than 1; * represents the bonding position, chemical formula ( In 3a), X ^31a represents a hydrogen atom or -L ^31a -(R ^31a )p _31a , each of R ^31a independently represents a substituent; at least one of R ^31a represents a substituent whose σp exceeds 0 in Hammet's law; L ^31a Represents a single bond or p _31a + 1-valent linking group; L ^32a represents a single bond or a divalent linking group; p _31a represents an integer of 1 or more, wherein, when L ^31a represents a single bond, p _31a represents 1; Ar ^31a represents an aromatic ring group; * represents a bonding position. In chemical formula (4a), X ^41a represents a hydrogen atom or -L ^41a -(R ^41a )p _41a ; X ^42a represents a hydrogen atom or -L ^42a -(R ^42a )p _42a ; R ^41a and R ^42a independently represent a substituent; at least one of R ^41a and R ^42a represents a substituent whose σp exceeds 0 in Hammet's law; L ^41a represents a single bond or a linking group of p _41a +1 valence; L ^42a represents a single bond or p _42a +1-valent linking group; L ^43a represents a single bond or a divalent linking group; R ^41a and R ^42a can be bonded to each other to form a ring; p _41a and p _42a each independently represent 1 In the above integers, when L ^41a represents a single bond, p _41a represents 1; when L ^42a represents a single bond, p _42a represents 1; * represents a bonding position. The actinic radiation-sensitive or radiation-sensitive resin composition according to claim 1 or 2, wherein the compound represented by any one of the chemical formulas (1) to (4) has a σp exceeding 0.5 in Hammet's law Substituents. The actinic radiation-sensitive or radiation-sensitive resin composition as described in claim 1, which satisfies at least one of the following conditions: It further includes a compound represented by any one of the chemical formulas (1) to (3), so The resin further has a group whose polarity is increased by decomposition by the action of an acid; and, the resin further has a repeating unit a, and the repeating unit a has a formula from any one of the chemical formulas (1) to (3) In the residue formed by removing one or two hydrogen atoms in the indicated compound, the content of the repeating unit a is 10 mol% or more relative to all the repeating units of the resin. As the actinic radiation-sensitive or radiation-sensitive resin composition described in claim 1, claim 2 or claim 4, the resin further has the repeating unit a, relative to all repeating units of the resin, the The content of the repeating unit a is 40 mol% or more. The actinic radiation-sensitive or radiation-sensitive resin composition as described in claim 1, claim 2 or claim 4, the resin further includes repeating unit b, and the repeating unit b has the ability to be decomposed by the action of the acid And the group with increased polarity. The actinic radiation-sensitive or radiation-sensitive resin composition as described in claim 1, claim 2 or claim 4, the resin further includes repeating unit b, and the repeating unit b has the ability to be decomposed by the action of the acid As for the group with increased polarity, the repeating unit b includes at least one selected from the group consisting of repeating units represented by any one of the chemical formulas (M1) to (M5), [chemical formula 4]

In the chemical formula (M1), R ^m11 ～R ^m13 independently represent a hydrogen atom, an alkyl group, a cycloalkyl group, a halogen atom, a cyano group or an alkoxycarbonyl group; L ^m11 represents a single bond or a divalent linking group; R ^m14 ～ R ^m16 independently represents an alkyl group, a cycloalkyl group, an aryl group, an aralkyl group or an alkenyl group; at least two of R ^m14 ~R ^m16 can be bonded to each other to form a ring, and in the chemical formula (M2), R ^m21 ~ R ^m24 each independently represents a hydrogen atom or an organic group, wherein at least one of R ^m21 and R ^m22 represents an organic group; X ^m21 represents -CO-, -SO- or -SO ₂ -; Y ^m21 represents -O-, -S-, -SO-, -SO ₂ -or -NR ³⁴ -; R ³⁴ represents a hydrogen atom or an organic group; L ^m21 represents a single bond or a divalent linking group; R ^m25 ~ ^{R m27} independently represent an alkyl group , cycloalkyl, aryl, aralkyl or alkenyl; at least two of R ^m25 ~ R ^m27 can be bonded to each other to form a ring, in the chemical formula (M3), R ^m31 and R ^m32 each independently represent a hydrogen atom or an organic group; R ^m33 and R ^m34 independently represent a hydrogen atom, an alkyl group, a cycloalkyl group, an aryl group, an aralkyl group or an alkenyl group; at least two of R ^m31 ~ R ^m34 can be bonded to each other to form a ring , in the chemical formula (M4), R ^m41 ~ R ^m43 each independently represent a hydrogen atom, an alkyl group, a cycloalkyl group, a halogen atom, a cyano group or an alkoxycarbonyl group; L ^m41 represents a single bond or a divalent linking group; Ar ^m41 represents an aromatic ring group; R ^m44 ～R ^m46 each independently represent a hydrogen atom, an alkyl group, a cycloalkyl group, an aryl group, an aralkyl group or an alkenyl group; at least two of R ^m44 ～R ^m46 can be bonded to each other to form Ring, in the chemical formula (M5), R ^m51 ~ R ^m53 each independently represent a hydrogen atom, an alkyl group, a cycloalkyl group, a halogen atom, a cyano group or an alkoxycarbonyl group; L ^m51 represents a single bond or a divalent linking group; R ^m54 and R ^m55 independently represent hydrogen atom, alkyl, cycloalkyl, aryl, aralkyl or alkenyl; R ^m56 represent alkyl, cycloalkyl, aryl, aralkyl or alkenyl; R ^m54 At least two of ~R ^m56 may be bonded to each other to form a ring. The actinic radiation-sensitive or radiation-sensitive resin composition according to claim 7, wherein the repeating unit b comprises a repeating unit selected from the chemical formula (M4) and a repeating unit represented by the chemical formula (M5) At least one of the group of units. A resist film formed using the actinic radiation-sensitive or radiation-sensitive resin composition according to any one of claims 1 to 8. A pattern forming method comprising: using the actinic radiation-sensitive or radiation-sensitive resin composition as described in any one of Claims 1 to 8 to form a resist film on a substrate; exposing the resist a film manufacturing process; and, a process of developing the exposed resist film using a developing solution. A method of manufacturing electronic components, which includes the pattern forming method described in claim 10.