TW202323231A - Actinic ray-sensitive or radiation-sensitive resin composition, resist film, pattern formation method, and electronic device manufacturing method - Google Patents

Abstract

Provided are: an actinic ray-sensitive or radiation-sensitive resin composition comprising a compound (N) containing a cation having a specific substituent, and a resin (A) that decomposes under the action of acid and increases in polarity; a resist film that uses the actinic ray-sensitive or radiation-sensitive resin composition; an actinic ray-sensitive or radiation-sensitive resin composition with which a pattern having an excellent pattern shape can be formed in ultra-fine pattern formation by a pattern formation method and an electronic device manufacturing method; a resist film that uses the actinic ray-sensitive or radiation-sensitive resin composition; a pattern formation method; and an electronic device manufacturing method.

Description

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

The present invention relates to an actinic radiation-sensitive or radiation-sensitive resin composition, a photoresist film, a method for forming a pattern, and a method for manufacturing an electronic device. More specifically, the present invention relates to manufacturing processes applicable to super LSI (Large Scale Integration, large-scale integrated circuits) and high-capacity microchips, manufacturing processes of nanoimprint molds, and manufacturing processes of high-density information recording media, etc. Ultralithography process, as well as actinic radiation-sensitive or radiation-sensitive resin composition suitable for other photosensitive etching processes, photoresist film using the above-mentioned actinic radiation-sensitive or radiation-sensitive composition, pattern forming method, and Methods of manufacturing electronic devices.

Conventionally, in the manufacturing process of semiconductor devices such as ICs (Integrated Circuits) and LSIs, microfabrication has been performed by photolithography using photoresist compositions. In recent years, with the high integration of integrated circuits, it is required to form ultrafine patterns in the sub-micron region or the quarter-micron region. Accompanied by this, the exposure wavelength is also changing from g-rays to i-rays, and then to KrF excimer laser light, etc., showing a trend of shorter wavelengths. At present, an exposure machine using ArF excimer laser with a wavelength of 193nm as a light source has been developed. Also, as a technique for further improving the resolution, a so-called liquid immersion method is being developed in which a liquid with a high refractive index (hereinafter also referred to as "immersion liquid") is filled between the projection lens and the sample.

In addition, photolithography using electron beams (EB), X-rays, extreme ultraviolet rays (EUV) and the like are currently being developed in addition to excimer laser light. Along with this, a chemically amplified photoresist composition that effectively senses various radiations and has excellent sensitivity and resolution has been developed.

Onium salts are often used in actinic radiation-sensitive or radiation-sensitive resin compositions such as photoresist compositions. For example, Patent Documents 1 to 5 describe photoresist compositions containing a columium salt having a fluorine atom group. [Prior Art Literature] [Patent Document]

Patent Document 1: International Publication No. 2021/039244 Patent Document 2: Japanese Patent Laid-Open No. 2018-158892 Patent Document 3: Japanese Patent Laid-Open No. 2020-15716 Patent Document 4: Japanese Patent Laid-Open No. 2012-136511 Patent Document 5: Japanese Patent Laid-Open No. 2010-120924

[Problem to be Solved by the Invention] In recent years, the miniaturization of the formed pattern is progressing. For example, in the case of forming an extremely fine pattern such as a 1:1 line and space pattern with a line width of 14 nm or less, it is also required to form an excellent shape (the cross-sectional shape of the pattern is a rectangular or nearly rectangular shape).

The object of the present invention is to provide an actinic radiation-sensitive or radiation-sensitive resin composition capable of forming an extremely fine pattern (for example, a 1:1 line and space pattern with a line width of 14 nm or less), which is excellent in pattern shape picture of. Also, the object of the present invention is to provide a photoresist film using the above-mentioned actinic radiation-sensitive or radiation-sensitive resin composition, a method for forming a pattern, and a method for manufacturing an electronic device. [Means to solve the problem]

The inventors of the present invention found that the above-mentioned subject can be achieved by the following configuration.

[1] An actinic radiation-sensitive or radiation-sensitive resin composition, which contains: a compound (N) containing at least one selected from the group consisting of a cation represented by the following general formula (N1) and a cation represented by the following general formula (N2); and Resin (A) whose polarity is increased by decomposition by the action of acid.

[chemical formula 1]

[chemical formula 2]

In the general formula (N1) and the general formula (N2), Ar ^N1 and Ar ^N3 independently represent at least one substituent represented by the following general formula (N3) bonded to at least one carbon atom in the aromatic ring. Aromatic base. Ar ^N2 represents an aromatic group having at least one substituent selected from the group consisting of an organic group and a halogen atom. Wherein, Ar ^N2 is a group different from Ar ^N1 . R ^N1 and R ^N2 each independently represent an organic group. k1+k2+k3 is 3, k1 represents an integer of 1-3, k2 represents an integer of 0-2, and k3 represents 0 or 1. Wherein, when k1 represents 1, k2 represents 1 or 2. At least two of Ar ^N1 , Ar ^N2 and R ^N1 may be bonded by a single bond or a linker to form a ring. When a plurality of Ar ^N1 exists, the plurality of Ar ^N1 may be the same or different. When there are a plurality of Ar ^N2 , the plurality of Ar ^N2 may be the same or different. k4+k5 is 2, k4 represents 1 or 2, and k5 represents 0 or 1. When there are a plurality of Ar ^N3 , the plurality of Ar ^N3 may be the same or different. Ar ^N3 and R ^N2 , or two Ar ^N3 may be bonded by a single bond or a linker to form a ring.

[chemical formula 3]

In the general formula (N3), Y ^N1 represents an oxygen atom or a sulfur atom. Z ^N1 represents a group represented by the following general formula (N4) or (N5). ＊Indicates the bonding position.

[chemical formula 4]

In the general formula (N4), R ^N3 and R ^N4 each independently represent a hydrogen atom, a fluorine atom, a fluorinated alkyl group or an alkyl group, and at least one -CH ₂ - contained in the above-mentioned alkyl group may be substituted by -CO-. ＊Indicates the bonding position.

[chemical formula 5]

In the general formula (N5), Rf ^N1 represents a perfluoroalkyl group. R ^N5 represents a fluorinated alkyl group or an alkyl group, and at least one -CH ₂ - contained in the above-mentioned alkyl group may be substituted by -CO-. R ^N6 represents a hydrogen atom, a fluorinated alkyl group or an alkyl group, and at least one -CH ₂ - contained in the above-mentioned alkyl group may be substituted by -CO-. ＊Indicates the bonding position. [2] The actinic radiation-sensitive or radiation-sensitive resin composition according to [1], wherein R ^N3 in the general formula (N4) represents a fluorine atom or a fluorinated alkyl group. [3] The actinic radiation-sensitive or radiation-sensitive resin composition according to [1], wherein R ^N5 in the general formula (N5) represents a fluorinated alkyl group. [4] The actinic radiation-sensitive or radiation-sensitive resin composition according to [1] or [2], wherein Z ^N1 in the above general formula (N3) represents a group represented by the above general formula (N4) . [5] The actinic radiation-sensitive or radiation-sensitive resin composition as described in any one of [1] to [4], wherein Ar ^N2 in the above-mentioned general formula (N1) represents a compound selected from halogen atoms and containing An aromatic group of at least one substituent in the group consisting of an organic group of a halogen atom. [6] The actinic radiation-sensitive or radiation-sensitive resin composition as described in any one of [1] to [5], wherein Ar ^N2 in the above-mentioned general formula (N1) represents a group consisting of fluorine atoms and An aromatic group of at least one substituent in the group consisting of organic groups of fluorine atoms. [7] The actinic radiation-sensitive or radiation-sensitive resin composition according to any one of [1] to [6], wherein the above-mentioned compound (N) contains at least one cation represented by the above-mentioned general formula (N1) . [8] The actinic radiation-sensitive or radiation-sensitive resin composition according to any one of [1] to [7], wherein Ar ^N1 and Ar ^N3 in the above general formulas (N1) and (N2) are respectively independently represents a group represented by the following general formula (N6).

[chemical formula 6]

In the general formula (N6), R ^N7 to R ^N11 each independently represent a hydrogen atom, a halogen atom, an alkyl group, an alkoxy group, or a substituent represented by the above general formula (N3). However, at least one of R ^N7 to R ^N11 represents a substituent represented by the above general formula (N3). ＊Indicates the bonding position. [9] The actinic radiation-sensitive or radiation-sensitive resin composition according to any one of [1] to [8], wherein the compound (N) has a group selected from the group represented by the following general formula (N7): At least one of the group consisting of group, *-SO ₃ ^- and *-CO ₂ ^- .

[chemical formula 7]

L ^N1 and L ^N2 each independently represent -SO ₂ - or -CO-. ＊Indicates the bonding position. [10] The actinic radiation-sensitive or radiation-sensitive resin composition according to any one of [1] to [9], wherein the above-mentioned actinic radiation-sensitive or radiation-sensitive resin composition further contains a solvent and a solid content The concentration is 0.5 to 14.0% by mass. [11] A photoresist film formed using the actinic radiation-sensitive or radiation-sensitive resin composition described in any one of [1] to [10]. [12] A pattern forming method, comprising: using the actinic radiation-sensitive or radiation-sensitive resin composition described in any one of [1] to [10] to form a photoresist film on a substrate; exposing the above-mentioned light The process of resisting film; and the process of developing the above-mentioned photoresist film exposed by developer. [13] The pattern forming method according to [12], wherein the process of exposing the photoresist film is a process of subjecting the photoresist film to EUV exposure. [14] A method of manufacturing an electronic device, including the pattern forming method described in [12] or [13]. [Invention effect]

According to the present invention, it is possible to provide a method for producing an actinic radiation-sensitive or radiation-sensitive resin composition capable of forming an extremely fine pattern (for example, a 1:1 line and space pattern with a line width of 14 nm or less, etc.) A pattern with excellent pattern shape. Also, according to the present invention, there can be provided a photoresist film using the above-mentioned actinic radiation-sensitive or radiation-sensitive resin composition, a method for forming a pattern, and a method for manufacturing an electronic device.

Hereinafter, the present invention will be described in detail. The description of the constituent elements described below may be based on representative embodiments of the present invention, but the present invention is not limited to these embodiments. Regarding the expression of a group (atomic group) in this specification, as long as it does not deviate from the gist of the present invention, the expression not describing substitution and unsubstituted includes a group without a substituent and also includes a group containing a substituent. For example, the term "alkyl" includes not only an unsubstituted alkyl group (unsubstituted alkyl group) but also an alkyl group having a substituent (substituted alkyl group). Also, in this specification, the term "organic group" refers to a group containing at least one carbon atom. As a substituent, unless otherwise specified, a monovalent substituent is preferable.

In the present specification, when "may have a substituent", the kind of the substituent, the position of the substituent, and the number of the substituent are not particularly limited. The number of substituents may be, for example, one, two, three or more. Examples of substituents include monovalent non-metallic atomic groups other than hydrogen atoms, and can be selected from the following substituent T, for example.

(substituent T) Examples of substituent T include halogen atoms such as fluorine atom, chlorine atom, bromine atom, and iodine atom; alkoxy groups such as methoxy, ethoxy, and tert-butoxy; phenoxy, p-tolyloxy, etc. Aryloxy; Alkoxycarbonyl such as methoxycarbonyl, butoxycarbonyl and phenoxycarbonyl; Acyloxy such as acetyloxy, propionyloxy and benzoyloxy; Acetyl, benzoyl, Acyl groups such as isobutyryl, acryl, methacryl, and methyl oxalyl; alkylsulfanyl groups such as methylmercapto and tert-butylsulfanyl; phenylthiopropyl and p-tolylsulfane Aryl mercapto group, etc.; alkyl group (for example, carbon number 1-10); cycloalkyl group (for example, carbon number 3-20); aryl group (for example, carbon number 6-20); heteroaryl group; hydroxyl group; carboxyl group ;formyl;sulfo;cyano;alkylaminocarbonyl;arylaminocarbonyl;sulfonamide;silyl;amine;monoalkylamino;dialkylamino;arylamino ; nitro; formyl; and combinations thereof.

In this specification, "actinic ray" or "radiation" refers to, for example, the bright-line spectrum of a mercury lamp, extreme ultraviolet rays represented by excimer lasers, extreme ultraviolet rays (EUV light: Extreme Ultraviolet), X-rays, and electron beams. (EB: Electron Beam). In this specification, "light" refers to actinic rays or radiation. In this specification, the term "exposure" includes not only exposure using the bright line spectrum of a mercury lamp, extreme ultraviolet rays typified by excimer lasers, extreme ultraviolet rays (EUV: Extreme ultraviolet), X-rays, etc., unless otherwise specified. Exposure also includes drawing using particle beams such as electron beams and ion beams. In this specification, "-" is used in the meaning which includes the numerical value described before and after that as a lower limit and an upper limit.

In this specification, unless otherwise specified, the bonding direction of the described divalent linking group is not limited. For example, when Y in the compound represented by the formula "X-Y-Z" is -COO-, Y may be -CO-O- or -O-CO-. The above compound may be "X-CO-O-Z" or "X-O-CO-Z".

In this specification, (meth)acrylate means acrylate and methacrylate, and (meth)acryl means acrylic acid and methacryl. In this specification, weight average molecular weight (Mw), number average molecular weight (Mn) and degree of dispersion (hereinafter also referred to as "molecular weight distribution") (Mw/Mn) are determined by using a GPC (Gel Permeation Chromatography) device (HLC-8120GPC manufactured by Tosoh Corporation) GPC measurement (solvent: tetrahydrofuran, flow rate (sample injection volume): 10 μL, column: TSK gel Multipore HXL-M manufactured by Tosoh Corporation, column temperature: 40°C, flow rate: 1.0 mL/ Points, detectors: differential refractive index detector (Refractive Index Detector) obtained by the polystyrene conversion value to define.

In this specification, the acid dissociation constant (pKa) means the pKa in an aqueous solution. Specifically, the following software package 1 is used to borrow the value based on Hammett's substituent constant and a database of known literature values. The value obtained by calculation. Software Package 1: Advanced Chemistry Development (ACD/Labs) Software V8.14 for Solaris (1994-2007 ACD/Labs).

pKa was also obtained by molecular orbital calculation. As a specific method, there is a method of calculating pKa by calculating the H ⁺ dissociation free energy in an aqueous solution based on a thermodynamic cycle. The calculation method of the H ⁺ dissociation free energy can be calculated by, for example, DFT (density functional theory), and various other methods have also been reported in literature and the like, and are not limited thereto. Furthermore, there are several types of software capable of implementing DFT, and one example is Gaussian16.

In this specification, the so-called pKa refers to the value obtained by calculation based on Hammett's substituent constant and the value of the database of known literature values using the software package 1 as described above. However, in this When the pKa cannot be calculated by the method, the value obtained by Gaussian16 based on DFT (density functional theory) is used. In this specification, pKa refers to "pKa in aqueous solution" as described above, but when pKa in aqueous solution cannot be calculated, "pKa in dimethylsulfoxide (DMSO) solution" is used. . The term "solid content" refers to components that form an actinic radiation-sensitive or radiation-sensitive film (typically a photoresist film), excluding solvents. In addition, as long as it is a component that forms an actinic ray-sensitive or radiation-sensitive film, even if its property is liquid, it is regarded as a solid component.

Hereinafter, the present invention will be described in detail.

[Actinic radiation-sensitive or radiation-sensitive resin composition] The actinic radiation-sensitive or radiation-sensitive resin composition of the present invention (hereinafter also referred to as "the composition of the present invention") contains: a cation selected from the following general formula (N1) and represented by the following general formula (N2 ) at least one compound (N) in the group consisting of cations represented by ), and a resin (A) whose polarity is increased by decomposition by the action of an acid.

[chemical formula 8]

[chemical formula 9]

In the general formulas (N1) and (N2), Ar ^N1 and Ar ^N3 each independently represent an aromatic ring having at least one substituent represented by the following general formula (N3) bonded to at least one carbon atom constituting the aromatic ring. base. Ar ^N2 represents an aromatic group having at least one substituent selected from the group consisting of an organic group and a halogen atom. Wherein, Ar ^N2 is a group different from Ar ^N1 . R ^N1 and R ^N2 each independently represent an organic group. k1+k2+k3 is 3, k1 represents an integer of 1-3, k2 represents an integer of 0-2, and k3 represents 0 or 1. Wherein, when k1 represents 1, k2 represents 1 or 2. At least two of Ar ^N1 , Ar ^N2 and R ^N1 may be bonded by a single bond or a linker to form a ring. When a plurality of Ar ^N1 exists, the plurality of Ar ^N1 may be the same or different. When there are a plurality of Ar ^N2 , the plurality of Ar ^N2 may be the same or different. k4+k5 is 2, k4 represents 1 or 2, and k5 represents 0 or 1. When there are a plurality of Ar ^N3 , the plurality of Ar ^N3 may be the same or different. Ar ^N3 and R ^N2 , or two Ar ^N3 may be bonded by a single bond or a linker to form a ring.

[chemical formula 10]

In the general formula (N3), Y ^N1 represents an oxygen atom or a sulfur atom. Z ^N1 represents a group represented by the following general formula (N4) or (N5). ＊Indicates the bonding position.

[chemical formula 11]

In the general formula (N4), R ^N3 and R ^N4 each independently represent a hydrogen atom, a fluorine atom, a fluorinated alkyl group or an alkyl group. At least one -CH ₂ - contained in the alkyl group may be substituted by -CO-. ＊Indicates the bonding position.

[chemical formula 12]

In the general formula (N5), Rf ^N1 represents a perfluoroalkyl group. R ^N5 represents a fluorinated alkyl or alkyl group. At least one -CH ₂ - contained in the alkyl group may be substituted by -CO-. R ^N6 represents a hydrogen atom, a fluorinated alkyl group or an alkyl group. At least one -CH ₂ - contained in the alkyl group may be substituted by -CO-. ＊Indicates the bonding position.

The composition of the present invention is typically a photoresist composition, which can be a positive photoresist composition or a negative photoresist composition. The photoresist composition can be a photoresist composition for alkaline development, or a photoresist composition for organic solvent development. The composition of the present invention can be a chemically amplified photoresist composition or a non-chemically amplified photoresist composition. The composition of the present invention is preferably a chemically amplified photoresist composition. The film formed using the composition of the present invention is an actinic radiation-sensitive or radiation-sensitive film, typically a photoresist film.

The reason why the composition according to the present invention can form a pattern having an excellent pattern shape in the pattern formation of an ultrafine pattern (for example, a 1:1 line and space pattern with a line width of 14 nm or less, etc.) has not been elucidated in detail, but the present invention et al. speculate as follows. The compound (N) contained in the composition of the present invention contains a cation having a substituent represented by the general formula (N3). The substituent represented by the general formula (N3) has a structure in which Z ^N1 (group represented by the general formula (N4) or (N5)) is bonded to Y ^N1 (an oxygen atom or a sulfur atom), and has high electron attraction. As a result, it is considered that the electron density of the central atom (sulfur atom or iodine atom) of the compound (N) decreases, and the acid group that the compound (N) and the resin (A) may have or is generated from a photoacid typically used in a photoresist composition The interaction of acids generated by agents (for example, compound (N) or a photoacid generator (B) described later) is improved and the acid diffusibility is suppressed, so it is possible to form a pattern with excellent pattern shape in the formation of ultrafine patterns. Furthermore, since the substituent represented by the general formula (N3) has extremely high hydrophobicity, the compatibility between the compound (N) and the resin (A) is also excellent. As a result, it is considered that the compound (N) is uniformly distributed in the photoresist film formed from the composition of the present invention, and it is possible to form a pattern having an excellent pattern shape in the formation of an ultrafine pattern.

<Compound (N)> The compound (N) is a compound containing at least one selected from the group consisting of cations represented by the general formula (N1) (Cerium ions) and cations represented by the general formula (N2) (Iodide ions). The cations selected from the group consisting of the cations represented by the general formula (N1) and the cations represented by the general formula (N2) are also referred to as “specific cations”. The compound (N) preferably contains at least one cation represented by the general formula (N1). Compound (N) preferably also contains anions in addition to at least one specific cation. In addition, the compound (N) may contain other cations in addition to at least one specific cation. Depending on the type of anion, the compound (N) can be used as a photoacid generator or an acid diffusion controller (quencher).

The molecular weight of the compound (N) is not limited, and may be a low molecular weight compound or a high molecular weight compound. When the compound (N) is a low molecular weight compound, the molecular weight of the compound (N) is preferably from 200 to 3500, more preferably from 300 to 3000, even more preferably from 400 to 2500. When the compound (N) is a polymer compound, the weight average molecular weight (Mw) of the compound (N) is preferably from 3,000 to 50,000, more preferably from 4,000 to 40,000, still more preferably from 5,000 to 30,000. When the compound (N) is a polymer compound, the degree of dispersion (molecular weight distribution, Mw/Mn) of the compound (N) is preferably 1 to 5, more preferably 1 to 3, further preferably 1.2 to 3.0, particularly preferably 1.2～2.0. As an aspect in which the compound (N) is a polymer compound, an aspect containing a resin having an anion and a cation selected from the group consisting of the cation represented by the general formula (N1) and the cation represented by the general formula (N2) is mentioned. at least one cation in the group. In addition, as an aspect in which the compound (N) is a polymer compound, an aspect containing an anion and a resin having a cation selected from the group represented by the general formula (N1) and the compound represented by the general formula (N2) can also be mentioned. At least one cation in the group consisting of cations.

(cation represented by general formula (N1)) The cation represented by the general formula (N1) will be described.

[chemical formula 13]

In the general formula (N1), Ar ^N1 represents an aromatic group having at least one substituent represented by the general formula (N3) bonded to at least one carbon atom constituting the aromatic ring. Ar ^N2 represents an aromatic group having at least one substituent selected from the group consisting of an organic group and a halogen atom. R ^N1 represents an organic group. k1+k2+k3 is 3, k1 represents an integer of 1-3, k2 represents an integer of 0-2, and k3 represents 0 or 1. Wherein, when k1 represents 1, k2 represents 1 or 2. At least two of Ar ^N1 , Ar ^N2 and R ^N1 may be bonded by a single bond or a linker to form a ring. When a plurality of Ar ^N1 exists, the plurality of Ar ^N1 may be the same or different. When there are a plurality of Ar ^N2 , the plurality of Ar ^N2 may be the same or different.

The aromatic group represented by Ar ^N1 may be an aromatic hydrocarbon group or an aromatic heterocyclic group.

The aromatic hydrocarbon group (aryl group) represented by Ar ^N1 may be a monocyclic aromatic group or a polycyclic aromatic group. The aromatic hydrocarbon group may have a substituent. The aromatic hydrocarbon group is preferably an aryl group having 6 to 20 carbons, more preferably an aryl group having 6 to 10 carbons, for example, phenyl, naphthyl, anthracenyl, etc., preferably phenyl or Naphthyl, more preferably phenyl.

The aromatic heterocyclic group represented by Ar ^N1 is preferably an aromatic heterocyclic group containing at least one heteroatom selected from the group consisting of nitrogen atom, sulfur atom and oxygen atom. The aromatic heterocyclic group may be a monocyclic aromatic heterocyclic group or a polycyclic aromatic heterocyclic group. The aromatic heterocyclic group may have a substituent. The aromatic hydrocarbon group is preferably an aromatic hydrocarbon group having 2 to 20 carbon atoms, more preferably an aromatic hydrocarbon group having 3 to 10 carbon atoms.

At least one substituent represented by the general formula (N3) is bonded to at least one of the carbon atoms constituting the aromatic ring of the aromatic group represented by Ar ^N1 .

[chemical formula 14]

In the general formula (N3), Y ^N1 represents an oxygen atom or a sulfur atom. Z ^N1 represents a group represented by general formula (N4) or (N5). ＊Indicates the bonding position.

[chemical formula 15]

In the general formula (N4), R ^N3 and R ^N4 each independently represent a hydrogen atom, a fluorine atom, a fluorinated alkyl group or an alkyl group. At least one -CH ₂ - contained in the alkyl group may be substituted by -CO-. ＊Indicates the bonding position.

[chemical formula 16]

In the general formula (N5), Rf ^N1 represents a perfluoroalkyl group. R ^N5 represents a fluorinated alkyl or alkyl group. At least one -CH ₂ - contained in the alkyl group may be substituted by -CO-. R ^N6 represents a hydrogen atom, a fluorinated alkyl group or an alkyl group. At least one -CH ₂ - contained in the alkyl group may be substituted by -CO-. ＊Indicates the bonding position.

Y ^N1 in the general formula (N3) preferably represents an oxygen atom.

R ^N3 and R ^N4 in the general formula (N4) each independently represent a hydrogen atom, a fluorine atom, a fluorinated alkyl group or an alkyl group.

The fluorinated alkyl groups represented by R ^N3 and R ^N4 may be linear or branched. The number of carbon atoms in the fluorinated alkyl group is preferably 1-12, more preferably 1-8, further preferably 1-5, particularly preferably 1-4. The fluorinated alkyl group may be a fluorinated alkyl group in which some of the hydrogen atoms in the alkyl group are replaced by fluorine atoms, or may be a perfluoroalkyl group, preferably a perfluoroalkyl group. The fluorinated alkyl group may have a substituent. As a substituent, the above-mentioned substituent T (however, fluorine atom is not included.) is mentioned, for example. When the substituent is an organic group, the carbon number of the organic group is preferably 1-12, more preferably 1-8, further preferably 1-5, particularly preferably 1-4.

The alkyl groups represented by R ^N3 and R ^N4 may be linear or branched. The number of carbon atoms in the alkyl group is preferably 1-12, more preferably 1-8, further preferably 1-5, particularly preferably 1-4. Examples of the alkyl group include methyl, ethyl, n-propyl, isopropyl, n-butyl, isobutyl, tert-butyl and the like. An alkyl group may have a substituent. As a substituent, the above-mentioned substituent T (however, fluorine atom is not included.) is mentioned, for example. When the substituent is an organic group, the carbon number of the organic group is preferably 1-12, more preferably 1-8, further preferably 1-5, particularly preferably 1-4. An alkoxy group is mentioned as a preferable example of a substituent.

R ^N3 in the general formula (N4) preferably represents a fluorine atom or a fluorinated alkyl group, more preferably represents a fluorine atom or a fluorinated alkyl group with 1 to 5 carbon atoms, and further preferably represents a fluorine atom or a fluorinated alkyl group with a carbon number of 1 ~4 fluorinated alkyl groups.

Rf ^N1 in the general formula (N5) represents a perfluoroalkyl group. The perfluoroalkyl group represented by Rf ^N1 may be linear or branched. The carbon number of the perfluoroalkyl group is preferably 1-12, more preferably 1-8, further preferably 1-5, particularly preferably 1-4.

The description, specific examples and preferred ranges of the fluorinated alkyl and alkyl represented by R ^N5 and R ^N6 in the general formula (N5) are respectively related to the fluorinated alkyl represented by R ^N3 and R ^N4 in the general formula (N4) Same as described for alkyl.

R ^N5 in the general formula (N5) preferably represents a fluorinated alkyl group. Rf ^N1 and R ^N5 in the general formula (N5) each independently preferably represent a perfluoroalkyl group having 1 to 5 carbon atoms, and more preferably represent a perfluoroalkyl group having 1 to 4 carbon atoms.

Ar ^N1 in the general formula (N1) preferably represents a group represented by the following general formula (N6).

[chemical formula 17]

In the general formula (N6), R ^N7 to R ^N11 each independently represent a hydrogen atom, a halogen atom, an alkyl group, an alkoxy group, or a substituent represented by the general formula (N3). However, at least one of R ^N7 to R ^N11 represents a substituent represented by the general formula (N3). ＊Indicates the bonding position.

The halogen atom represented by R ^N7 to R ^N11 is preferably a fluorine atom, a chlorine atom, a bromine atom or an iodine atom, more preferably a fluorine atom. The alkyl groups represented by R ^N7 to R ^N11 may be linear or branched. The number of carbon atoms in the alkyl group is preferably 1-12, more preferably 1-8, further preferably 1-5, particularly preferably 1-3. Examples of the alkyl group include methyl, ethyl, n-propyl, isopropyl, n-butyl, isobutyl, tert-butyl and the like. An alkyl group may have a substituent. As a substituent, the substituent T mentioned above is mentioned, for example. The alkoxy groups represented by R ^N7 to R ^N11 may be linear or branched. The number of carbon atoms in the alkoxy group is preferably 1-12, more preferably 1-8, further preferably 1-5, particularly preferably 1-3. As an alkoxy group, a methoxy group, an ethoxy group etc. are mentioned, for example. An alkoxy group may have a substituent. As a substituent, the substituent T mentioned above is mentioned, for example.

In order to have a better pattern shape, Z ^N1 in the general formula (N3) preferably represents a group represented by the general formula (N4).

Ar ^N2 in the general formula (N1) represents an aromatic group having at least one substituent selected from the group consisting of an organic group and a halogen atom.

The aromatic group represented by Ar ^N2 may be an aromatic hydrocarbon group or an aromatic heterocyclic group.

The aromatic hydrocarbon group (aryl group) represented by Ar ^N2 may be a single-ring aromatic group or a polycyclic aromatic group. The aromatic hydrocarbon group may have a substituent. The aromatic hydrocarbon group is preferably an aryl group having 6 to 20 carbons, more preferably an aryl group having 6 to 10 carbons, for example, phenyl, naphthyl, anthracenyl, etc., preferably phenyl or Naphthyl, more preferably phenyl.

The aromatic heterocyclic group represented by Ar ^N2 is preferably an aromatic heterocyclic group containing at least one heteroatom selected from the group consisting of nitrogen atom, sulfur atom and oxygen atom. The aromatic heterocyclic group may be a monocyclic aromatic heterocyclic group or a polycyclic aromatic heterocyclic group. The aromatic heterocyclic group may have a substituent. The aromatic hydrocarbon group is preferably an aromatic hydrocarbon group having 2 to 20 carbon atoms, more preferably an aromatic hydrocarbon group having 3 to 10 carbon atoms.

The aromatic group represented by Ar ^N2 has at least one selected from the group consisting of organic groups and halogen atoms as a substituent. The aforementioned halogen atom is preferably a fluorine atom, chlorine atom, bromine atom or iodine atom, more preferably a fluorine atom. The number of carbon atoms in the organic group is preferably 1-15, more preferably 1-10. The aforementioned organic groups are not particularly limited, but are preferably alkyl, cycloalkyl, alkenyl, aryl, alkoxy, aryloxy, alkylcarbonyloxy, arylcarbonyloxy, acyl, alkoxycarbonyl , or aryloxycarbonyl, more preferably alkyl, alkoxy, aryloxy or arylcarbonyloxy. These substituents may have substituents, if possible. As a substituent, for example, the substituent T mentioned above is mentioned, Preferably it is a halogen atom, More preferably, it is a fluorine atom, a chlorine atom, a bromine atom, or an iodine atom, More preferably, it is a fluorine atom.

Ar ^N2 in the general formula (N1) preferably represents an aromatic group having at least one substituent selected from the group consisting of a halogen atom and an organic group containing a halogen atom, more preferably represents an aromatic group selected from the group consisting of fluorine At least one aromatic group as a substituent from the group consisting of atoms and organic groups containing fluorine atoms.

R ^N1 in the general formula (N1) represents an organic group. The carbon number of the organic group represented by R ^N1 is preferably 1-15, more preferably 1-10, further preferably 1-6. The aforementioned organic groups are not particularly limited, but are preferably alkyl, cycloalkyl, alkenyl, aryl, alkoxy, aryloxy, alkylcarbonyloxy, arylcarbonyloxy, acyl, alkoxycarbonyl , or aryloxycarbonyl, more preferably alkyl, alkoxy, aryloxy or arylcarbonyloxy. The aforementioned organic groups are not particularly limited, and are preferably alkyl, cycloalkyl, alkenyl, aryl, heterocyclic, alkoxy, aryloxy, heteroepoxy, alkylcarbonyloxy, arylcarbonyl Oxy, acyl, alkoxycarbonyl or aryloxycarbonyl, more preferably alkyl or aryl. The alkyl group may be linear or branched. Examples of the alkyl group include methyl, ethyl, n-propyl, isopropyl, n-butyl, isobutyl, tert-butyl and the like. The aryl group may be a monocyclic aryl group or a polycyclic aryl group. Examples of the aryl group include phenyl, naphthyl, anthracenyl and the like, preferably phenyl or naphthyl, more preferably phenyl. The heterocyclic group may be an aromatic heterocyclic group or a non-aromatic heterocyclic group. The heterocyclic group is preferably a 5-membered ring group or a 6-membered ring group. The heterocyclic group is also preferably a condensed ring group consisting of a 5-membered ring and a 5- or 6-membered ring. The heterocyclic group is also preferably a condensed ring group composed of a 6-membered ring and a 5- or 6-membered ring. The aromatic heterocyclic group (heteroaryl group) is preferably an aromatic heterocyclic group containing at least one heteroatom selected from the group consisting of nitrogen atom, sulfur atom and oxygen atom. A carbon atom contained as a ring member in the aromatic heterocyclic group may be substituted with an oxo group (=O). The non-aromatic heterocyclic group (aliphatic heterocyclic group) is preferably a non-aromatic heterocyclic group containing at least one heteroatom selected from the group consisting of a nitrogen atom, a sulfur atom, and an oxygen atom. Carbon atoms included as ring members in the non-aromatic heterocyclic group may be substituted with an oxo group (=O). The organic group represented by R ^N1 may have a substituent. As a substituent, the substituent T mentioned above is mentioned, for example.

R ^N1 in the general formula (N1) may represent a repeating unit constituting a polymer chain.

In general formula (N1), k1+k2+k3 is 3, k1 represents the integer of 1-3, k2 represents the integer of 0-2, and k3 represents 0 or 1. Wherein, when k1 represents 1, k2 represents 1 or 2. k1 preferably represents 2 or 3, more preferably represents 3. k2 preferably represents 0 or 1, more preferably represents 0. It is preferable that k3 represents 0.

At least two of Ar ^N1 , Ar ^N2 and R ^N1 may be bonded by a single bond or a linker to form a ring. As the linking group, preferably -O-, -CO-, -SO ₂ -, -S-, -SO-hydrocarbyl (such as alkylene, cycloalkylene, alkenylene, arylylene, etc.), and The divalent linking group formed by combining two or more selected from these is more preferably -CO- or -SO ₂ -.

(Cations represented by general formula (N2)) The cation represented by the general formula (N2) will be described.

[chemical formula 18]

In the general formula (N2), Ar ^N3 represents an aromatic group having at least one substituent represented by the above general formula (N3) bonded to at least one of the carbon atoms constituting the aromatic ring. R ^N2 represents an organic group. k4+k5 is 2, k4 represents 1 or 2, and k5 represents 0 or 1. When there are a plurality of Ar ^N3 , the plurality of Ar ^N3 may be the same or different. Ar ^N3 and R ^N2 or two Ar ^N3 may be bonded by a single bond or a linking group to form a ring.

The description, specific examples, and preferred ranges of Ar ^N3 in the general formula (N2) are the same as those described for Ar ^N1 in the above general formula (N1).

The general formulas (N3), (N4) and (N5) are as described above.

Ar ^N3 in the general formula (N2) preferably represents a group represented by the above general formula (N6).

R ^N2 in the general formula (N2) represents an organic group. The description, specific examples, and preferred ranges of R ^N2 are the same as those described for R ^N1 in the above general formula (N1).

k4+k5 is 2, k4 represents 1 or 2, and k5 represents 0 or 1. k4 preferably represents 2. It is preferable that k5 represents 0.

Ar ^N3 and R ^N2 or two Ar ^N3 may be bonded to each other via a single bond or a linker to form a ring. As the linking group, preferably -O-, -CO-, -SO ₂ -, -S-, -SO-hydrocarbyl (such as alkylene, cycloalkylene, alkenylene, arylylene, etc.), and The divalent linking group formed by combining two or more selected from these is more preferably -CO- or -SO ₂ -.

The specific cation may have an acid decomposable group. About the acid-decomposable group, it is the same as that of the resin (A) mentioned later. In a preferable aspect, the cation represented by the general formula (N1) and the cation represented by the general formula (N2) do not have an acid decomposable group.

For example, specific cations can be synthesized by a method according to the following literature or the like. ･J.Org.Chem.,Vol.53,No.23,1988 ･Chemical Communications (2018), 54 (64), 8810-8813

Specific examples of specific cations are listed below, but the present invention is not limited thereto.

[chemical formula 19]

[chemical formula 20]

[chemical formula 21]

[chemical formula 22]

[chemical formula 23]

The compound (N) preferably has at least one selected from the group consisting of a group represented by the following general formula (N7), -SO ₃ ^- and -CO ₂ ^- . The compound (N) contains a specific cation and an organic anion, and ^the organic anion preferably has at least one selected from the group represented by the following general formula (N7), *-SO ₃ ^- and *-CO ₂ A sort of. ＊Indicates the bonding position.

[chemical formula 24]

In the general formula (N7), L ^N1 and L ^N2 each independently represent -SO ₂ - or -CO-. ＊Indicates the bonding position.

(Organic anion) In a preferred aspect of the compound (N), the compound (N) is a compound represented by "M ⁺ X ^- ". M ⁺ denotes a specific cation as described above. X ^- represents an organic anion. The organic anion is not particularly limited, and monovalent or divalent or higher organic anions can be mentioned. As the organic anion, an anion having a remarkably low ability to cause a nucleophilic reaction is preferable, and a non-nucleophilic anion is more preferable.

Examples of non-nucleophilic anions include sulfonate anions (aliphatic sulfonate anions, aromatic sulfonate anions, and camphorsulfonate anions, etc.), carboxylate anions (aliphatic carboxylate anions, aromatic carboxylate anions, and aralkylcarboxylate anion, etc.), sulfonyl imide anion, bis(alkylsulfonyl)imide anion, and tris(alkylsulfonyl)methide anion.

The aliphatic part in the aliphatic sulfonate anion and the aliphatic carboxylate anion can be a linear or branched alkyl group, or a cycloalkyl group, preferably a straight chain or branched group with 1 to 30 carbon atoms. A chain alkyl group or a cycloalkyl group having 3 to 30 carbon atoms. The above-mentioned alkyl group may be, for example, a fluoroalkyl group (may have a substituent other than a fluorine atom. It may be a perfluoroalkyl group).

The aryl group in the aromatic sulfonate anion and the aromatic carboxylate 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. The substituent is not particularly limited, and examples thereof include halogen atoms such as nitro groups, fluorine atoms, and chlorine atoms; carboxyl groups, hydroxyl groups, amino groups, cyano groups, alkoxy groups (preferably having 1 to 15 carbon atoms), Alkyl (preferably 1-10 carbons), cycloalkyl (preferably 3-15 carbons), aryl (preferably 6-14 carbons), alkoxycarbonyl (preferably 2 carbons ~7), acyl (preferably 2-12 carbons), alkoxycarbonyloxy (preferably 2-7 carbons), alkylthio (preferably 1-15 carbons), alkylsulfonyl Acyl group (preferably having 1 to 15 carbon atoms), alkyliminosulfonyl group (preferably having 1 to 15 carbon atoms) and aryloxysulfonyl group (preferably having 6 to 20 carbon atoms).

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

Examples of the sulfonimide anion include saccharin anion.

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 cycloalkylaryloxy groups. A sulfonyl 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 may be bonded to each other to form a ring structure. Thereby, the acid strength increases.

Examples of other non-nucleophilic anions include phosphorus fluoride (eg, PF ₆ ^- ), boron fluoride (eg, BF ₄ ^- ), and antimony fluoride (eg, SbF ₆ ^- ).

As the non-nucleophilic anion, preferred are aliphatic sulfonate anions in which at least the alpha position of sulfonic acid is substituted by fluorine atoms, aromatic sulfonate 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 replaced by a fluorine atom. Among them, perfluoroaliphatic sulfonate anion (preferably having 4 to 8 carbon atoms) or benzenesulfonate anion having a fluorine atom is more preferred, and nonafluorobutanesulfonate anion and perfluorooctanesulfonate anion are further preferred. anion, pentafluorobenzenesulfonate anion or 3,5-bis(trifluoromethyl)benzenesulfonate anion.

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

[chemical formula 25]

In formula (AN1), R ¹ and R ² each independently represent a hydrogen atom or a substituent. The substituent is not particularly limited, but is preferably a non-electron-withdrawing group. Examples of the non-electron-withdrawing group include a hydrocarbon group, a hydroxyl group, an oxyhydrocarbyl group, an oxycarbonylhydrocarbyl group, an amine group, a hydrocarbon-substituted amino group, and a hydrocarbon-substituted amide group. The groups that are non-electron-withdrawing groups are each independently preferably -R', -OH, -OR', -OCOR', -NH ₂ , -NR' ₂ , -NHR' or -NHCOR'. 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 groups such as butynyl groups and butynyl groups; cycloalkyl groups such as cyclopropyl groups, cyclobutyl groups, cyclopentyl groups, cyclohexyl groups, norbornyl groups, and adamantyl groups; Monovalent alicyclic hydrocarbon groups such as cyclopropenyl, cyclobutenyl, cyclopentenyl and norbornenyl; phenyl, tolyl, xylyl, mesityl, naphthyl, methyl Aryl groups such as naphthyl, anthracenyl, and methyl anthracenyl; monovalent aromatic hydrocarbon groups such as benzyl, phenethyl, phenylpropyl, naphthyl methyl, and anthracenyl aralkyl groups. Among them, it is preferred that R ¹ and R ² independently represent a hydrocarbon group (preferably a cycloalkyl group) or a hydrogen atom.

L represents a divalent linking group. When there are plural Ls, each L may be the same or different. Examples of divalent linking groups include -O-CO-O-, -COO-, -CONH-, -CO-, -O-, -S-, -SO-, -SO ₂ -, alkane group (preferably having 1 to 6 carbon atoms), cycloalkylene group (preferably having 3 to 15 carbon atoms), alkenylene group (preferably having 2 to 6 carbon atoms) and combinations of these A divalent linker. Among them, the divalent linking group is preferably -O-CO-O-, -COO-, -CONH-, -CO-, -O-, -SO ₂ -, -O-CO-O-alkane -, -COO-alkylene- or -CONH-alkylene-, more preferably -O-CO-O-, -O-CO-O-alkylene-, -COO-, -CONH-, -SO ₂ -or -COO-alkylene-.

L is preferably, for example, a group represented by the following formula (AN1-1). * ^a - (CR ^2a ₂ ) _X -Q- (CR ^2b ₂ ) _Y - * ^b (AN1-1)

In formula (AN1-1), * ^a represents the bonding position with R ³ in formula (AN1). * ^b represents the bonding position with -C(R ¹ )(R ² )- in the formula (AN1). X and Y each independently represent an integer of 0-10, preferably an integer of 0-3. R ^2a and R ^2b each independently represent a hydrogen atom or a substituent. When there are plural R ^2a and R ^2b respectively, the plural 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 formula (AN1) is a group 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 . However, when X+Y in formula (AN1-1) is 1 or more, and either of R ^2a and R ^2b in formula (AN1-1) 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 -SO ₂ -* ^B. * ^A represents the bonding position on the R ³ side in the formula (AN1), and * ^B represents the bonding position on the -SO ₃ ^- side in the formula (AN1).

In formula (AN1), R ³ represents an organic group. The above-mentioned organic group is not particularly limited as long as it has more than one carbon atom, and may be a straight-chain group (such as a straight-chain alkyl group) or a branched-chain group (such as a branched-chain group such as a tert-butyl group). Alkyl group), can also be a cyclic group. The above organic group may or may not have a substituent. The above-mentioned organic group may or may not have a heteroatom (oxygen atom, sulfur atom, and/or nitrogen atom, etc.).

Among them, ^R3 is preferably an organic group with a ring structure. The above-mentioned ring structure may be monocyclic or polycyclic, and may have a substituent. The ring in the organic group including a ring structure is preferably directly bonded to L in the formula (AN1). The organic group having the above ring structure may or may not have a hetero atom (oxygen atom, sulfur atom, nitrogen atom, etc.), for example. A heteroatom may be substituted with one or more carbon atoms constituting the ring structure. The organic group having the above-mentioned cyclic structure is preferably, for example, a hydrocarbon group having a cyclic structure, a lactone ring group, and a sultone ring group. Among them, the organic group having the above-mentioned cyclic structure is preferably a hydrocarbon group having a cyclic structure. The hydrocarbon group of the above-mentioned cyclic structure is preferably a monocyclic or polycyclic cycloalkyl group. These groups may have substituents. The above-mentioned cycloalkyl group may be monocyclic (cyclohexyl, etc.) or polycyclic (adamantyl, etc.), and the carbon number is preferably 5-12. Examples of the above-mentioned lactone group and sultone group include structures represented by formulas (LC1-1) to (LC1-21) and structures represented by formulas (SL1-1) to (SL1-3) described later. In either structure, a group obtained by removing one hydrogen atom from the ring member atoms constituting the lactone structure or the sultone structure is preferable.

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

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

[chemical formula 26]

In formula (AN2), o represents the integer of 1-3. p represents an integer of 0-10. q represents an integer of 0-10.

Xf represents a hydrogen atom, a fluorine atom, an alkyl group substituted with at least one fluorine atom, or an organic group not having a fluorine atom. The carbon number of the alkyl group is preferably 1-10, more preferably 1-4. The alkyl group substituted with at least one fluorine atom is preferably a perfluoroalkyl group. Xf is preferably a fluorine atom or a perfluoroalkyl group having 1 to 4 carbons, more preferably a fluorine atom or CF ₃ , further preferably two Xf are fluorine atoms.

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 plural R ⁴ and R ⁵ , R ⁴ and R ⁵ may be the same or different. The alkyl groups represented by R ⁴ and R ⁵ preferably have 1-4 carbon atoms. The above-mentioned alkyl group may have a substituent. R ₄ and R ₅ are preferably hydrogen atoms.

L represents a divalent linking group. The definition of L has the same meaning as L in formula (AN1).

W represents an organic group including a ring structure. Among them, a cyclic organic group is preferable. As a cyclic organic group, an alicyclic group, an aryl group, and a heterocyclic group are mentioned, for example. The alicyclic group may 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 aryl group include phenyl, naphthyl, phenanthrenyl and anthracenyl. A heterocyclic group can be monocyclic or polycyclic. Among them, when it is a polycyclic heterocyclic group, the diffusion of acid can be further suppressed. A heterocyclic group may or may not be aromatic. 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. As a heterocyclic ring which does not have aromaticity, a tetrahydropyran ring, a lactone ring, a sultone ring, and a decahydroisoquinoline ring are mentioned, for example. The heterocyclic ring in the heterocyclic group is preferably a furan ring, a thiophene ring, a pyridine ring or a decahydroisoquinoline ring.

The above-mentioned cyclic organic group may have a substituent. As the above-mentioned substituent, 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 spiro Any one of the rings, preferably having 3 to 20 carbon atoms), aryl group (preferably having 6 to 14 carbon atoms), hydroxyl group, alkoxy group, ester group, amido group, urethane group, Urea group, thioether group, sulfonamide group and sulfonate group. In addition, the carbon constituting the cyclic organic group (the carbon that contributes to ring formation) may be carbonyl carbon.

As the anion represented by the formula (AN2), 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. However, L, q, and W are the same as in formula (AN2). q' represents the integer of 0-10.

As the non-nucleophilic anion, an aromatic sulfonate anion represented by the following formula (AN3) is also preferable.

[chemical formula 27]

In formula (AN3), Ar represents an aryl group (phenyl group, etc.), and may further have a substituent other than a sulfonate 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 more preferable, 3 is still more preferable.

D represents a single bond or a divalent linking group. Examples of the divalent linking group include an ether group, a thioether group, a carbonyl group, an arylene group, a sulfo group, a sulfonate group, an ester group, and a group composed of a combination of two or more of these.

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

As the non-nucleophilic anion, disulfonamide anion is also preferred. The disulfonamide anion is, for example, an anion represented by N ^- (SO ₂ -R ^q ) ₂ . Here, ^Rq 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. The group formed by bonding two R ^q to each other is preferably an alkylene group which may have a substituent, more preferably a fluoroalkylene group, and still more preferably a perfluoroalkylene group. The carbon number of the said alkylene group is preferably 2-4.

Moreover, as a non-nucleophilic anion, the anion represented by following formula (d1-1)-(d1-4) is also mentioned.

[chemical formula 28]

[chemical formula 29]

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

In formula (d1-2), Z ^2c represents a hydrocarbon group having 1 to 30 carbon atoms which may have a substituent (wherein the carbon atom adjacent to S is not substituted with a fluorine atom). The above-mentioned hydrocarbon group in Z ^2c may be linear or branched, or may have a cyclic structure. Also, a carbon atom in the above hydrocarbon group (preferably a carbon atom serving as a ring member atom when the above hydrocarbon group has a ring structure) may be carbonyl carbon (—CO—). As said hydrocarbon group, the group which has the norbornyl group which may have a substituent, for example is mentioned. The carbon atom forming the above-mentioned norbornyl group may be a carbonyl carbon. "Z ^2c -SO ₃ ^- " in the formula (d1-2) is preferably different from the anion represented by the above formulas (AN1) to (AN3). For example, Z ^2c is preferably a group other than aryl. For example, the atoms at the α-position and β-position with respect to -SO ₃ ^- in Z ^2c are preferably atoms other than carbon atoms having a fluorine atom as a substituent. For example, in Z ^2c , the atom at the α position and/or the atom at the β position with respect to -SO ₃ ^- is preferably a ring member atom in a cyclic group.

In formula (d1-3), R ⁵² represents an organic group (preferably a hydrocarbon group with a fluorine atom), Y ³ represents a linear, branched or cyclic alkylene, arylylene, or carbonyl group, Rf represents a hydrocarbon group.

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

One type of organic anions may be used alone, or two or more types may be used.

Compound (N) is also preferably at least one selected from the group consisting of compound (NI) and compound (NII).

(Compound (NI)) Compound (NI) is a compound having one or more of the following structural site X and one or more of the following structural site Y, which is produced by irradiation with actinic rays or radiation containing A compound of an acid derived from the following first acidic site of X and the following second acidic site of structural site Y described below. Structural site X: a structural site composed of anionic site A ₁ ⁻ and cationic site M ₁ ⁺ , and the first acidic site represented by HA ₁ is formed by irradiation with actinic rays or radiation Structural site Y: anionic site A ₂ The compound (NI) which is composed of ^- and the cationic site M ₂ ⁺ and forms the second acidic site represented by HA ₂ by irradiation with actinic rays or radiation satisfies the following condition I.

Condition I: In the above-mentioned compound (NI), the compound PNI obtained by substituting the above-mentioned cationic site M ₁ ⁺ in the above-mentioned structural site X and the above-mentioned cationic site M ₂ ⁺ in the above-mentioned structural site Y with H ⁺ has an acid dissociation constant a1 and Acid dissociation constant a2, and the above acid dissociation constant a2 is larger than the above acid dissociation constant a1, and the acid dissociation constant a1 is derived from the acidity represented by HA ₁ obtained by substituting the above cationic site M ₁ ⁺ in the above structural site X with H ⁺ site, the acid dissociation constant a2 is derived from the acidic site represented by HA ₂ obtained by substituting the above-mentioned cationic site M ₂ ⁺ in the above-mentioned structural site Y with H ⁺ .

Hereinafter, condition I will be described more specifically. In the case where the compound (NI) is, for example, a compound that produces an acid having one of the above-mentioned first acidic sites from the above-mentioned structural site X and one of the above-mentioned second acidic sites from the above-mentioned structural site Y, the compound PNI is equivalent to "has HA ₁ and HA ₂ compounds". Regarding the acid dissociation constant a1 and the acid dissociation constant a2 of the compound PNI, if it is more specifically described, when the acid dissociation constant of the compound PNI is obtained, the compound PNI is "a compound having A ₁ ^- and HA ₂ ” is the acid dissociation constant a1, and the pKa when the above-mentioned “compound having A ₁ ^- and HA ₂ ” is the “compound having A ₁ ^- and A ₂ ^- ” is the acid dissociation constant a2.

In the case where the compound (NI) is, for example, a compound that produces an acid having two of the above-mentioned first acidic sites from the above-mentioned structural site X and one of the above-mentioned second acidic sites from the above-mentioned structural site Y, the compound PNI is equivalent to "having two A compound of one HA ₁ and one HA ₂ ". In the case of obtaining the acid dissociation constant of compound PNI, the acid dissociation constant when compound PNI is "a compound with one A ₁ ^- , one HA ₁ and one HA ₂ " and "a compound with one A ₁ ^- , one HA ₁ and The acid dissociation constant when the "one HA ₂ compound" is "the compound having two A ₁ ^- and one HA ₂ " corresponds to the above-mentioned acid dissociation constant a1. When the "compound having two A ₁ ^- and one HA ₂ " is "the compound having two A ₁ ^- and A ₂ ^- ", the acid dissociation constant corresponds to the acid dissociation constant a2. That is, in the case of the compound PNI, when it has a plurality of acid dissociation constants derived from the acidic site represented by HA ₁ obtained by substituting the above-mentioned cationic site M ₁ ⁺ in the above-mentioned structural site X with H ⁺ , The value of the acid dissociation constant a2 is greater than the largest value among the plurality of acid dissociation constants a1. Furthermore, the acid dissociation constant when the compound PNI is "a compound having one A ₁ ^- , one HA ₁ and one HA ₂ " is set to aa and "the compound having one A ₁ ^- , one HA ₁ and one HA ₂ When the acid dissociation constant of "compound" is "a compound having two A ₁ ^- and one HA ₂ " is ab, the relationship between aa and ab satisfies aa<ab.

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

In the above compound PNI, the difference (absolute value) between the acid dissociation constant a1 (the maximum value when there are multiple acid dissociation constants a1) and the acid dissociation constant a2 is preferably 0.1 or more, more preferably 0.5 or more, and further preferably Preferably, it is 1.0 or more. The upper limit of the difference (absolute value) between the acid dissociation constant a1 (the maximum value when a plurality of acid dissociation constants a1 exists) and the acid dissociation constant a2 is not particularly limited, and is, for example, 16 or less.

In the above compound PNI, the acid dissociation constant a2 is preferably 20 or less, more preferably 15 or less. Furthermore, the lower limit of the acid dissociation constant a2 is preferably -4.0 or more.

In the above compound PNI, the acid dissociation constant a1 is preferably 2.0 or less, more preferably 0 or less. Furthermore, the lower limit of the acid dissociation constant a1 is preferably -20.0 or more.

Anion site A ₁ ^- and anion site A ₂ ^- are structural sites containing negatively charged atoms or atomic groups, for example, selected from formulas (AA-1) to (AA-3) and formula (BB) shown below The structural parts in the group consisting of -1)～(BB-6). The anion site A ₁ ^- is preferably an acid site capable of forming an acidic site with a small acid dissociation constant, among them, any one of the formulas (AA-1) to (AA-3) is more preferred, and the formula (AA -1) and (AA-3). Also, the anion site A ₂ ^- is preferably an acidic site capable of forming an acidic site with a higher acid dissociation constant than the anion site A ₁ ^- , more preferably any one of the formulas (BB-1) to (BB-6), and further It is preferably any one of formulas (BB-1) and (BB-4). In addition, in the following formulas (AA-1) to (AA-3) and formulas (BB-1) to (BB-6), * represents a bonding position. In formula (AA-2), R ^A represents a monovalent organic group. The monovalent organic group represented by ^RA is not particularly limited, and examples thereof include a cyano group, a trifluoromethyl group, and a methanesulfonyl group.

[chemical formula 30]

[chemical formula 31]

The anion site A ₁ ^- and the anion site A ₂ ^- preferably have at least one selected from the group consisting of the group represented by the above general formula (N7), -SO ₃ ^- and -CO ₂ ^- .

The cationic site M ₁ ⁺ and the cationic site M ₂ ⁺ are structural sites containing positively charged atoms or atomic groups, and examples thereof include organic cations with a monovalent charge. At least one of M ₁ ⁺ and M ₂ ⁺ is a specific cation as described above.

The specific structure of the compound (NI) is not particularly limited, and examples thereof include compounds represented by formula (Ia-1) to formula (Ia-5) described later.

-Compound represented by formula (Ia-1)- Hereinafter, first, the compound represented by the formula (Ia-1) will be described.

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

The compound represented by the formula (Ia-1) generates an acid represented by HA ₁₁ -L ₁ -A ₁₂ H upon irradiation with actinic rays or radiation.

In 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 compound PNIa (HA ₁₁ -L ₁ -A ₁₂ H) obtained by substituting the cations represented by M ₁₁ ⁺ and M ₁₂ ⁺ with H ⁺ in the above formula (Ia-1), from A ₁₂ H The acid dissociation constant a2 of the represented acid site is greater than the acid dissociation constant a1 from the acid site represented by HA ₁₁ . In addition, suitable values of the acid dissociation constant a1 and the acid dissociation constant a2 are as described above. Compound PNIa is the same acid that is generated from the compound represented by formula (Ia-1) by irradiation with actinic rays or radiation. Also, 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 formula (Ia-1), at least one of M ₁₁ ⁺ and M ₁₂ ⁺ is the specific cation as described above.

The monovalent anionic functional group represented by A ₁₁ ^- means a monovalent group including the above-mentioned anionic moiety A ₁ ^- . Also, the monovalent anionic functional group represented by A ₁₂ ^- means a monovalent group including the above-mentioned anionic moiety A ₂ ^- . The monovalent anionic functional groups represented by A ₁₁ ^- and A ₁₂ ^- are preferably included in the above formulas (AA-1) to (AA-3) and formulas (BB-1) to (BB-6). A monovalent anionic functional group at any anion site, more preferably selected from the group consisting of formulas (AX-1) to (AX-3) and formulas (BX-1) to (BX-7) A monovalent anionic functional group. Among them, the monovalent anionic functional group represented by A ₁₁ ^- is preferably a monovalent anionic functional group represented by any one of the formulas (AX-1) to (AX-3). The monovalent anionic functional group represented by A ₁₂ ^- is preferably a monovalent anionic functional group represented by any one of the formulas (BX-1) to (BX-7), and more preferably It is a monovalent anionic functional group represented by any one of formula (BX-1) - (BX-6).

[chemical formula 32]

In formulas (AX-1) to (AX-3), R ^A1 and R ^A2 each independently represent a monovalent organic group. ＊Indicates the bonding position. The monovalent organic group represented by R ^A1 is not particularly limited, and examples thereof include a cyano group, a trifluoromethyl group, and a methanesulfonyl group.

The monovalent organic group represented by R ^A2 is preferably a linear, branched or cyclic alkyl group or aryl group. The carbon number of the said alkyl group becomes like this. Preferably it is 1-15, More preferably, it is 1-10, More preferably, it is 1-6. The above-mentioned alkyl group may have a substituent. The substituent is preferably a fluorine atom or a cyano group, more preferably a fluorine atom. When the above-mentioned alkyl group has a fluorine atom as a substituent, it may be a perfluoroalkyl group.

The aryl group is preferably a phenyl group or a naphthyl group, more preferably a phenyl group. The above-mentioned aryl group may have a substituent. The substituent is preferably a fluorine atom, an iodine atom, a perfluoroalkyl group (for example, preferably having 1 to 10 carbon atoms, more preferably 1 to 6 carbon atoms), or a cyano group, more preferably a fluorine atom or an iodine atom or perfluoroalkyl.

In formulas (BX-1) to (BX-4) and formula (BX-6), R ^B represents a monovalent organic group. ＊Indicates the bonding position. The monovalent organic group represented by R ^B is preferably a linear, branched or cyclic alkyl group or aryl group. The carbon number of the said alkyl group becomes like this. Preferably it is 1-15, More preferably, it is 1-10, More preferably, it is 1-6. The above-mentioned alkyl group may have a substituent. The substituent is not particularly limited, but the substituent is preferably a fluorine atom or a cyano group, more preferably a fluorine atom. When the above-mentioned alkyl group has a fluorine atom as a substituent, it may be a perfluoroalkyl group. Furthermore, when the carbon atom serving as the bonding position in the alkyl group has a substituent, it is also preferably a substituent other than a fluorine atom or a cyano group. Here, the so-called carbon atoms serving as bonding positions in the alkyl group, for example, in the case of formulas (BX-1) and (BX-4), correspond to - In the case of formulas (BX-2) and (BX-3), the carbon atom directly bonded to CO- corresponds to the carbon atom directly bonded to -SO ₂ - shown in the formula in the alkyl group, in In the case of the formula (BX-6), it corresponds to the carbon atom directly bonded to ^N- indicated in the formula in the alkyl group. Carbon atoms of the above-mentioned alkyl groups may be substituted with carbonyl carbons.

The aryl group is preferably a phenyl group or a naphthyl group, more preferably a phenyl group. The above-mentioned aryl group may have a substituent. The substituent is preferably a fluorine atom, an iodine atom, a perfluoroalkyl group (for example, preferably having 1 to 10 carbon atoms, more preferably 1 to 6 carbon atoms), a cyano group, and an alkyl group (such as preferably having a carbon number of 1 to 6). 1 to 10, more preferably 1 to 6 carbons.), alkoxy (for example, preferably 1 to 10 carbons, more preferably 1 to 6 carbons.) or alkoxycarbonyl (for example, preferably carbon 2 to 10, more preferably 2 to 6 carbons), more preferably a fluorine atom, an iodine atom, a perfluoroalkyl group, an alkyl group, an alkoxy group or an alkoxycarbonyl group.

In formula (Ia-1), the divalent linking group represented by _L1 is not particularly limited, and examples thereof include -CO-, -NR-, -O-, -S-, -SO-, -SO ₂ -, alkylene group (preferably having 1 to 6 carbon atoms, which can be linear or branched), cycloalkylene group (preferably having 3 to 15 carbon atoms), alkenylene group (preferably having carbon number 2-6), divalent aliphatic heterocyclic group (preferably a 5-10 membered ring with at least one N atom, O atom, S atom or Se atom in the ring structure, more preferably a 5-7 membered ring ring, further preferably a 5-6 membered ring.), a divalent aromatic heterocyclic group (preferably a 5-10 membered ring with at least one N atom, O atom, S 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 hydrocarbon ring group (preferably a 6-10-membered ring, further preferably a 6-membered ring.) and A divalent linking group formed by combining a plurality of these. Examples of the above-mentioned R include a hydrogen atom or a monovalent organic group. The monovalent organic group is not particularly limited, and is preferably, for example, an alkyl group (preferably having 1 to 6 carbon atoms). The above-mentioned alkylene group, the above-mentioned cycloalkylene group, the above-mentioned alkenylene group, the above-mentioned divalent aliphatic heterocyclic group, divalent aromatic heterocyclic group and divalent aromatic hydrocarbon ring group may have a substituent. As a substituent, a halogen atom (preferably a fluorine atom) is mentioned, for example.

Among them, the divalent linking group represented by L ₁ is preferably a divalent linking group represented by formula (L1).

[chemical formula 33]

In formula (L1), L ₁₁₁ represents a single bond or a divalent linking group. The divalent linking group represented by L ₁₁₁ is not particularly limited, and examples thereof include -CO-, -NH-, -O-, -SO-, -SO ₂ -, alkylene groups which may have substituents (Preferably having 1 to 6 carbon atoms. Either straight chain or branched chain may be possible), optionally substituted cycloalkylene group (preferably having 3 to 15 carbon atoms), optionally having a substituent An aryl group (preferably having 6 to 10 carbon atoms) and a divalent linking group obtained by combining a plurality of these. It does not specifically limit as a substituent, For example, a halogen atom is mentioned. p represents the integer of 0-3, Preferably it represents the integer of 1-3. 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. The alkyl group substituted with at least one fluorine atom is preferably a perfluoroalkyl group. Xf ₂ each independently represent a hydrogen atom, an alkyl group which may have a fluorine atom as a substituent, or a fluorine atom. The carbon number of the alkyl group is preferably 1-10, more preferably 1-4. Among them, Xf ₂ preferably represents a fluorine atom or an alkyl group substituted with 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 . In particular, it is further preferred that both Xf ₁ and Xf ₂ are fluorine atoms. ＊Indicates the bonding position. When L ₁₁ in formula (Ia-1) represents a divalent linking group represented by formula (L1), it is preferable that the bond (*) on the side of L ₁₁₁ in formula (L1) is the same as the formula ( A ₁₂ ^-bonding in Ia-1).

-Compounds represented by formulas (Ia-2) to (Ia-4)- Next, the compounds represented by the formulas (Ia-2) to (Ia-4) will be described.

[chemical formula 34]

In 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 monovalent group including the above-mentioned anion site A ₁ ^- . The monovalent anionic functional groups represented by A _21a ^- and A _21b ^- are not particularly limited, and examples thereof include those selected from the group consisting of the above formulas (AX-1) to (AX-3). Monovalent anionic functional group. A ₂₂ ^- represents a divalent anionic functional group. Here, the divalent anionic functional group represented by A ₂₂ ^- means a divalent linking group including the above-mentioned anion site A ₂ ^- . Examples of the divalent anionic functional group represented by A ₂₂ ^- include divalent anionic functional groups represented by the following formulas (BX-8) to (BX-11).

[chemical formula 35]

M _21a ⁺ , M _21b ⁺ and M ₂₂ ⁺ each independently represent an organic cation. At least one of M _21a ⁺ , M _21b ⁺ and M ₂₂ ⁺ is the specific cation as described above. L ₂₁ and L ₂₂ each independently represent a divalent organic group.

In the above formula (Ia-2), in the compound PNIa-2 obtained by substituting the organic cations represented _by M _21a ⁺ , M _21b ⁺ and M ₂₂ ⁺ with H ⁺ , the The acid dissociation constant a2 is greater than the acid dissociation constant a1-1 derived from A _21a H and the acid dissociation constant a1-2 derived from the acid site represented by A _21b H. In addition, the acid dissociation constant a1-1 and the acid dissociation constant a1-2 correspond to the above-mentioned acid dissociation constant a1. In addition, A _21a ^- and A _21b ^- may be the same as or different from each other. M _21a ⁺ , M _21b ⁺ and M ₂₂ ⁺ may be the same as or different from each other. 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 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 above formula (Ia-2), and the preferred aspects are also the same. The monovalent anionic functional group represented by A ₃₂ ^- means a monovalent group including the above-mentioned anionic moiety A ₂ ^- . The monovalent anionic functional group represented by A ₃₂ ^- is not particularly limited, and examples thereof include monovalent anions selected from the group consisting of the above formulas (BX-1) to (BX-7) Sexual functional groups. A _31b ^- represents a divalent anionic functional group. Here, the divalent anionic functional group represented by A _31b ^- means a divalent linking group including the above-mentioned anionic site A ₁ ^- . Examples of the divalent anionic functional group represented by A _31b ^- include divalent anionic functional groups represented by the following formula (AX-4).

[chemical formula 36]

M _31a ⁺ , M _31b ⁺ and M ₃₂ ⁺ each independently represent a monovalent organic cation. At least one of M _31a ⁺ , M _31b ⁺ and M ₃₂ ⁺ is the specific cation as described above. L ₃₁ and L ₃₂ each independently represent a divalent organic group.

In the above formula (Ia-3), in _the compound PNIa-3 obtained by substituting the organic cations represented by M _31a ⁺ , M _31b ⁺ and M ₃₂ ⁺ with H ⁺ , the The acid dissociation constant a2 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 above-mentioned acid dissociation constant a1. In addition, A _31a ^- and A ₃₂ ^- may be the same as or different from each other. Also, M _31a ⁺ , M _31b ⁺ and M ₃₂ ⁺ may be the same as or different from each other. 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 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 above formula (Ia-2). The definition of the monovalent anionic functional group represented by A ₄₂ ^- is the same as that of A ₃₂ ^- in the above formula (Ia-3), and the preferred aspects are also the same. M _41a ⁺ , M _41b ⁺ and M ₄₂ ⁺ each independently represent an organic cation. L ₄₁ represents a trivalent organic group.

In the above formula (Ia-4), in _the compound PNIa-4 obtained by substituting the organic cations represented by M _41a ⁺ , M _41b ⁺ and M ₄₂ ⁺ with H ⁺ , the The acid dissociation constant a2 is greater than the acid dissociation constant a1-5 derived from the acid site represented by _A41aH and the acid dissociation constant a1-6 derived from the acid site represented by _A41bH . In addition, the acid dissociation constant a1-5 and the acid dissociation constant a1-6 correspond to the above-mentioned acid dissociation constant a1. In addition, A _41a ^- , A _41b ^- and A ₄₂ ^- may be the same as or different from each other. Also, M _41a ⁺ , M _41b ⁺ and M ₄₂ ⁺ may be the same as or different from each other. 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.

The divalent organic groups represented by L ₂₁ and L ₂₂ in formula (Ia-2) and L ₃₁ and L ₃₂ in formula (Ia-3) are not particularly limited, and examples thereof include -CO- , -NR-, -O-, -S-, -SO-, -SO ₂ -, alkylene (preferably having 1 to 6 carbons, can be linear or branched), cycloalkylene (preferably having 3 to 15 carbons), alkenyl (preferably having 2 to 6 carbons), divalent aliphatic heterocyclic group (preferably having at least one N atom, O atom, 5-10 membered ring of S atom or Se atom, more preferably 5-7 membered ring, further preferably 5-6 membered ring.), divalent aromatic heterocyclic group (preferably within the ring structure 5-10 membered rings having at least one N atom, O atom, S atom or Se atom, more preferably 5-7 membered rings, further preferably 5-6 membered rings.), divalent aromatic hydrocarbon ring group (Preferably a 6-10-membered ring, more preferably a 6-membered ring.) And a divalent organic group obtained by combining a plurality of these. Examples of R in the above -NR- include a hydrogen atom or a monovalent organic group. The monovalent organic group is not particularly limited, and is preferably, for example, an alkyl group (preferably having 1 to 6 carbon atoms). The above-mentioned alkylene group, the above-mentioned cycloalkylene group, the above-mentioned alkenylene group, the above-mentioned divalent aliphatic heterocyclic group, divalent aromatic heterocyclic group and divalent aromatic hydrocarbon ring group may have a substituent. 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 formula (Ia-2) and L ₃₁ and L ₃₂ in formula (Ia-3), those represented by, for example, the following formula (L2) are also preferable: Represents a divalent organic radical.

[chemical formula 37]

In formula (L2), q represents the integer of 1-3. ＊Indicates the bonding 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. The alkyl group substituted with at least one fluorine atom is preferably a perfluoroalkyl group. Xf is preferably a fluorine atom or a perfluoroalkyl group having 1 to 4 carbons, more preferably a fluorine atom or CF ₃ . In particular, it is further preferred that two of Xf are fluorine atoms.

L _A represents a single bond or a divalent linking group. The divalent linking group represented by L _A is not particularly limited, and examples thereof include -CO-, -O-, -SO-, -SO ₂ -, alkylene (preferably having 1 to 6 carbon atoms) It can be linear or branched), cycloalkylene (preferably 3 to 15 carbons), divalent aromatic hydrocarbon ring (preferably 6 to 10 membered ring, more preferably 6 Member ring.) and a divalent linking group formed by combining a plurality of these. The alkylene group, the cycloalkylene group, and the divalent aromatic hydrocarbon 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 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 -*. Furthermore, the phenylene group Ph may have a substituent is preferably 1,4-phenylene group. The substituent is not particularly limited, and is preferably an alkyl group (for example, preferably having 1 to 10 carbon atoms, more preferably 1 to 6 carbon atoms), an alkoxy group (such as preferably having 1 to 10 carbon atoms, More preferably, it is a carbon number 1-6.) or an alkoxycarbonyl group (for example, Preferably it is a carbon number 2-10, More preferably, it is a carbon number 2-6.). When L ₂₁ and L ₂₂ in the formula (Ia-2) represent a divalent organic group represented by the formula (L2), the bond (*) on _{the LA} side in the formula (L2) is preferably It is bonded to A _21a ^- and A _21b ^- in the formula (Ia-2). When L ₃₁ and L ₃₂ in the formula (Ia-3) represent a divalent organic group represented by the formula (L2), the bond (*) on _{the LA} side in the formula (L2) is preferably It is bonded to A _31a ^- and A ₃₂ ^- in the formula (Ia-3).

-Compound represented by formula (Ia-5)- Next, Formula (Ia-5) will be described.

[chemical formula 38]

In 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 monovalent group including the aforementioned anionic site A ₁ ^- . The monovalent anionic functional groups represented by A _51a ^- , A _51b ^- and A _51c ^- are not particularly limited, and examples thereof include those selected from the above formulas (AX-1) to (AX-3). A monovalent anionic functional group in the group. A _52a ^- and A _52b ^- represent divalent anionic functional groups. Here, the divalent anionic functional group represented by A _52a ^- and A _52b ^- refers to a divalent linking group including the above-mentioned anion site A ₂ ^- . Examples of the divalent anionic functional group represented by A ₂₂ ^- include divalent anionic functional groups selected from the group consisting of the above formulas (BX-8) to (BX-11).

M _51a ⁺ , M _51b ⁺ , M _51c ⁺ , M _52a ⁺ and M _52b ⁺ each independently represent an organic cation. At least one of M _51a ⁺ , M _51b ⁺ , M _51c ⁺ , M _52a ⁺ and M _52b ⁺ is the specific cation as described 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 meanings as L ₂₁ and L ₂₂ in the above formula (Ia-2), and their preferred aspects 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 above formula (Ia-4), and its preferred aspects are also the same.

In the above formula (Ia-5), the organic cation represented by M _51a ⁺ , M _51b ⁺ , M _51c ⁺ , M _52a ⁺ and M _52b ⁺ is replaced by H ⁺ in the compound PNIa-5, from A The acid dissociation constant a2-1 of the acid site represented by _52a H and the acid dissociation constant a2-2 from the acid site represented by A _52b H are greater than the acid dissociation constant a1-1 from A _51a H, the acid dissociation constant a1-1 from A _51b H The acid dissociation constant a1-2 of the acid site and the acid dissociation constant a1-3 from the acid site represented by A _51c H. In addition, the acid dissociation constants a1-1 to a1-3 correspond to the above-mentioned acid dissociation constant a1, and the acid dissociation constants a2-1 and a2-2 correspond to the above-mentioned acid dissociation constant a2. In addition, A _51a ^- , A _51b ^- and A _51c ^- may be the same as or different from each other. Also, A _52a ^- and A _52b ^- may be the same as or different from each other. M _51a ⁺ , M _51b ⁺ , M _51c ⁺ , M _52a ⁺ and M _52b ⁺ may be the same as or different from each other. 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 substituent.

(compound (NII)) Compound (NII) is a compound having two or more of the above-mentioned structural site X and one or more of the following structural site Z, which is produced by irradiation with actinic rays or radiation. A compound having an acidic site and an acid of the above structural site Z. Structural site Z: a non-ionic site capable of neutralizing acid

In compound (NII), the definition of structural site X, and the definitions of A ₁ ^- and M ₁ ⁺ have the same meaning as the definition of structural site X, A ₁ ^- and M ₁ ⁺ in compound (NI) above, and are more The same goes for good looks.

In the above-mentioned compound (NII), in the compound PNII obtained by substituting the above-mentioned cationic site M ₁ ⁺ in the above-mentioned structural site X with H ⁺ , the compound PNII is obtained by substituting the above-mentioned cationic site M ₁ ⁺ in the above-mentioned structural site X with H ⁺ The suitable range of the acid dissociation constant a1 of the acid site represented by HA ₁ is the same as the acid dissociation constant a1 in the above-mentioned compound PNI. Furthermore, when the compound (NII) is, for example, a compound that generates an acid having two of the above-mentioned first acidic site from the above-mentioned structural site X and the above-mentioned structural site Z, the compound PNII is equivalent to "a compound having two HA ₁ ". In the case of obtaining the acid dissociation constant of the compound PNII, the acid dissociation constant when the compound PNII 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 of the "compound having two A ₁ ^- " corresponds to the acid dissociation constant a1.

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

The nonionic portion capable of neutralizing the acid in the structural portion Z is not particularly limited, and is preferably, for example, a group capable of electrostatic interaction with protons or a portion containing a functional group having electrons. Examples of groups capable of electrostatic interaction with protons or functional groups having electrons include functional groups having macrocyclic structures such as cyclic polyethers, or functional groups having nitrogen atoms that do not participate in π-conjugated unshared electron pairs. base. A nitrogen atom having a non-shared electron pair that does not participate in π-conjugation is, for example, a nitrogen atom having a partial structure represented by the following formula.

[chemical formula 39]

Examples of partial structures having groups capable of electrostatic interaction with protons or functional groups of electrons include crown ether structures, azacrown ether structures, primary to tertiary amine structures, pyridine structures, imidazole structures, and pyrazine structures. structure, among them, a primary to tertiary amine structure is preferred.

The compound (NII) is not particularly limited, and examples thereof include compounds represented by the following formula (IIa-1) and the following formula (IIa-2).

[chemical formula 40]

In the above formula (IIa-1), A _61a ^- and A _61b ^- have the same meanings as A ₁₁ ^- in the above formula (Ia-1), and preferred embodiments are also the same. Also, M _61a ⁺ and M _61b ⁺ have the same meanings as M ₁₁ ⁺ in the above formula (Ia-1), and preferred embodiments are also the same. In the above formula (IIa-1), L ₆₁ and L ₆₂ have the same meanings as L ₁ in the above formula (Ia-1), and preferred embodiments are also the same.

In formula (IIa-1), R _2X represents a monovalent organic group. The monovalent organic group represented by _R2X is not particularly limited, and examples thereof include alkyl (preferably having 1 to 10 carbon atoms, which may be linear or branched), cycloalkyl (preferably carbon number 3-15) or alkenyl (preferably carbon number 2-6). The -CH _{2 -} contained in the alkyl group, cycloalkyl group and alkenyl group in the monovalent organic group represented by R _2X can be selected from -CO-, -NH-, -O-, -S-, - One or a combination of two or more of the group consisting of SO- and -SO ₂ - is substituted. The above-mentioned alkylene group, the above-mentioned cycloalkylene group, and the above-mentioned alkenylene group may have a substituent. It does not specifically limit as a substituent, For example, a halogen atom (preferably a fluorine atom) is mentioned.

In the above formula (IIa-1), the compound PNIIa-1, which is obtained by substituting the organic cations represented by M _61a ⁺ and M _61b ⁺ with H ⁺ , has an acid dissociation constant a1 derived from the acidic site represented by A _61a H -7 and the acid dissociation constant a1-8 derived from the acid site represented by A _61b H correspond to the above-mentioned acid dissociation constant a1. Furthermore, in the above formula (IIa-1), the compound PNIIa-1 obtained by substituting the above-mentioned cationic sites M _61a ⁺ and M _61b ⁺ in the above-mentioned structural site X with H ⁺ corresponds to HA _61a -L ₆₁ -N(R _2X ) -L ₆₂ -A _61b H. Also, compound PNIIa-1 is the same as the acid of formula (IIa-1) produced from the compound represented by formula (IIa-1) by irradiation with actinic rays or radiation. 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 above formula (IIa-2), A _71a ^- , A _71b ^- and A _71c ^- have the same meanings as A ₁₁ ^- in the above formula (Ia-1), and preferred embodiments are also the same. M _71a ⁺ , M _71b ⁺ , and M _71c ⁺ have the same meanings as M ₁₁ ⁺ in the above formula (Ia-1), and preferred embodiments are also the same. In the above formula (IIa-2), L ₇₁ , L ₇₂ , and L ₇₃ have the same meanings as L ₁ in the above formula (Ia-1), and preferred embodiments are also the same.

In the above formula (IIa-2), in the compound PNIIa-2 obtained by substituting the organic cations represented by M _71a ⁺ _, M _71b ⁺ and M _71c ⁺ with H ⁺ , the The acid dissociation constant a1-9, 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 correspond to the above-mentioned acid dissociation constant a1. Furthermore, the compound PNIIa-2 obtained by substituting the above-mentioned cationic sites M _71a ⁺ , M _71b ⁺ and M _71c ⁺ in the above-mentioned structural site X in the above-mentioned formula (IIa-1) with H ⁺ corresponds to HA _71a -L ₇₁ -N( _L73 - _A71cH ) _-L72 - _A71bH . Also, compound PNIIa-2 is the same acid that is generated from the compound represented by formula (IIa-2) by irradiation with actinic rays or radiation. At least one of M _71a ⁺ , M _71b ⁺ , M _71c ⁺ , A _71a ⁻ , A _71b ⁻ , A _71c ⁻ , L ₇₁ , L ₇₂ and L ₇₃ has an acid decomposable group as a substituent.

The sites other than the cation that the compound (NI) and the compound (NII) can have are exemplified below.

[chemical formula 41]

[chemical formula 42]

In the composition of the present invention, the compound (N) may be used alone or in combination of two or more.

The content of the compound (N) in the composition of the present invention is not particularly limited. For example, when the compound (N) is used as the photoacid generator, the content of the compound (N) in the composition of the present invention is preferably 0.5% by mass or more with respect to the total solid content of the composition of the present invention, more preferably Preferably, it is at least 1.0% by mass. The content of the compound (N) in the composition of the present invention is preferably 55.0% by mass or less, more preferably 30.0% by mass or less, further preferably 25.0% by mass or less, based on the total solid content of the composition of the present invention. In addition, for example, when the compound (N) is used as an acid diffusion control agent, the content of the compound (N) in the composition of the present invention is preferably 0.1 to 15.0% by mass relative to the total solid content of the composition of the present invention, More preferably, it is 1.0-15.0 mass %.

<Resin (A) whose polarity is increased by the action of acid> The resin (A) whose polarity is increased by the action of an acid (also simply referred to as "resin (A)") will be described. The resin (A) usually contains a group whose polarity increases when it is decomposed by the action of an acid (also called "acid decomposable group"), and preferably contains a repeating unit having an acid decomposable group. In the case where the resin (A) has an acid-decomposable group, in the pattern forming method of this specification, typically, when an alkaline developer is used as the developer, it is suitable for forming a positive pattern, and an organic developer is used as the developer. When liquid, it is suitable for negative pattern formation. As the repeating unit having an acid-decomposable group, in addition to the repeating unit having an acid-decomposable group described later, a repeating unit having an acid-decomposable group including an unsaturated bond is also preferable.

(repeating units with acid decomposable groups) The term "acid decomposable group" refers to a group whose polarity is increased by decomposition by the action of an acid. The acid-decomposable group preferably has a structure in which a polar group is protected by a group detached by the action of an acid (leaving group). That is, the resin (A) has a repeating unit having a group that is decomposed by the action of an acid to generate a polar group. The resin with this repeating unit has increased polarity due to the action of acid, so the solubility to alkaline developer solution increases, and the solubility to organic solvent decreases. As the polar group, preferably an alkali-soluble group, for example: carboxyl group, phenolic hydroxyl group, fluorinated alcohol group, sulfonic acid group, phosphoric acid group, sulfonamide group, sulfonimide group, (alkyl Sulfonyl)(alkylcarbonyl)methylidene, (alkylsulfonyl)(alkylcarbonyl)imidene, bis(alkylcarbonyl)methylidene, bis(alkylcarbonyl)imidene , bis(alkylsulfonyl)methylidene, bis(alkylsulfonyl)amidoidene, tri(alkylcarbonyl)methylidene and tri(alkylsulfonyl)methidemide and other acidic groups; and alcoholic hydroxyl groups. Among them, the polar group is preferably a carboxyl group, a phenolic hydroxyl group, a fluorinated alcohol group (preferably a hexafluoroisopropanol group), or a sulfonic acid group.

Examples of groups detached by the action of an acid include groups represented by formulas (Y1) to (Y4). Formula (Y1): -C(Rx ₁ )(Rx ₂ )(Rx ₃ ) Formula (Y2): -C(=O)OC(Rx ₁ )(Rx ₂ )(Rx ₃ ) Formula (Y3): -C (R ₃₆ ) (R ₃₇ ) (OR ₃₈ ) Formula (Y4): -C(Rn)(H)(Ar)

In formula (Y1) and formula (Y2), Rx ₁ to Rx ₃ independently represent an alkyl group (linear or branched), cycloalkyl (monocyclic or polycyclic), alkenyl (linear or branched) or aryl (monocyclic or polycyclic). Furthermore, when all of Rx ₁ to Rx ₃ are alkyl groups (linear or branched), at least two of Rx ₁ to Rx ₃ are preferably methyl groups. Among them, it is preferable that Rx ₁ to Rx ₃ each independently represent a linear or branched alkyl group, and it is more preferable that Rx ₁ to Rx ₃ each independently represent a linear alkyl group. Two of Rx ₁ to Rx ₃ may be bonded to form a monocyclic ring or a polycyclic ring. The alkyl group of Rx ₁ to Rx ₃ is preferably an alkyl group having 1 to 5 carbon atoms such as methyl group, ethyl group, n-propyl group, isopropyl group, n-butyl group, isobutyl group and tert-butyl group. As the cycloalkyl group of Rx ₁ to Rx ₃ , monocyclic cycloalkyl groups such as cyclopentyl and cyclohexyl, and polycyclic groups such as norbornyl, tetracyclodecanyl, tetracyclododecyl, and adamantyl are preferable. Cycloalkyl rings. The aryl group of Rx ₁ to Rx ₃ is preferably an aryl group having 6 to 10 carbon atoms, and examples thereof include phenyl, naphthyl and anthracenyl. The alkenyl group for Rx ₁ to Rx ₃ is preferably a vinyl group. A ring formed as two bonds among Rx ₁ to Rx ₃ is preferably a cycloalkyl group. The cycloalkyl group formed as two bonds among Rx ₁ to Rx ₃ is preferably a monocyclic cycloalkyl group such as cyclopentyl group or cyclohexyl group, or norbornyl group, tetracyclodecanyl group, tetracyclododecyl group, etc. A polycyclic cycloalkyl group such as an alkyl group or an adamantyl group is more preferably a monocyclic cycloalkyl group having 5 to 6 carbon atoms. For a cycloalkyl group formed by bonding two of Rx ₁ to Rx ₃ , one of the methylene groups constituting the ring may be replaced by a heteroatom such as an oxygen atom, a group containing a heteroatom such as a carbonyl group, or a vinylene group. replace. In these cycloalkyl groups, one or more ethylidene groups constituting the cycloalkane ring may be substituted with vinylene groups. The group represented by formula (Y1) or formula (Y2) is preferably such that, for example, Rx ₁ is a methyl group or an ethyl group, and Rx ₂ and Rx ₃ are bonded to form the aforementioned cycloalkyl group. When the actinic radiation-sensitive or radiation-sensitive resin composition is, for example, a photoresist composition for EUV exposure, the alkyl group, cycloalkyl group, alkenyl group, aryl group represented by Rx ₁ to Rx ₃ and Rx ₁ to Rx The ring formed by bonding two of ₃ also preferably has a fluorine atom or an iodine atom as a substituent.

In formula (Y3), R ₃₆ to R ₃₈ each independently represent a hydrogen atom or a monovalent organic group. R ₃₇ and R ₃₈ may be bonded to each other to form a ring. As a monovalent organic group, an alkyl group, a cycloalkyl group, an aryl group, an aralkyl group, and an alkenyl group are mentioned. R ₃₆ is also preferably a hydrogen atom. Furthermore, heteroatoms such as an oxygen atom and/or groups containing heteroatoms such as a carbonyl group may be contained in the above-mentioned alkyl group, cycloalkyl group, aryl group, and aralkyl group. For example, among the aforementioned alkyl groups, cycloalkyl groups, aryl groups, and aralkyl groups, one or more methylene groups may be substituted with heteroatoms such as oxygen atoms and/or heteroatom-containing groups such as carbonyl groups. R ₃₈ may be bonded to another substituent of the main chain of the repeating unit to form a ring. The group formed by bonding R ₃₈ and another substituent in the main chain of the repeating unit is preferably an alkylene group such as a methylene group. When the actinic radiation-sensitive or radiation-sensitive resin composition is, for example, a photoresist composition for EUV exposure, a monovalent organic group represented by R ₃₆ to R ₃₈ and R ₃₇ and R ₃₈ are bonded to each other. It is also preferable that the ring further has a fluorine atom or an iodine atom as a substituent.

As formula (Y3), a group represented by the following formula (Y3-1) is preferable.

[chemical formula 43]

Wherein, L ₁ and L ₂ each independently represent a hydrogen atom, an alkyl group, a cycloalkyl group, an aryl group, or a combination thereof (for example, a combination of an alkyl group and an aryl group). M represents a single bond or a divalent linking group. Q represents an alkyl group that may contain heteroatoms, a cycloalkyl group that may contain heteroatoms, an aryl group that may contain heteroatoms, an amino group, an ammonium group, a mercapto group, a cyano group, an aldehyde group, or a combination of these groups (for example, groups formed by combining alkyl and cycloalkyl). In an alkyl group and a cycloalkyl group, for example, one of the methylene groups may be substituted with a heteroatom such as an oxygen atom or a group containing a heteroatom such as a carbonyl group. Furthermore, it is preferable that one of L ₁ and L ₂ is a hydrogen atom, and the other is an alkyl group, a cycloalkyl group, an aryl group, or a combination of an alkylene group and an aryl group. At least two _of Q, M and L may be bonded to form a ring (preferably a 5-membered or 6-membered ring). In terms of pattern miniaturization, L ₂ is preferably a secondary or tertiary alkyl group, more preferably a tertiary alkyl group. Examples of the secondary alkyl group include isopropyl group, cyclohexyl group, and norbornyl group, and examples of the tertiary alkyl group include t-butyl group and adamantyl group. In these aspects, Tg (glass transition temperature) and activation energy become high, so not only film strength is ensured, but also fogging can be suppressed.

When the actinic radiation-sensitive or radiation-sensitive resin composition is, for example, a photoresist composition for EUV exposure, the alkyl group, cycloalkyl group, aryl group represented by _L1 and _L2 and combinations thereof It is also preferable that the group further has a fluorine atom or an iodine atom as a substituent. It is also preferable that the above-mentioned alkyl group, cycloalkyl group, aryl group and aralkyl group contain heteroatoms such as oxygen atoms in addition to fluorine atoms and iodine atoms. Specifically, among the above-mentioned alkyl groups, cycloalkyl groups, aryl groups, and aralkyl groups, for example, one methylene group may be substituted by a heteroatom such as an oxygen atom, or a group containing a heteroatom such as a carbonyl group. When the actinic radiation-sensitive or radiation-sensitive resin composition is, for example, a photoresist composition for EUV exposure, Q represents an alkyl group that may contain a heteroatom, a cycloalkyl group that may contain a heteroatom, a cycloalkyl group that may contain a heteroatom In the aryl group, amino group, ammonium group, mercapto group, cyano group, aldehyde group and the group formed by combining them, the heteroatom is preferably a heteroatom selected from fluorine atom, iodine atom and oxygen atom .

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

From the viewpoint of excellent acid decomposability of the repeating unit, it is also preferable that, in the leaving group protecting the polar group, when the non-aromatic ring is directly bonded to the polar group (or its residue), the above-mentioned non-aromatic The ring member atom adjacent to the ring member atom directly bonded to the polar group (or its residue) in the ring does not have a halogen atom such as a fluorine atom as a substituent.

In addition, the group released by the action of acid can also be 2-cyclopentenyl with substituents (alkyl, etc.) like 3-methyl-2-cyclopentenyl and 1,1 , 4,4-Tetramethylcyclohexyl-like cyclohexyl with substituents (alkyl, etc.).

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

[chemical formula 44]

L ₁ represents a divalent linking group that may have a fluorine atom or an iodine atom, and R ₁ represents a hydrogen atom, a fluorine atom, an iodine atom, an alkyl group that may have a fluorine atom or an iodine atom, or an aromatic group that may have a fluorine atom or an iodine atom. _R2 represents a leaving group that is released by the action of an acid and may have a fluorine atom or an iodine atom. However, at least one of L ₁ , R ₁ and R ₂ has a fluorine atom or an iodine atom. Examples of divalent linking groups that may have a fluorine atom or an iodine atom represented by L ₁ include -CO-, -O-, -S-, -SO-, -SO ₂ -, and may have a fluorine atom or iodine atom. Atomic hydrocarbon groups (such as alkylene, cycloalkylene, alkenylene and arylylene, etc.) and a linking group formed by linking a plurality of these. Among them, as L ₁ , preferably -CO-, arylylene, or -arylylene-fluorine atom or iodine atom-containing alkene-, more preferably -CO-, or -arylylene-fluorine atom Or an alkylene group- having an iodine atom. The arylylene group is preferably a phenylene group. The alkylene group may be linear or branched. The carbon number of the alkylene group is not particularly limited, but is preferably 1-10, more preferably 1-3. The total number of fluorine atoms and iodine atoms contained in the alkylene group having a fluorine atom or an iodine atom is not particularly limited, but is preferably 2 or more, more preferably 2-10, and still more preferably 3-6.

The alkyl group represented by R ₁ may be linear or branched. The carbon number of the alkyl group is not particularly limited, but is preferably 1-10, more preferably 1-3. The total number of fluorine atoms and iodine atoms contained in the alkyl group having a fluorine atom or an iodine atom represented by _R1 is not particularly limited, but is preferably 1 or more, more preferably 1 to 5, and still more preferably 1 ~3. The alkyl group represented by R ₁ may contain heteroatoms such as oxygen atoms other than halogen atoms.

Examples of the leaving group represented by R ₂ that may have a fluorine atom or an iodine atom include leaving groups represented by the above formulas (Y1) to (Y4) that have a fluorine atom or an iodine atom.

As the repeating unit having an acid-decomposable group, a repeating unit represented by formula (AI) is also preferable.

[chemical formula 45]

In formula (AI), Xa ₁ represents a hydrogen atom or an optionally substituted alkyl group. T represents a single bond or a divalent linking group. Rx ₁ to Rx ₃ independently represent alkyl (straight-chain or branched), cycloalkyl (monocyclic or polycyclic), alkenyl (straight-chain or branched) or aryl (monocyclic or polycyclic). Among them, when all of Rx ₁ to Rx ₃ are alkyl groups (linear or branched), at least two of Rx ₁ to Rx ₃ are preferably methyl groups. Two of Rx ₁ to Rx ₃ may be bonded to form a monocyclic or polycyclic ring (monocyclic or polycyclic cycloalkyl group, etc.).

Examples of the optionally substituted alkyl group represented by Xa ₁ include a methyl group or a group represented by —CH ₂ —R ₁₁ . R ₁₁ represents a halogen atom (fluorine atom, etc.), a hydroxyl group or a monovalent organic group. Examples of the _monovalent organic group represented by R include an alkyl group having 5 or less carbon atoms which may be substituted by a halogen atom, an acyl group having 5 or less carbon atoms which may be substituted by a halogen atom, and an acyl group which may be substituted by a halogen atom. The alkoxy group having 5 or less carbon atoms is preferably an alkyl group having 3 or less carbon atoms, more preferably a methyl group. Xa ₁ is preferably a hydrogen atom, a methyl group, a trifluoromethyl group or a hydroxymethyl group.

Examples of the divalent linking group of T include an alkylene group, an aromatic ring group, a -COO-Rt- group, and a -O-Rt- group. In the formula, Rt represents an alkylene or cycloalkylene group. T is preferably a single bond or a -COO-Rt- group. When T represents a -COO-Rt- group, Rt is preferably an alkylene group with 1 to 5 carbons, more preferably a -CH ₂ - group, -(CH ₂ ) ₂ - group or -(CH ₂ ) ₃ -base.

The alkyl group for Rx ₁ to Rx ₃ is preferably an alkyl group having 1 to 4 carbon atoms such as methyl group, ethyl group, n-propyl group, isopropyl group, n-butyl group, isobutyl group and tert-butyl group. The cycloalkyl group of Rx ₁ to Rx ₃ is preferably a monocyclic cycloalkyl group such as cyclopentyl or cyclohexyl, or a polycyclic group such as norbornyl, tetracyclodecanyl, tetracyclododecyl, or adamantyl. Cycloalkyl rings. The aryl group of Rx ₁ to Rx ₃ is preferably an aryl group having 6 to 10 carbon atoms, and examples thereof include phenyl, naphthyl and anthracenyl. The alkenyl group for Rx ₁ to Rx ₃ is preferably a vinyl group. As the cycloalkyl group formed by bonding two of Rx ₁ to Rx ₃ , monocyclic cycloalkyl groups such as cyclopentyl and cyclohexyl are preferable. Also, polycyclic cycloalkyl groups such as norbornyl, tetracyclodecanyl, tetracyclododecyl, and adamantyl are also preferred. Among them, a monocyclic cycloalkyl group having 5 to 6 carbon atoms is preferred. Among the cycloalkyl groups formed by bonding two of Rx ₁ to Rx ₃ , for example, one of the methylene groups constituting the ring may be replaced by a heteroatom such as an oxygen atom, a group containing a heteroatom such as a carbonyl group, or a vinylene group. replace. In addition, in these cycloalkyl groups, one or more ethylidene groups constituting the cycloalkane ring may be substituted with vinylene groups. The repeating unit represented by formula (AI) is preferably such that, for example, Rx ₁ is a methyl group or an ethyl group, and Rx ₂ and Rx ₃ are bonded to form the aforementioned cycloalkyl group.

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

The repeating unit represented by the formula (AI) is preferably an acid-decomposable tertiary alkyl (meth)acrylate repeating unit (a repeating unit in which Xa ₁ represents a hydrogen atom or a methyl group and T represents a single bond).

Specific examples of the repeating unit having an acid-decomposable group are shown below, but are not limited thereto. In addition, in the formula, Xa ₁ represents H, CH ₃ , CF ₃ or CH ₂ OH, and Rxa and Rxb each independently represent a linear or branched alkyl group having 1 to 5 carbon atoms.

[chemical formula 46]

[chemical formula 47]

[chemical formula 48]

[chemical formula 49]

[chemical formula 50]

The resin (A) may have a repeating unit having an acid-decomposable group including an unsaturated bond as the repeating unit having an acid-decomposable group. The repeating unit having an acid-decomposable group containing an unsaturated bond is preferably a repeating unit represented by formula (B).

[chemical formula 51]

In formula (B), Xb represents a hydrogen atom, a halogen atom, or an alkyl group which may have a substituent. L represents a single bond or a divalent linking group which may have a substituent. Ry ₁ to Ry ₃ each independently represent a linear or branched alkyl group, a monocyclic or polycyclic cycloalkyl group, an alkenyl group, an alkynyl group, or a monocyclic or polycyclic aryl group. Among them, at least one of Ry ₁ to Ry ₃ represents an alkenyl group, an alkynyl group, a monocyclic or polycyclic cycloalkenyl group, or a monocyclic or polycyclic aryl group. Two of Ry ₁ to Ry ₃ may be bonded to form a monocyclic or polycyclic ring (monocyclic or polycyclic cycloalkyl group, cycloalkenyl group, etc.).

Examples of the optionally substituted alkyl group represented by Xb include a methyl group or a group represented by -CH ₂ -R ₁₁ . _R11 represents a halogen atom (fluorine atom, etc.), a hydroxyl group, or a monovalent organic group, for example, an alkyl group having 5 or less carbon atoms that may be substituted by a halogen atom, and an acyl group having 5 or less carbon atoms that may be substituted by a halogen atom and an alkoxy group having 5 or less carbon atoms which may be substituted by a halogen atom, preferably an alkyl group having 3 or less carbon atoms, more preferably a methyl group. Xb is preferably a hydrogen atom, a fluorine atom, a methyl group, a trifluoromethyl group or a hydroxymethyl group.

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

The alkyl group of Ry ₁ to Ry ₃ is preferably an alkyl group having 1 to 4 carbon atoms such as methyl group, ethyl group, n-propyl group, isopropyl group, n-butyl group, isobutyl group and tert-butyl group. The cycloalkyl group of Ry ₁ to Ry ₃ is preferably a monocyclic cycloalkyl group such as cyclopentyl and cyclohexyl, or a polycyclic group such as norbornyl, tetracyclodecanyl, tetracyclododecyl, or adamantyl. Cycloalkyl rings. The aryl group of Ry ₁ to Ry ₃ is preferably an aryl group having 6 to 10 carbon atoms, and examples thereof include phenyl, naphthyl and anthracenyl. The alkenyl group for Ry ₁ to Ry ₃ is preferably vinyl. The alkynyl group for Ry ₁ to Ry ₃ is preferably an ethynyl group. The cycloalkenyl group of Ry ₁ to Ry ₃ preferably has a structure including a double bond in a part of a monocyclic cycloalkyl group such as cyclopentyl and cyclohexyl. The cycloalkyl group formed by two bonds among Ry ₁ to Ry ₃ is preferably a monocyclic cycloalkyl group such as cyclopentyl and cyclohexyl, or norbornyl, tetracyclodecanyl, tetracyclododecyl, etc. Polycyclic cycloalkyl groups such as alkyl groups and adamantyl groups. Among them, a monocyclic cycloalkyl group having 5 to 6 carbon atoms is more preferable. Among the cycloalkyl or cycloalkenyl groups formed by bonding two of Ry ₁ to Ry ₃ , for example, one of the methylene groups constituting the ring may be replaced by a heteroatom such as an oxygen atom, a carbonyl group, a -SO ₂ ^- group, and a - It is substituted by a heteroatom-containing group such as an SO ₃ ^- group, a vinylene group, or a combination thereof. In addition, in these cycloalkyl groups or cycloalkenyl groups, one or more ethylidene groups constituting the cycloalkane ring or cycloalkene ring may be substituted with vinylene groups. The repeating unit represented by formula (B) is preferably, for example, Ry ₁ is methyl, ethyl, vinyl, allyl or aryl, and Ry ₂ and Ry ₃ are bonded to form the above-mentioned cycloalkyl or cycloalkene base form.

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

As the repeating unit represented by formula (B), acid-decomposable (meth)acrylate tertiary ester repeating units (Xb represents a hydrogen atom or a methyl group, and L represents a -CO- group repeating unit), acid Decomposable hydroxystyrene tertiary alkyl ether repeating unit (Xb represents a hydrogen atom or a methyl group, and L represents a phenyl repeating unit), acid decomposable styrene carboxylic acid tertiary ester repeating unit (Xb represents a hydrogen atom Or methyl, and L represents the repeating unit of -Rt-CO- group (Rt is an aromatic group).

The content of the repeating unit having an acid-decomposable group containing an unsaturated bond is preferably at least 15 mol %, more preferably at least 20 mol %, and still more preferably 30 mol %, relative to all the repeating units in the resin (A). More than mole%. Also, the upper limit is preferably 80 mol% or less, more preferably 70 mol% or less, and further preferably 60 mol% or less with respect to all repeating units in the resin (A).

Specific examples of the repeating unit having an acid-decomposable group containing an unsaturated bond are shown below, but are not limited thereto. Furthermore, in the formula, Xb and _L1 represent any one of the above-mentioned substituents and linking groups, Ar represents an aromatic group, R represents a hydrogen atom, an alkyl group, a cycloalkyl group, an aryl group, an aralkyl group, Alkenyl, hydroxyl, alkoxy, acyloxy, cyano, nitro, amino, halogen atom, ester (-OCOR''' or -COOR''', R''' is 1 to 20 carbons Alkyl or fluorinated alkyl) or carboxyl and other substituents, R'represents linear or branched alkyl, monocyclic or polycyclic cycloalkyl, alkenyl, alkynyl, or monocyclic Or a polycyclic aryl group, Q represents a heteroatom such as an oxygen atom, a carbonyl group, a group containing a heteroatom such as a -SO ₂ -base and a -SO ₃ -base, a vinylene group, or a combination thereof, n, m and l represents an integer of 0 or more.

[chemical formula 52]

[chemical formula 53]

[chemical formula 54]

[chemical formula 55]

The content of the repeating unit having an acid-decomposable group is preferably at least 15 mol%, more preferably at least 20 mol%, and further preferably at least 30 mol%, based on all repeating units in the resin (A). Also, the upper limit thereof is preferably at most 90 mol%, more preferably at most 80 mol%, further preferably at most 70 mol%, with respect to all repeating units in the resin (A), particularly preferably It is less than 60 mole%.

The resin (A) may contain at least one repeating unit selected from the group consisting of the following A group, and/or at least one repeating unit selected from the following group consisting of the B group. Group A: a group consisting of the following repeating units (20) to (25). (20) The following repeating units having an acid group (21) A repeating unit having a fluorine atom, a bromine atom or an iodine atom, which does not have any of an acid decomposable group or an acid group, as described below (22) The following repeating unit having a lactone group, sultone group or carbonate group (23) The repeating unit having a photoacid generating group described later (24) A repeating unit represented by formula (V-1) or the following formula (V-2) described later (25) Repeating unit for reducing the mobility of the main chain In addition, the repeating units represented by the formulas (A) to (E) described later correspond to (25) the repeating unit for reducing the mobility of the main chain. Group B: a group consisting of the following repeating units (30) to (32). (30) The following repeating unit having at least one group selected from a lactone group, a sultone group, a carbonate group, a hydroxyl group, a cyano group, and an alkali-soluble group (31) Repeating units described later that have an alicyclic hydrocarbon structure and do not exhibit acid decomposability (32) A repeating unit represented by formula (III) described below that does not have any of a hydroxyl group and a cyano group

The resin (A) preferably has an acid group, and preferably contains a repeating unit having an acid group as will be described later. In addition, the definition of an acidic group will be described later together with a preferred aspect of the repeating unit having an acidic group. When the resin (A) has an acid group, the interaction between the resin (A) and the acid generated by the photoacid generator is more excellent. As a result, the diffusion of acid can be further suppressed, so that the cross-sectional shape of the formed pattern becomes closer to a rectangle.

The resin (A) may have at least one repeating unit selected from the group consisting of the above-mentioned group A. In the case where the actinic radiation-sensitive or radiation-sensitive resin composition is used as the actinic radiation-sensitive or radiation-sensitive resin composition for EUV exposure, the resin (A) preferably has a At least one repeating unit in the group. The resin (A) may contain at least one of fluorine atoms and iodine atoms. In the case where the actinic radiation-sensitive or radiation-sensitive resin composition is used as the actinic radiation-sensitive or radiation-sensitive resin composition for EUV exposure, the resin (A) preferably contains at least one of a fluorine atom and an iodine atom. By. In the case where the resin (A) contains both fluorine atoms and iodine atoms, the resin (A) may have one repeating unit containing both fluorine atoms and iodine atoms, and the resin (A) may also contain repeating units having fluorine atoms and Repeating units with iodine atoms These two repeating units. The resin (A) may have a repeating unit having an aromatic group. When the actinic radiation-sensitive or radiation-sensitive resin composition is used as the actinic radiation-sensitive or radiation-sensitive resin composition for EUV exposure, it is also preferable that the resin (A) has a repeating unit having an aromatic group. The resin (A) may have at least one repeating unit selected from the group consisting of the aforementioned group B. In the case where the actinic radiation-sensitive or radiation-sensitive resin composition is used as the actinic radiation-sensitive or radiation-sensitive resin composition for ArF, the resin (A) preferably has a At least one repeating unit in the group. Furthermore, when the actinic radiation-sensitive or radiation-sensitive resin composition is used as the actinic radiation-sensitive or radiation-sensitive resin composition for ArF, the resin (A) preferably does not contain fluorine atoms and silicon atoms. any of the When the actinic radiation-sensitive or radiation-sensitive resin composition is used as the actinic radiation-sensitive or radiation-sensitive resin composition for ArF, the resin (A) preferably does not have an aromatic group.

(Repeating Unit Having Acid Group) The resin (A) may contain a repeating unit having an acid group. As the acid group, an acid group having a pKa of 13 or less is preferable. The acid dissociation constant of the above acid group is preferably 13 or less, more preferably 3-13, further 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 not particularly limited, but is often 0.2 to 6.0 mmol/g. Among them, 0.8-6.0 mmol/g is preferable, 1.2-5.0 mmol/g is more preferable, and 1.6-4.0 mmol/g is still more preferable. If the content of the acid group is within the above range, image development will proceed favorably, the pattern shape to be formed will be excellent, and the resolution will also be excellent. As the acid group, for example, a carboxyl group, a phenolic hydroxyl group, a fluorinated alcohol group (preferably a hexafluoroisopropanol group), a sulfonic acid group, a sulfonamide group or an isopropanol group is preferred. In the above hexafluoroisopropanol group, one or more (preferably 1 to 2) fluorine atoms may be substituted with groups other than fluorine atoms (alkoxycarbonyl group, etc.). The acid group is also preferably -C(CF ₃ )(OH)-CF ₂ - thus formed. 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 is preferably the same as the above-mentioned repeating unit having a structure in which a polar group is protected by a group released by the action of an acid, and the repeating unit having a lactone group, a sultone group or a carbonate group described later. The repeating units of different repeating units. The repeating unit having an acid group may have a fluorine atom or an iodine atom.

The following repeating units are mentioned as a repeating unit which has an acid group.

[chemical formula 56]

As the repeating unit having an acid group, a repeating unit represented by the following formula (1) is preferable.

[chemical formula 57]

In formula (1), A represents a hydrogen atom, an alkyl group, a cycloalkyl group, a halogen atom or a cyano group. R represents a halogen atom, an alkyl group, a cycloalkyl group, an aryl group, an alkenyl group, an aralkyl group, an alkoxy group, an alkylcarbonyloxy group, an alkylsulfonyloxy group, an alkoxycarbonyl group or an aryloxycarbonyl group, and there are plural They can be the same or different from each other. When there are plural Rs, they may jointly form a ring. R is preferably a hydrogen atom. a represents an integer of 1-3. b represents an integer of 0 to (5-a).

Hereinafter, the repeating unit which has an acidic group is illustrated. In the formula, a represents 1 or 2.

[chemical formula 58]

[chemical formula 59]

[chemical formula 60]

[chemical formula 61]

In addition, among the above-mentioned repeating units, the repeating units specifically described below are preferable. In the formula, R represents a hydrogen atom or a methyl group, and a represents 2 or 3.

[chemical formula 62]

[chemical formula 63]

The content of the repeating unit having an acid group is preferably at least 10 mol %, more preferably at least 15 mol %, based on all the repeating units in the resin (A). Also, the upper limit is preferably 70 mol% or less, more preferably 65 mol% or less, and further preferably 60 mol% or less with respect to all repeating units in the resin (A).

(A repeating unit having a fluorine atom, a bromine atom, or an iodine atom that does not have any of an acid decomposable group or an acid group) The resin (A) may have a repeating unit different from the aforementioned <repeating unit having an acid decomposable group> and <repeating unit having an acid group>, and the repeating unit does not have any of an acid decomposable group or an acid group. Or a repeating unit having a fluorine atom, a bromine atom or an iodine atom (hereinafter also referred to as unit X.). The <repeating unit having no acid decomposable group or acid group but having a fluorine atom, bromine atom or iodine atom> mentioned here is preferably the same as <having a lactone group, a sultone group or Carbonate group repeating unit> and <repeating unit having a photoacid generating group> are different from other types of repeating units belonging to group A.

As the unit X, a repeating unit represented by formula (C) is preferable.

[chemical formula 64]

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

Repeating units having a fluorine atom or an iodine atom are exemplified below.

[chemical formula 65]

The content of the unit X is preferably at least 0 mol%, more preferably at least 5 mol%, and further preferably at least 10 mol%, based on all repeating units in the resin (A). Also, the upper limit is preferably 50 mol% or less, more preferably 45 mol% or less, and further preferably 40 mol% or less with respect to all repeating units in the resin (A).

Among the repeating units of the resin (A), the total content of repeating units containing at least one of fluorine atoms, bromine atoms, and iodine atoms is preferably 10 mol% or more, relative to all the repeating units of the resin (A), More preferably, it is at least 20 mol%, further preferably at least 30 mol%, and most preferably at least 40 mol%. The upper limit is not particularly limited, and is, for example, 100 mol% or less based on all repeating units of the resin (A). Furthermore, as the repeating unit containing at least one of a fluorine atom, a bromine atom, and an iodine atom, for example: a repeating unit having a fluorine atom, a bromine atom, or an iodine atom and having an acid-decomposable group; A repeating unit having a bromine atom or an iodine atom and having an acid group, and a repeating unit having a fluorine atom, a bromine atom or an iodine atom.

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

As a lactone group or a sultone group, what is necessary is just to have a lactone structure or a sultone structure. The lactone structure or the sultone structure is preferably a 5-7 membered cyclic lactone structure or a 5-7 membered cyclic sultone structure. Among them, a structure formed by condensing a 5- to 7-membered cyclic lactone structure and other ring structures in the form of a bicyclic structure or a spiro ring structure, or a structure formed by forming a 5- to 7-membered cyclic sultone structure and other ring structures A structure formed by condensing rings in the form of a bicyclic structure or a spiro ring structure. The resin (A) preferably has a repeating unit having a lactone structure represented by any one of the following formulas (LC1-1) to (LC1-21) or the following formula (SL1-1 )～(SL1-3) The lactone group or sultone group formed by removing one or more hydrogen atoms from the ring member atom of the sultone structure represented by any one of (SL1-3), lactone group or sultone group Can be directly bonded to the main chain. For example, a ring member atom of a lactone group or a sultone group may constitute the main chain of the resin (A).

[chemical formula 66]

The aforementioned lactone structure or sultone structure may have a substituent (Rb ₂ ). Preferred substituents (Rb ₂ ) include alkyl groups having 1 to 8 carbons, cycloalkyl groups having 4 to 7 carbons, alkoxy groups having 1 to 8 carbons, and alkyl groups having 1 to 8 carbons. Oxycarbonyl group, carboxyl group, halogen atom, cyano group and acid decomposable group. n2 represents an integer of 0-4. When n2 is 2 or more, the plurality of Rb ₂ existing may be different, or the plurality of Rb ₂ existing may be bonded to each other to form a ring.

As a sultone having a lactone structure represented by any of formulas (LC1-1) to (LC1-21) or represented by any of formulas (SL1-1) to (SL1-3) The repeating unit of the structural group includes, for example, a repeating unit represented by the following formula (AI).

[chemical formula 67]

In formula (AI), Rb ₀ represents a hydrogen atom, a halogen atom, or an alkyl group having 1 to 4 carbon atoms. A hydroxyl group and a halogen atom are mentioned as a preferable substituent which the alkyl group of _Rb0 may have. Examples of the halogen atom of Rb ₀ include a fluorine atom, a chlorine atom, a bromine atom, and an iodine atom. 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, an ester group, a carbonyl group, a carboxyl group, or a divalent link combining these base. Among them, Ab is preferably a single bond or a linking group represented by -Ab ₁ -CO ₂ -. Ab ₁ is a linear or branched alkylene group, or a monocyclic or polycyclic cycloalkylene group, preferably methylene, ethylidene, cyclohexylene, adamantyl or norbornene base. V represents a group obtained by removing one hydrogen atom from the ring member atom of the lactone structure represented by any one of the formulas (LC1-1) to (LC1-21), or a group obtained from the formulas (SL1-1) to A group obtained by removing one hydrogen atom from a ring member atom of the sultone structure represented by any of (SL1-3).

When an optical isomer exists in the repeating unit having a lactone group or a sultone group, any optical isomer can be used. Also, one optical isomer may be used alone, or a plurality of optical isomers may be used in combination. When mainly using one type of optical isomer, the optical purity (ee) thereof is preferably 90 or higher, more preferably 95 or higher.

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

[chemical formula 68]

In the 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, the plurality of R _A ² that exist may be the same or different. A represents a single bond or a divalent linking group. As the above-mentioned divalent linking group, preferably an alkylene group, a divalent linking group having a monocyclic or polycyclic alicyclic hydrocarbon structure, an ether group, an ester group, a carbonyl group, a carboxyl group, or a combination thereof A divalent linking group. Z represents an atomic group forming a monocyclic or polycyclic ring together with a group represented by -O-CO-O- in the formula.

Unit Y is exemplified below. In the formula, Rx represents a hydrogen atom, -CH ₃ , -CH ₂ OH or -CF ₃ .

[chemical formula 69]

[chemical formula 70]

The content of the unit Y is preferably at least 1 mol %, more preferably at least 10 mol %, based on all the repeating units in the resin (A). Also, the upper limit is preferably at most 85 mol %, more preferably at most 80 mol %, further preferably at most 70 mol %, particularly preferably at most, relative to all repeating units in the resin (A). It is less than 60 mole%.

(repeating units with photoacid generating groups) As a repeating unit other than the above, the resin (A) may have a repeating unit having a group (also referred to as a “photoacid generating group”) that generates an acid upon irradiation with actinic rays or radiation. The repeating unit represented by formula (4) is mentioned as a repeating unit which has a photoacid generating group.

[chemical formula 71]

R ⁴¹ represents a hydrogen atom or a methyl group. L ⁴¹ represents a single bond or a divalent linking group. L ⁴² represents a divalent linking group. R ⁴⁰ represents a structural site in which an acid is generated in a side chain when decomposed by irradiation with actinic rays or radiation. Repeating units having a photoacid generating group are exemplified below.

[chemical formula 72]

In addition, examples of the repeating unit represented by formula (4) include repeating units described in paragraphs [0094] to [0105] of JP-A-2014-041327 and paragraphs of WO2018/193954A The repeating unit described in [0094].

The content of the repeating unit having a photoacid generating group is preferably at least 1 mol %, more preferably at least 5 mol %, relative to all the repeating units in the resin (A). Also, the upper limit thereof is preferably at most 40 mol%, more preferably at most 35 mol%, and further preferably at most 30 mol%, based on all repeating units in the resin (A).

(repeating unit represented by formula (V-1) or the following formula (V-2)) The resin (A) may have a repeating unit represented by the following formula (V-1) or the following formula (V-2). The repeating unit represented by the following formula (V-1) and the following formula (V-2) is preferably a repeating unit different from the above-mentioned repeating unit.

[chemical formula 73]

In the formula, R ₆ and R ₇ independently represent a hydrogen atom, hydroxyl, alkyl, alkoxy, acyloxy, cyano, nitro, amine, halogen atom, ester group (-OCOR or -COOR: R C1-6 alkyl or fluorinated alkyl) or carboxyl. The alkyl group is preferably a linear, branched or cyclic alkyl group having 1 to 10 carbon atoms. n ₃ represents an integer of 0-6. n ₄ represents an integer of 0-4. X ₄ is a methylene group, an oxygen atom or a sulfur atom. The repeating unit represented by formula (V-1) or (V-2) is exemplified below. Examples of the repeating unit represented by formula (V-1) or (V-2) include those described in paragraph [0100] of International Publication No. 2018/193954.

(repeating unit used to make the main chain less mobile) The resin (A) preferably has a high glass transition temperature (Tg) from the viewpoint of being able to suppress excessive diffusion of generated acid or pattern collapse during image development. Tg is preferably greater than 90°C, more preferably greater than 100°C, further preferably greater than 110°C, particularly preferably greater than 125°C. Furthermore, Tg is preferably 400° C. or less, more preferably 350° C. or less, from the viewpoint of excellent dissolution rate in a developer. In addition, in this specification, the glass transition temperature (Tg) (henceforth "Tg of a repeating unit") of polymers, such as resin (A), is calculated by the following method. First, the Tgs of the homopolymers consisting only of each repeating unit contained in the polymer were respectively calculated by the Bicerano method. Next, the mass ratio (%) of each repeating unit to all repeating units in the polymer is calculated. Next, Tg at each mass ratio was calculated using Fox's 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). Calculation of Tg by the Bicerano method can be performed using polymer property estimation software MDL Polymer (MDL Information Systems, Inc.).

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). The methods of reducing the mobility of the main chain of the resin (A) include the following methods (a) to (e). (a) introducing bulky substituents into the main chain; (b) introducing multiple substituents into the main chain; (c) introducing substituents that induce interactions between resins (A) near the main chain; ( d) forming the main chain in the ring structure; (e) linking the ring structures on the main chain. Furthermore, the resin (A) preferably has a repeating unit whose homopolymer Tg shows 130° C. or higher. Furthermore, the type of repeating unit whose Tg of the homopolymer is 130° C. or higher is not particularly limited, as long as it is a repeating unit whose Tg of the homopolymer calculated by the Bicerano method is 130° C. or higher. In addition, depending on the type of functional group in the repeating unit represented by the formula (A) to formula (E) described later, the repeating unit whose Tg corresponds to a homopolymer shows 130° C. or higher.

As an example of specific means for realizing the above (a), a method of introducing a repeating unit represented by the formula (A) into the resin (A) is mentioned.

[chemical formula 74]

Formula (A), R _A represents a group containing a polycyclic structure. R _x represents a hydrogen atom, a methyl group or an ethyl group. The group containing a polycyclic structure refers to a group containing a plurality of ring structures, and the plurality of ring structures may or may not be condensed. Specific examples of the repeating unit represented by the formula (A) include repeating units described in paragraphs [0107] to [0119] of International Publication No. 2018/193954.

An example of a specific means for realizing the above (b) includes a method of introducing a repeating unit represented by the formula (B) into the resin (A).

[chemical formula 75]

In formula (B), R _b1 to R _b4 each independently represent a hydrogen atom or an organic group, and at least two or more of R _b1 to R _b4 represent an organic group. In the case where at least one organic group is a group directly linked to a ring structure on the main chain in the repeating unit, the type of other organic groups is not particularly limited. In addition, when any organic group is not a group directly connected to a ring structure on the main chain in the repeating unit, at least two or more organic groups are substituents having three or more constituent atoms other than hydrogen atoms . Specific examples of the repeating unit represented by the formula (B) include repeating units described in paragraphs [0113] to [0115] of International Publication No. 2018/193954.

As an example of specific means for realizing the above (c), there is a method of introducing a repeating unit represented by the formula (C) into the resin (A).

[chemical formula 76]

In formula (C), R _c1 to R _c4 each independently represent a hydrogen atom or an organic group, and at least one of R _c1 to R _c4 is a group containing a hydrogen-bonding hydrogen atom within 3 atoms from the main chain carbon. group. Among them, in terms of inducing interaction between the main chains of the resin (A), hydrogen atoms having hydrogen bonding within 2 atoms (closer to the main chain side) are preferable. Specific examples of the repeating unit represented by the formula (C) include repeating units described in paragraphs [0119] to [0121] of International Publication No. 2018/193954.

An example of a specific means for realizing the above (d) includes a method of introducing a repeating unit represented by the formula (D) into the resin (A).

[chemical formula 77]

In formula (D), "Cyclic" represents a group that forms a main chain with a cyclic structure. The number of atoms constituting the ring is not particularly limited. Specific examples of the repeating unit represented by the formula (D) include repeating units described in paragraphs [0126] to [0127] of International Publication No. 2018/193954.

As an example of specific means for realizing the above (e), there is a method of introducing a repeating unit represented by the formula (E) into the resin (A).

[chemical formula 78]

In 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 which may have a substituent are mentioned, for example. "Cyclic" is a cyclic group containing carbon atoms in the main chain. The number of atoms contained in the cyclic group is not particularly limited. Specific examples of the repeating unit represented by the formula (E) include repeating units described in paragraphs [0131] to [0133] of International Publication No. 2018/193954.

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

The resin (A) may have a repeating unit having a hydroxyl group or a cyano group. Thereby, the board|substrate adhesiveness and developer affinity are improved. The repeating unit having a hydroxyl group or a cyano group is preferably a repeating unit having an alicyclic hydrocarbon structure substituted with a hydroxyl group or a cyano group. It is preferable that the repeating unit which has a hydroxyl group or a cyano group does not have an acid-decomposable group. Examples of the repeating unit having a hydroxyl group or a cyano group include those described in paragraphs [0081] to [0084] of JP-A-2014-098921.

The resin (A) may have a repeating unit having an alkali-soluble group. Examples of alkali-soluble groups include carboxyl groups, sulfonamide groups, sulfonimide groups, bissulfonamide groups, and aliphatic alcohol groups (such as hexafluoroisopropanol, base), preferably carboxyl. The resolution in the contact hole application is increased by the resin (A) including the repeating unit having an alkali-soluble group. Examples of the repeating unit having an alkali-soluble group include those described in paragraphs [0085] and [0086] of JP-A-2014-098921.

(repeating unit having an alicyclic hydrocarbon structure and not showing acid decomposability) The resin (A) may have a repeating unit that has an alicyclic hydrocarbon structure and does not show acid decomposability. Thereby, it is possible to reduce the elution of low-molecular components from the photoresist film into the immersion liquid during immersion exposure. Examples of the repeating unit having an alicyclic hydrocarbon structure and not exhibiting acid decomposability include 1-adamantyl (meth)acrylate, diadamantyl (meth)acrylate, Repeating unit of tricyclodecanyl ester or cyclohexyl (meth)acrylate.

(Repeating unit represented by formula (III) not having any of hydroxyl group and cyano group) Resin (A) may have the repeating unit represented by formula (III) which does not have any of a hydroxyl group and a cyano group.

[chemical formula 79]

In formula (III), R ₅ represents a hydrocarbon group having at least one cyclic structure and not having any of a hydroxyl group and a cyano group. Ra represents a hydrogen atom, an alkyl group or a -CH ₂ -O-Ra ₂ group. In the formula, Ra ₂ represents a hydrogen atom, an alkyl group or an acyl group. Examples of the repeating unit represented by the formula (III) having neither a hydroxyl group nor a cyano group include those described in paragraphs [0087] to [0094] of JP-A-2014-098921.

(other repeating units) Furthermore, the resin (A) may have other repeating units other than the above-mentioned repeating units. For example, the resin (A) may have a repeating unit selected from a repeating unit having a oxathiane ring group, a repeating unit having an oxazolone ring group, a repeating unit having a dioxane ring group, and a repeating unit having a hydantoin ring group. A repeating unit in a group of repeating units. Specific examples of other repeating units other than the above-mentioned repeating units are illustrated below.

[chemical formula 80]

The resin (A) may have various repeating structural units in addition to the above-mentioned repeating structural units in order to adjust dry etching resistance, standard developer compatibility, substrate adhesion, photoresist shape, resolution, heat resistance, and sensitivity.

As the resin (A), especially when the composition of the present invention is used as an actinic radiation-sensitive or radiation-sensitive resin composition for ArF, it is preferable that all repeating units are derived from Compounds are composed of repeating units. In particular, it is also preferable that all repeating units consist of (meth)acrylate-based repeating units. When all repeating units are composed of (meth)acrylate repeating units, all repeating units are methacrylate repeating units, all repeating units are acrylate repeating units, all repeating units are Either of the methacrylate repeating unit and the acrylate repeating unit can be used, and the acrylate repeating unit is preferably 50 mol% or less of the total repeating units.

Resin (A) can be synthesize|combined by a conventional method (for example, radical polymerization). The weight average molecular weight (Mw) of the resin (A) is preferably at most 30,000, more preferably 1,000 to 30,000, further preferably 3,000 to 30,000, and most preferably 5,000 to 15,000 in terms of polystyrene conversion by the GPC method. The degree of dispersion (molecular weight distribution, Mw/Mn) of the resin (A) is preferably from 1 to 5, more preferably from 1 to 3, further preferably from 1.2 to 3.0, particularly preferably from 1.2 to 2.0. The smaller the dispersion, the better the resolution and shape of the photoresist, and the smoother the sidewall of the photoresist pattern, the better the roughness performance.

In the actinic radiation-sensitive or radiation-sensitive resin composition, the content of the resin (A) is preferably 40.0 to 99.9% by mass, more preferably It is 60.0 to 90.0% by mass. One type of resin (A) may be used, and plural types may be used together.

<Compound (B) that generates acid by irradiation with actinic rays or radiation> In addition to the compound (N) described above, the composition of the present invention may also contain a compound (B) that generates an acid upon irradiation with actinic rays or radiation (also referred to as "compound (B)) other than the compound (N). )” or “photoacid generator (B)”). The photoacid generator (B) may be in the form of a low-molecular compound, or may be in a form incorporated into a part of a polymer (for example, a resin (A) described later). Moreover, the form of a low-molecular-weight compound and the form incorporated into a part of a polymer (for example, resin (A) mentioned later) can also be used together. When the photoacid generator (B) is in the form of a low molecular weight compound, the molecular weight of the photoacid generator is preferably 3000 or less, more preferably 2000 or less, further preferably 1000 or less. The lower limit is not particularly limited, but is preferably 100 or more. When the photoacid generator (B) is in the form of incorporating part of the polymer, part of the resin (A) may be incorporated, or a resin different from the resin (A) may be incorporated. In this specification, the photoacid generator (B) is preferably in the form of a low molecular weight compound.

The photoacid generator (B) includes, for example, a compound (onium salt) represented by "M ⁺ X ^- ", preferably a compound that generates an organic acid when exposed to light. Examples of the aforementioned organic acids include sulfonic acids (aliphatic sulfonic acids, aromatic sulfonic acids, and camphorsulfonic acids), carboxylic acids (aliphatic carboxylic acids, aromatic carboxylic acids, and aralkylcarboxylic acids, etc.), carbonyl Sulfonylimidic acid, bis(alkylsulfonyl)imidic acid, and tris(alkylsulfonyl)methylated acid.

In the compound represented by "M ⁺ X ^- ", M ⁺ represents an organic cation. There are no particular limitations on the organic cation. The valency of the organic cation may be one or more. Among them, as the above-mentioned organic cation, a cation represented by the above-mentioned formula (ZaI) (hereinafter also referred to as "cation (ZaI)") or a cation represented by the above-mentioned formula (ZaII) (hereinafter also referred to as "cation (ZaI)" is preferable. ZaII)".).

[chemical formula 81]

In the above 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 preferably 1-30, more preferably 1-20. Two of R ²⁰¹ to R ²⁰³ may be bonded to form a ring structure, and may also contain an oxygen atom, a sulfur atom, an ester group, an amido group or a carbonyl group in the ring. Examples of groups formed by bonding two of R ²⁰¹ to R ²⁰³ include alkylene groups (such as butylene groups and pentylene groups) and -CH ₂ -CH ₂ -O-CH ₂ -CH ₂ -.

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

First, the cation (ZaI-1) will be described. The cation (ZaI-1) is an aryl percolium cation, wherein at least one of R ²⁰¹ to R ²⁰³ in the formula (ZaI) is an aryl group. All of R ²⁰¹ to R ²⁰³ may be aryl groups, or some of R ²⁰¹ to R ²⁰³ may be aryl groups, and the rest may be alkyl or cycloalkyl groups. One of R ²⁰¹ to R ²⁰³ can be an aryl group, and the other two of R ²⁰¹ to R ²⁰³ can be bonded to form a ring structure, and the ring can also contain oxygen atoms, sulfur atoms, ester groups, amido groups or carbonyl. Examples of groups formed by two bonds among R ²⁰¹ to R ²⁰³ include alkane groups in which one or more methylene groups may be substituted by oxygen atoms, sulfur atoms, ester groups, amido groups, and/or carbonyl groups. (e.g. butyl, pentylene and _-CH2 - _CH2 -O- _CH2 - _CH2- ). Examples of the aryl cobaltium cation include triaryl cobaltium cations, diarylalkyl cobaltium cations, aryl dialkyl cobaltium cations, diarylcycloalkyl cobaltium cations, and arylbicycloalkyl cobaltium cations.

The aryl group contained in the aryl permedium cation is preferably a phenyl group or a naphthyl group, more preferably a phenyl group. The aryl group may be an aryl group having a heterocyclic structure having an oxygen atom, a nitrogen atom, a sulfur atom, or the like. 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 possessed by the aryl perium cation is preferably a linear alkyl group with 1 to 15 carbons, a branched chain alkyl group with 3 to 15 carbons, or a cycloalkane with 3 to 15 carbons. group, more preferably methyl, ethyl, propyl, n-butyl, sec-butyl, tert-butyl, cyclopropyl, cyclobutyl or cyclohexyl.

As substituents that the aryl, alkyl, and cycloalkyl groups of R ²⁰¹ to R ²⁰³ may have, preferably alkyl (eg, 1 to 15 carbons), cycloalkyl (eg, 3 to 15 carbons), aryl (such as carbon number 6-14), alkoxy group (such as carbon number 1-15), cycloalkylalkoxy group (such as carbon number 1-15), halogen atom (such as fluorine and iodine), hydroxyl group, carboxyl group, ester sulfinyl, sulfonyl, alkylthio or phenylthio. The substituent may further have a substituent if possible, and it is also preferable that the alkyl group has a halogen atom as a substituent to be a haloalkyl group such as a trifluoromethyl group. It is also preferable that the above-mentioned substituents form acid-decomposable groups by arbitrary combinations. Furthermore, the acid-decomposable group refers to a group that is decomposed by the action of an acid to generate a polar group, preferably a structure in which the polar group is protected by a group detached by the action of an acid. The aforementioned polar group and leaving group are as described above.

Next, the cation (ZaI-2) will be described. R ²⁰¹ to R ²⁰³ in the cation (ZaI-2)-based formula (ZaI) each independently represent a cation of an organic group having no aromatic ring. The term "aromatic ring" also includes aromatic rings containing heteroatoms. The carbon number of the organic group not having an aromatic ring as R ²⁰¹ to R ²⁰³ is preferably 1-30, more preferably 1-20. R ²⁰¹ to R ²⁰³ are each independently preferably an alkyl group, a cycloalkyl group, an allyl group or a vinyl group, and more preferably a linear or branched 2-oxoalkyl group or a 2-oxo ring group. An alkyl group or an alkoxycarbonylmethyl group is more preferably a linear or branched 2-oxoalkyl group.

The alkyl and cycloalkyl groups of R ²⁰¹ to R ²⁰³ include, for example, linear alkyl groups with 1 to 10 carbons or branched chain alkyl groups with 3 to 10 carbons (such as methyl, ethyl, propyl, butyl and pentyl) and cycloalkyl groups with 3 to 10 carbon atoms (such as 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. The substituents of R ²⁰¹ to R ²⁰³ are each independently preferably an acid-decomposable group formed by any combination of substituents.

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

[chemical formula 82]

In formula (ZaI-3b), R _1c to R _5c independently represent a hydrogen atom, alkyl, cycloalkyl, aryl, alkoxy, aryloxy, alkoxycarbonyl, alkylcarbonyloxy, cycloalkane carbonyloxy group, halogen atom, hydroxyl group, nitro group, alkylthio group or arylthio group. R _6c and R _7c each independently represent a hydrogen atom, an alkyl group (such as a t-butyl group, etc.), 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-oxoalkyl group, a 2-oxocycloalkyl group, an alkoxycarbonylalkyl group, an allyl group or a vinyl group. It is also preferable that the substituents of R _1c to R _7c , R _x and R _y each independently form 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 ring may be independently contain an oxygen atom, a sulfur atom, a ketone group, an ester bond or an amide bond. Examples of the ring include an aromatic or non-aromatic hydrocarbon ring, an aromatic or non-aromatic heterocycle, and a polycyclic condensed ring in which two or more of these rings are combined. Examples of the ring include 3 to 10 membered rings, preferably 4 to 8 membered rings, more preferably 5 or 6 membered rings.

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. Examples of the alkylene group include a methylene group and an ethylene group.

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

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

[chemical formula 83]

In formula (ZaI-4b), l represents the integer of 0-2, and r represents the integer of 0-8. R ₁₃ represents a hydrogen atom, a halogen atom (such as a fluorine atom and an iodine atom, etc.), a hydroxyl group, an alkyl group, a haloalkyl group, an alkoxy group, a carboxyl group, an alkoxycarbonyl group, or a group containing a cycloalkyl group (which may be a cycloalkyl group) itself, it may also be a group partially containing cycloalkyl). These groups may also have a substituent. R ₁₄ represents a hydroxyl group, a halogen atom (such as a fluorine atom and an iodine atom), an alkyl group, a haloalkyl 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 itself, or a group partially containing a cycloalkyl). These groups may have substituents. When _R14 exists in plural, each independently represents the above-mentioned groups such as a hydroxyl group. 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, a heteroatom such as an oxygen atom or a nitrogen atom may be contained in the ring skeleton. In one aspect, preferably two R ₁₅ are alkylene groups, and are bonded to each other to form a ring structure. In addition, the above-mentioned alkyl group, the above-mentioned cycloalkyl group, the above-mentioned naphthyl group, and a ring formed by bonding two R ₁₅ to each other may have a substituent.

In formula (ZaI-4b), the alkyl 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. The alkyl group is preferably methyl, ethyl, n-butyl or tert-butyl and the like. It is also preferable that each substituent of R ₁₃ to R ₁₅ and R _x and R _y independently form an acid-decomposable group by any combination of substituents.

Next, formula (ZaII) will be described. In formula (ZaII), R ²⁰⁴ and R ²⁰⁵ each independently represent an aryl group, an alkyl group or a cycloalkyl group. The aryl group for R ²⁰⁴ and R ²⁰⁵ is preferably phenyl or naphthyl, more preferably phenyl. 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 R ²⁰⁴ and R ²⁰⁵ are preferably linear alkyl groups with 1 to 10 carbons or branched chain alkyl groups with 3 to 10 carbons (such as methyl, ethyl, propyl, etc.) , butyl or pentyl), or a cycloalkyl group with 3 to 10 carbon atoms (such as 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, alkyl and cycloalkyl groups of R ²⁰⁴ and R ²⁰⁵ may have include, for example, alkyl groups (such as 1 to 15 carbons), cycloalkyls (such as 3 to 15 carbons), aromatic group (for example, carbon number 6-15), alkoxy group (for example, carbon number 1-15), halogen atom, hydroxyl group and phenylthio group. In addition, it is also preferable that the substituents of R ²⁰⁴ and R ²⁰⁵ independently form an acid-decomposable group by any combination of substituents.

Specific examples of organic cations are shown below, but the present invention is not limited thereto.

[chemical formula 84]

[chemical formula 85]

In the compound represented by "M ⁺ X ^- ", X ^- represents an anion. The description, specific examples, and preferred ranges of the anion are the same as those of the anion represented by X ⁻ of the above-mentioned compound (N).

The photoacid generator (B) is also preferably at least one selected from the group consisting of compound (I) and compound (II).

(Compound (I)) Compound (I) is a compound having one or more of the following structural site X and one or more of the following structural site Y, which is produced by irradiation with actinic rays or radiation containing A compound of an acid derived from the following first acidic site of X and the following second acidic site of structural site Y described below. Structural site X: a structural site composed of anionic site A ₁ ⁻ and cationic site M ₁ ⁺ , and the first acidic site represented by HA ₁ is formed by irradiation with actinic rays or radiation Structural site Y: anionic site A ₂ ^- and a cationic moiety M ₂ ⁺ , and a structural moiety that forms a second acidic moiety represented by HA ₂ by irradiation with actinic rays or radiation The above-mentioned compound (I) satisfies the following condition I.

Condition I: In the above-mentioned compound (I), the compound PI obtained by substituting the above-mentioned cationic site M ₁ ⁺ in the above-mentioned structural site X and the above-mentioned cationic site M ₂ ⁺ in the above-mentioned structural site Y with H ⁺ has an acid dissociation constant a1 and Acid dissociation constant a2, and the above acid dissociation constant a2 is larger than the above acid dissociation constant a1, and the acid dissociation constant a1 is derived from the acidity represented by HA ₁ obtained by substituting the above cationic site M ₁ ⁺ in the above structural site X with H ⁺ site, the acid dissociation constant a2 is derived from the acidic site represented by HA ₂ obtained by substituting the above-mentioned cationic site M ₂ ⁺ in the above-mentioned structural site Y with H ⁺ .

The cationic site M ₁ ⁺ and the cationic site M ₂ ⁺ in compound (I) are structural sites containing positively charged atoms or atomic groups, preferably monovalent organic cations, such as those represented by the above-mentioned M ⁺ of organic cations. Explanation, specific examples, and preferred ranges of parts other than cationic site M ₁ ⁺ and cationic site M ₂ ⁺ in compound (I) and cationic site M ₁ ⁺ and cationic site M ₂ ⁺ in compound (NI) above The descriptions of other parts are the same.

(compound (II)) Compound (II) is a compound having two or more of the above-mentioned structural site X and one or more of the following structural site Z, which is produced by irradiation with actinic rays or radiation. A compound having an acidic site and an acid of the above structural site Z. Structural site Z: a non-ionic site capable of neutralizing acid

In compound (II), the definition of structural site X, and the definition of A ₁ ^- and M ₁ ⁺ have the same meaning as the definition of structural site X, A ₁ ^- and M ₁ ⁺ in compound (I) above, and are more The same goes for good looks. The description, specific examples and preferred ranges about the structural part Z in the compound (II) are the same as the description about the structural part Z in the above-mentioned compound (NII). The description, specific examples, and preferred ranges of the moiety other than the cationic site M ₁ ⁺ in the compound (II) are the same as those described for the moiety other than the cationic site M ₁ ⁺ in the compound (NII).

Specific examples of sites other than cations that compound (I) and compound (II) may have are the same as specific examples of sites other than cations that compound (NI) and compound (NII) may have above.

Although the specific example of a photoacid generator (B) is shown below, it is not limited to these.

[chemical formula 86]

[chemical formula 87]

[chemical formula 88]

[chemical formula 89]

When the composition of the present invention contains the photoacid generator (B), its content is not particularly limited, but is preferably at least 0.5% by mass, more preferably 1.0% by mass, based on the total solid content of the composition of the present invention. %above. The above content is preferably at most 50.0% by mass, more preferably at most 30.0% by mass, and still more preferably at most 25.0% by mass, based on the total solid content of the composition of the present invention.

A photoacid generator (B) may be used individually by 1 type, and may use 2 or more types.

＜Acid diffusion control agent (C)＞ The composition of the present invention may contain an acid diffusion controller (C) other than the compound (N). The acid diffusion control agent (C) captures the acid generated by the photoacid generator etc. during exposure, and functions as a quencher that suppresses the reaction of the acid-decomposable resin in the unexposed part by the remaining generated acid . The type of acid diffusion control agent (C) is not particularly limited, and examples thereof include basic compounds (CA), low-molecular-weight compounds (CB) having nitrogen atoms and groups detached by the action of acids, and Compounds (CC) whose ability to control acid diffusion is reduced or lost upon exposure to chemical rays or radiation. Examples of the compound (CC) include an onium salt compound (CD) that becomes a relatively weak acid with respect to the photoacid generator (compound (N) or photoacid generator (B)), and an onium salt compound (CD) that is activated by actinic rays or radiation. Irradiation of basic compounds (CE) with reduced or lost alkalinity. Specific examples of basic compounds (CA) include basic compounds described in paragraphs [0132] to [0136] of International Publication No. 2020/066824. Specific examples of reduced or disappeared basic compounds (CE) include those described in paragraphs [0137] to [0155] of International Publication No. 2020/066824 and paragraphs [0164] of International Publication No. 2020/066824. As specific examples of the basic compound, a low-molecular compound (CB) having a nitrogen atom and a group detached by the action of an acid, paragraphs [0156] to [0163] of International Publication No. 2020/066824 can be cited. Recorded low molecular weight compounds. Specific examples of the onium salt compound (CD) that is a relatively weak acid relative to the photoacid generator include the onium salt compounds described in paragraphs [0305] to [0314] of International Publication No. 2020/158337.

In addition to the above, 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, and U.S. Patent Application Publication No. 2016 The known compounds disclosed in paragraphs [0403] to [0423] of No./0237190A1 and paragraphs [0259] to [0328] of US Patent Application Publication No. 2016/0274458A1 are used as acid diffusion control agents.

When the composition of the present invention contains an acid diffusion control agent (C), the content of the acid diffusion control agent (C) (the total amount of ) is preferably from 0.1 to 15.0% by mass, more preferably from 1.0 to 15.0% by mass. In the composition of the present invention, the acid diffusion controller (C) may be used alone or in combination of two or more.

＜Hydrophobic resin (D)＞ The composition of the present invention may further contain a hydrophobic resin different from the resin (A). The hydrophobic resin is preferably designed to be unevenly distributed on the surface of the photoresist film. Unlike surfactants, it does not necessarily need to have hydrophilic groups and polar substances in the molecule, and it may not promote the uniform mixing of non-polar substances. . Examples of the effects of adding a hydrophobic resin include controlling the static and dynamic contact angles of the photoresist film surface with respect to water and suppressing outgassing.

From the aspect of uneven distribution on the surface layer of the film, the hydrophobic resin preferably has any one or more of _CH3 moiety structures contained in fluorine atoms, silicon atoms, and side chains of the resin, more preferably two or more. more than one species. The above-mentioned hydrophobic resin preferably has a hydrocarbon group having 5 or more carbon atoms. These groups can exist in the main chain of the resin, and can also be substituted in the side chain. Examples of the hydrophobic resin include compounds described in paragraphs [0275] to [0279] of International Publication No. 2020/004306.

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

＜Surfactant (E)＞ The composition of the present invention may contain a surfactant. When a surfactant is included, 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. Examples of the fluorine-based and/or silicon-based surfactant include those disclosed in paragraphs [0218] and [0219] of International Publication No. 2018/19395.

These surfactants may be used alone or in combination of two or more.

When the composition of the present invention contains a surfactant, the content of the surfactant is preferably 0.0001 to 2.0% by mass, more preferably 0.0005 to 1.0% by mass, based on the total solid content of the composition of the present invention, and further Preferably it is 0.1-1.0 mass %.

<Solvent (F)> The composition of the present invention preferably contains a solvent. The solvent preferably contains at least one of the following components: (M1) propylene glycol monoalkyl ether carboxylate; (M2) selected from propylene glycol monoalkyl ether, lactate, acetate, alkoxy propionate , chain ketones, cyclic ketones, lactones and at least one of the group consisting of alkylene carbonates. In addition, the above-mentioned solvent may further contain components other than components (M1) and (M2).

Combining the above-mentioned solvent with the above-mentioned resin is preferable from the viewpoint of improving the applicability of the composition of the present invention and reducing the number of development defects in patterns. The above-mentioned solvent makes the solubility, boiling point, and viscosity of the above-mentioned resin well-balanced, so it is possible to suppress uneven film thickness of the photoresist film, generation of precipitates during spin coating, and the like. The details of the component (M1) and the component (M2) are described in paragraphs [0218] to [0226] of International Publication No. 2020/004306, and these contents are incorporated in this specification.

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

The content of the solvent in the composition of the present invention is preferably determined so that the solid content concentration becomes 1 to 30% by mass, more preferably 0.5 to 14.0% by mass. Accordingly, the applicability of the composition of the present invention can be further improved. In addition, a photoresist film having a film thickness suitable for ArF liquid immersion exposure and EUV exposure for forming high-precision fine patterns can be obtained.

＜Other additives＞ The composition of the present invention may further contain a dissolution inhibiting compound, a dye, a plasticizer, a photosensitizer, a light absorber and/or a compound that promotes solubility in a developer (for example, a phenolic compound with a molecular weight of 1000 or less or a carboxyl group-containing cycloaliphatic or aliphatic compounds).

The above-mentioned "dissolution inhibiting compound" is a compound having a molecular weight of 3000 or less whose solubility in an organic developer is reduced by decomposition by the action of an acid.

The composition of the present invention can be suitably used as a photosensitive composition for EUV exposure. 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 when exposed at the same sensitivity is small. Therefore, the "photon shot noise" in which the number of photons varies in probability has a large influence, leading to deterioration of LER and bridging defects. In order to reduce photon shot noise, there is a method of increasing the exposure amount to increase the number of incident photons, but it needs to be compromised with the requirement of high sensitivity.

When the A value obtained from the following formula (1) is high, the absorption efficiency of EUV light and electron beams of the photoresist 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 photoresist film. 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) The A value is preferably at least 0.120. The upper limit is not particularly limited, but when the A value is too large, the EUV light and electron beam transmittance of the photoresist film will decrease, the optical image profile in the photoresist film will deteriorate, and as a result, it is difficult to obtain a good pattern shape, so it is preferably 0.240 or less, more preferably 0.220 or less.

In formula (1), [H] represents the molar ratio of hydrogen atoms derived from all solid components in the composition of the present invention relative to all atoms in all solid components, and [C] represents the molar ratio of hydrogen atoms derived from all solid components in the composition of the present invention. The molar ratio of carbon atoms in all solid components to all atoms in all solid components, and [N] represents the molar ratio of nitrogen atoms in all solid components in the composition of the present invention to all atoms in all solid components Ratio, [O] represents the molar ratio of oxygen atoms derived from the total solid content of the composition of the present invention to all atoms of the total solid content, and [F] represents the total solid content derived from the composition of the present invention [S] represents the molar ratio of the sulfur atoms derived from the total solid content of the composition of the present invention relative to the total atoms of the total solid content, [I ] represents the molar ratio of iodine atoms derived from all solid components in the composition of the present invention relative to all atoms in all solid components. For example, when the composition of the present invention contains compound (N), resin (A), photoacid generator (B), acid diffusion control agent (C) and solvent, it is equivalent to compound (N), resin (A), Solid components of the photoacid generator (B) and the acid diffusion controller (C). That is, all atoms in the total solid content correspond to all atoms derived from the compound (N), all atoms derived from the resin (A), all atoms derived from the photoacid generator (B), and all atoms derived from the acid diffusion control agent (C) The sum of all atoms. For example, [H] represents the molar ratio of hydrogen atoms derived from all solid components to the total number of atoms in all solid components, and based on the above example, [H] represents hydrogen atoms derived from all atoms of compound (N) , the sum of the hydrogen atoms derived from all the atoms of the resin (A), the hydrogen atoms derived from all the atoms of the photoacid generator (B), and the hydrogen atoms derived from all the atoms of the acid diffusion control agent (C) relative to Mo of the sum of all atoms derived from the compound (N), all atoms derived from the resin (A), all atoms derived from the photoacid generator (B), and all atoms derived from the acid diffusion control agent (C) Ear ratio.

Calculation of the A value can be calculated by calculating the ratio of the number of atoms contained in the composition of the present invention when the structures and contents of the constituent components of all solid components are known. Moreover, even when the constituent components are unknown, the constituent atomic ratio can be calculated by analytical methods such as elemental analysis with respect to the photoresist film obtained by evaporating the solvent component of the composition of the present invention.

＜Photoresist film, pattern forming method＞ The steps of the pattern forming method using the composition of the present invention are not particularly limited, and preferably have the following process. Process 1: A process for forming a photoresist film on a substrate using the composition of the present invention Process 2: The process of exposing the photoresist film Process 3: The process of developing the exposed photoresist film using a developer Hereinafter, the steps of each of the above-mentioned manufacturing processes will be described in detail.

(Process 1: Photoresist film formation process) Process 1 is a process for forming a photoresist film on a substrate using the composition of the present invention. The composition of the present invention is as described above.

As a method of forming a photoresist film on a substrate using the composition of the present invention, for example, a method of applying the composition of the present invention to a substrate is mentioned. Furthermore, it is preferable to filter the composition of this invention with a filter as needed before coating. The pore size of the filter is preferably 0.1 μm or less, more preferably 0.05 μm or less, further preferably 0.03 μm or less. The filter is preferably made of polytetrafluoroethylene, polyethylene or nylon.

The composition of the present invention can be applied to a substrate (eg, silicon-coated, silicon dioxide-coated) for manufacturing integrated circuit elements by an appropriate coating method such as a spin coater or a coater. The coating method is preferably spin coating using a spin coater. The rotational speed when performing spin coating using a spin coater is preferably 1000 to 3000 rpm. The photoresist film can be obtained by drying the substrate after coating the composition of the present invention. Furthermore, various base films (inorganic film, organic film, antireflection film) may be formed on the lower layer of the photoresist film as needed.

As a drying method, the method of heating and drying is mentioned, for example. Heating can be implemented by means equipped with a normal exposure machine and/or a developing machine, and can implement using a hot plate etc. also. The heating temperature is preferably from 80 to 150°C, more preferably from 80 to 140°C, further preferably from 80 to 130°C. The heating time is preferably from 30 to 1000 seconds, more preferably from 60 to 800 seconds, further preferably from 60 to 600 seconds.

The film thickness of the photoresist film is not particularly limited, but is preferably 10 to 120 nm from the viewpoint of being able to form a fine pattern with high precision. Among them, in the case of EUV exposure, the film thickness of the photoresist film is more preferably 10 to 65 nm, further preferably 15 to 50 nm. In the case of performing ArF immersion exposure, the film thickness of the photoresist film is more preferably 10 to 120 nm, further preferably 15 to 90 nm.

Furthermore, an overcoat layer may be formed on an upper layer of the photoresist film using an overcoat composition. Preferably, the overcoat composition can be further uniformly coated on the upper layer of the photoresist film without being mixed with the photoresist film. The overcoat layer is not particularly limited, and a conventionally known overcoat layer can be formed by a conventionally known method. For example, the overcoat layer can be formed based on the description in paragraphs [0072] to [0082] of JP-A-2014-059543 layer. For example, it is preferable to form an overcoat layer containing a basic compound on a photoresist film as described in JP-A-2013-61648. Specific examples of the basic compound that can be contained in the overcoat layer include basic compounds that can be contained in an actinic radiation-sensitive or radiation-sensitive resin composition. The overcoat layer is also preferably a compound comprising 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 for exposing the photoresist film. As a method of exposure, a method of irradiating actinic rays or radiation to the formed photoresist film through a predetermined mask is mentioned. Examples of actinic rays or radiation include infrared light, visible light, ultraviolet light, extreme ultraviolet light, extreme ultraviolet light, X-rays, and electron beams, preferably 250 nm or less, more preferably 220 nm or less, particularly preferably 1 to 200 nm Far-ultraviolet light with a certain wavelength, specifically KrF excimer laser (248nm), ArF excimer laser (193nm), F ₂ excimer laser (157nm), EUV (13.5nm), X-rays and electron beams. The exposure process of the photoresist film is preferably a process of exposing the photoresist film to EUV.

Baking (heating) is preferably performed after exposure and before image development. Accelerate the reaction of the exposed part by baking, and make the sensitivity and pattern shape better. The heating temperature is preferably from 80 to 150°C, more preferably from 80 to 140°C, further preferably from 80 to 130°C. The heating time is preferably from 10 to 1000 seconds, more preferably from 10 to 180 seconds, further preferably from 30 to 120 seconds. Heating can be implemented by the mechanism equipped with the usual exposure machine and/or developing machine, and can also be performed using a hot plate etc. as well. This process is also called post-exposure bake.

(Process 3: Development process) Process 3 is a process of developing the exposed photoresist film with a developer to form a pattern. The developer may be an alkaline developer or a developer containing an organic solvent (hereinafter also referred to as an organic developer).

Examples of developing methods include: a method in which the substrate is immersed in a tank filled with a developer for a certain period of time (dipping method); solution (puddle) method); method of spraying the developer onto the surface of the substrate (spray method); and method of continuously discharging the developer onto the substrate rotating at a certain speed while scanning the developer discharge nozzle at a certain speed (dynamic distribution Law). Moreover, after the process of image development, the process of stopping image development while replacing with another solvent can also be implemented. The development time is not particularly limited as long as the resin in the unexposed portion is sufficiently dissolved, but it is preferably from 10 to 300 seconds, more preferably from 20 to 120 seconds. The temperature of the developer is preferably from 0 to 50°C, more preferably from 15 to 35°C.

It is preferable to use the alkali aqueous solution containing alkali as an alkaline developing solution. The type of aqueous alkali solution is not particularly limited, and examples include aqueous alkali 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 an aqueous solution of a quaternary ammonium salt represented by tetramethylammonium hydroxide (TMAH). Alcohols, surfactants, etc. can be added in an appropriate amount in the alkaline developer. The alkali concentration of the alkaline developing solution is preferably usually 0.1 to 20% by mass. The pH of the alkaline developing solution is preferably usually from 10.0 to 15.0.

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 above-mentioned solvents may be mixed in plural, and may be mixed with solvents other than the above-mentioned ones or water. The moisture content of the developer is preferably less than 50% by mass, more preferably less than 20% by mass, further preferably less than 10% by mass, and particularly preferably substantially free of moisture. With respect to the total amount of the developer, the content of the organic solvent relative to the organic developer is preferably from 50% by mass to 100% by mass, more preferably from 80% by mass to 100% by mass, still more preferably 90 mass % or more and 100 mass % or less, especially preferably 95 mass % or more and 100 mass % or less.

(other processes) The above-mentioned pattern forming method preferably includes a cleaning process using a rinse solution after the process 3 .

As a rinsing liquid used in the rinsing process after the process of developing using an alkaline developing solution, pure water is mentioned, for example. Furthermore, a suitable amount of surfactant can be added to pure water. A suitable amount of surfactant can be added to the flushing solution.

The rinse solution used in the rinse process after the development 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 rinsing solution is preferably a rinsing solution 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 rinsing process is not particularly limited, and examples include: a method of continuously discharging a rinsing liquid onto a substrate rotating at a constant speed (spin coating method); a method of immersing a substrate in a tank filled with a rinsing liquid for a certain period of time ( dipping method); and a method of spraying a rinse solution on the substrate surface (spray method). Also, the pattern forming method may include a heating process (Post Bake) after the rinsing process. In this process, the developer and rinse solution remaining between the patterns and inside the patterns are removed by baking. Moreover, this manufacturing process also has the effect of smoothing the photoresist pattern and improving the surface roughness of the pattern. The heating process after the rinsing process is usually performed at 40 to 250° C. (preferably 90 to 200° C.) for usually 10 seconds to 3 minutes (preferably 30 seconds to 120 seconds).

Moreover, the etching process of a board|substrate can also be performed using the formed pattern as a mask. That is, the pattern formed in Process 3 may 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 underlying film and the substrate) is not particularly limited, and it is preferably formed on the substrate by dry etching the substrate (or the underlying film and the substrate) using the pattern formed in process 3 as a mask. pattern method. Dry etching is preferably oxygen plasma etching.

The composition of the present invention and various materials used in the pattern forming method of the present invention (for example, solvent, developer, rinse solution, composition for forming an antireflection film, composition for forming an overcoat layer, etc.) preferably do not contain Impurities such as metals. The content of impurities contained in these materials is preferably 1 mass ppm (parts per million) or less, more preferably 10 mass ppb (parts per billion) or less, further preferably 100 mass ppt (parts per trillion), The best is less than 10 quality ppt, and the best is less than 1 quality ppt. The lower limit is not particularly limited, but 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. Details of filtration using a filter are described in paragraph [0321] of International Publication No. 2020/004306.

As a method of reducing impurities such as metals contained in various materials, for example: a method of selecting raw materials with low metal content as raw materials constituting various materials; a method of filtering raw materials constituting various materials; A method in which distillation is carried out under conditions that suppress contamination as much as possible by lining the interior with Teflon (registered trademark) or the like.

In addition to filter filtration, adsorption materials can also be used to remove impurities, and filter filtration and adsorption materials can 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 above-mentioned various materials, it is necessary to prevent mixing of metal impurities in 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 100 ppt by mass or less, more preferably 10 ppt by mass or less, further preferably 1 ppt by mass or less. The lower limit is not particularly limited, but is preferably 0 mass ppt or more.

Conductive compounds can be added to organic treatment liquids such as flushing liquids in order to prevent malfunctions of chemical piping and various parts (filters, O-rings, tubes, etc.) . The conductive compound is not particularly limited, and examples thereof include methanol. The addition amount is not particularly limited, but is preferably at most 10% by mass, more preferably at most 5% by mass, in order to maintain good developing properties or flushing properties. The lower limit is not particularly limited, but is preferably at least 0.01% by mass. As the chemical piping, for example, various pipings coated with SUS (stainless steel), or antistatic-treated polyethylene, polypropylene, or fluororesin (polytetrafluoroethylene, perfluoroalkoxy resin, etc.) can be used. For the filter and the O-ring, antistatic-treated polyethylene, polypropylene, or fluororesin (polytetrafluoroethylene, perfluoroalkoxy resin, etc.) can be used similarly.

＜Manufacturing method of electronic devices＞ The present invention also relates to a method of manufacturing an electronic device including the above pattern forming method and an electronic device manufactured by the method. Preferred embodiments of the electronic device in this specification include embodiments mounted in electrical and electronic equipment (home appliances, OA (Office Automation), media-related equipment, optical equipment, communication equipment, and the like). [Example]

Hereinafter, the present invention will be described in more detail based on examples. Unless departing from the gist of the present invention, the materials, usage amounts, ratios, processing contents, processing steps, etc. shown in the following examples can be appropriately changed. Therefore, the scope of the present invention should not be limitedly interpreted by the Examples shown below.

The compounds used in Examples and Comparative Examples are described below.

<Compound (N)> As the compound (N), X-1 to X-24 were used. The repeating unit ratio of X-21 is the mass ratio (mass %) of each repeating unit contained in X-21 to all repeating units. The weight average molecular weight (Mw) of X-21 was 9200, and the degree of dispersion (Mw/Mn) was 1.63. Me represents a methyl group. In addition, in the comparative example, Z-1 to Z-6 were used. Although Z-1 to Z-6 are not compounds (N), they are listed in the column of compound (N) for convenience. Me represents a methyl group.

[chemical formula 90]

[chemical formula 91]

[chemical formula 92]

[chemical formula 93]

[chemical formula 94]

(Synthesis Example 1: Synthesis of X-1) The synthesis example of X-1 is shown below.

[chemical formula 95]

Magnesium (19.3 g) was added to tetrahydrofuran (THF) (850 mL) to obtain a mixture. 1-Bromo-4-(trifluoromethoxy)benzene (182.3 g) was added dropwise to the resulting mixture. The above mixture was then stirred for 1 hour to prepare Grignard reagent X-1-1. Grignard reagent X-1-1 was cooled to 0°C and thionyl chloride (45.0 g) was added dropwise. After the above mixture was stirred for 1 hour, 1 mol/L hydrochloric acid (800 mL) was added to the mixture while maintaining the temperature of the above mixture at 0°C. The reaction product generated in the above mixture was extracted with ethyl acetate (600 mL). The resulting organic phase was washed 3 times with water (500 mL), then the solvent was evaporated from the organic phase. The obtained concentrate was purified by silica gel column chromatography to obtain X-1-A (71.5 g) (yield 51%).

[chemical formula 96]

9.4 g of magnesium was added to 380 mL of tetrahydrofuran, 1-bromo-4-(trifluoromethoxy)benzene (89.8 g) was added dropwise, and stirred for 1 hour to prepare Grignard reagent X-1-2. Grignard reagent X-1-2 was cooled to 15°C and X-1-A (46.0 g) was added. Bromotrimethylsilane (TMSBr) (133.1 g) was then added dropwise to the above mixture. After stirring the above mixed solution for 1 hour, it was cooled to 0° C., and 500 mL of water was added dropwise. The resulting reaction product in the above mixture was extracted with dichloromethane (500 mL). The resulting organic phase was washed 3 times with water (500 mL), then the solvent was evaporated from the organic phase. The resulting concentrate was purified with diisopropyl ether (200 mL) to give X-1-B (29.6 g) (yield 40%).

[chemical formula 97]

Mix dichloromethane (100 mL) and water (100 mL), add X-1-3 (4.0 g) and X-1-B (6.0 g). After stirring for 1 hour, the aqueous layer was removed, and the organic layer was washed with 0.1 mol/L hydrochloric acid (100 mL) and water (100 mL). The solvent was distilled off to obtain X-1 (7.9 g) (yield 95%).

The other compound (N) was synthesized in the same manner as X-1.

<Resin (A)> As the resin (A), A-1 to A-25 were used. Table 1 shows the content (mole %), weight average molecular weight (Mw) and degree of dispersion (Mw/Mn) of each repeating unit contained in each resin. The repeating unit content is the ratio (molar ratio) of each repeating unit contained in each resin to all the repeating units. In Table 1, the value of the content of the repeating unit of each resin corresponds to the description order of the repeating unit in the structural formula of each resin shown below. For example, in A-1, the content of the repeating unit on the left is 25 mol%, the content of the repeating unit in the center is 30 mol%, and the content of the repeating unit on the right is 45 mol%. The weight-average molecular weight (Mw) and degree of dispersion (Mw/Mn) of the resin were measured by GPC (carrier: tetrahydrofuran (THF)) (the amount in terms of polystyrene). In addition, the content of the repeating unit was measured by ¹³ C-NMR (nuclear magnetic resonance, nuclear magnetic resonance).

[chemical formula 98]

[chemical formula 99]

[chemical formula 100]

[chemical formula 101]

[chemical formula 102]

[Table 1]

＜Photoacid generator (B)＞ As the photoacid generator (B), B-1 to B-11 were used.

[chemical formula 103]

[chemical formula 104]

＜Acid diffusion control agent＞ As the acid diffusion control agent, C-1 to C-7 were used.

[chemical formula 105]

<Hydrophobic resin> As the hydrophobic resin, D-1 to D-6 shown in Table 2 below were used. Table 2 shows the type and content (mol %), weight average molecular weight (Mw) and degree of dispersion (Mw/Mn) of each repeating unit contained in each resin. The repeating unit content is the ratio (molar ratio) of each repeating unit contained in each resin to all the repeating units. The kind of each repeating unit is shown by the structure of the corresponding monomer. The weight-average molecular weight (Mw) and degree of dispersion (Mw/Mn) of the resin were measured by GPC (carrier: tetrahydrofuran (THF)) (the amount in terms of polystyrene). In addition, the repeating unit content was measured by ¹³ C-NMR (nuclear magnetic resonance, nuclear magnetic resonance).

[Table 2]

The structures of monomers ME-1 to ME-13 corresponding to the respective repeating units constituting the hydrophobic resin shown in Table 2 are shown below.

[chemical formula 106]

＜Surfactant＞ As surfactants, E-1 to E-3 were used. E-1: MEGAFAC F176 (manufactured by DIC Co., Ltd., fluorine-based surfactant) E-2: MEGAFAC R08 (manufactured by DIC Co., Ltd., fluorine and silicon-based surfactant) E-3: PF656 (manufactured by OMNOVA, fluorine-based surfactant)

<Solvent> As solvents, F-1 to F-9 were used. F-1: Propylene Glycol Monomethyl Ether Acetate (PGMEA) F-2: Propylene Glycol Monomethyl Ether (PGME) F-3: Propylene glycol monoethyl ether (PGEE) F-4: Cyclohexanone F-5: Cyclopentanone F-6: 2-heptanone F-7: ethyl lactate F-8: γ-butyrolactone F-9: Propylene carbonate

[Preparation of Photoresist Composition] Each component shown in the following Table 3 and Table 4 was mixed so that the solid content concentration might become 2 mass %. Next, the obtained mixed solution is filtered through a polyethylene filter with a pore diameter of 50 nm, then a nylon filter with a pore diameter of 10 nm, and finally a polyethylene filter with a pore diameter of 5 nm. Thus, resist compositions (Re-1 to Re-40) were prepared. In the photoresist composition, the solid content refers to all components except the solvent. In Table 3 and Table 4, the content (mass %) of compound (N), resin (A), photoacid generator (B), acid diffusion control agent, hydrophobic resin, and surfactant refers to relative to photoresist The content ratio by mass of all solid components of the composition. The mixing ratio of solvents refers to the ratio (mass ratio) of each solvent when all solvents are 100%. When two or more components are used, separate the types and contents with "/". For example, "X-5/X-17" in the photoresist composition Re-23 means that X-5 and X-17 are used as compound (N), and "10.3/15.4" means that the content of X-5 is 10.3% by mass, and the content of X-17 was 15.4% by mass. The obtained photoresist compositions were used in Examples and Comparative Examples.

[table 3]

[Table 4]

[Pattern formation (1): EUV exposure, alkaline development] An underlayer film-forming composition AL412 (manufactured by Brewer Science) was coated on a silicon wafer, and baked at 205° C. for 60 seconds to form an underlayer film with a film thickness of 20 nm. The photoresist composition shown in Table 5 was coated on the lower layer film, and baked at 100° C. for 60 seconds to form a photoresist film with a film thickness of 30 nm. The silicon wafer having the obtained photoresist film was subjected to pattern irradiation using an EUV exposure apparatus (manufactured by Exitech, Micro Exposure Tool, NA0.3, Quadrupole (quadrupole), outer sigma 0.68, inner sigma 0.36). As a reticle, a mask with a line size=14 nm and a line:space=1:1 was used. After the exposed photoresist film was baked at 90° C. for 60 seconds, it was developed with a tetramethylammonium hydroxide aqueous solution (2.38% by mass) for 30 seconds, and then rinsed with pure water for 30 seconds. After that, it was spin-dried to obtain a positive pattern.

[Evaluation of pattern shape (EUV exposure, alkaline development)] Observe the cross-sectional shape of a line pattern with an average line width of 14 nm, and measure the pattern line width Lb at the bottom of the resist pattern and the pattern line width at the top of the resist pattern using a length-measuring scanning electron microscope (SEM Co., Ltd., Hitachi, Ltd. S-9380II) La, When 0.98＜(La/Lb)≤1.03, the evaluation is "A", When 1.03＜(La/Lb)≤1.06, the evaluation is "B", When 1.06＜(La/Lb)≤1.10, the evaluation is "C", When 1.10<(La/Lb)≤1.14, the evaluation is "D", When (La/Lb)>1.14, the evaluation was "E".

[table 5]

[Pattern formation (2): EUV exposure, organic solvent development] An underlayer film-forming composition AL412 (manufactured by Brewer Science) was coated on a silicon wafer, and baked at 205° C. for 60 seconds to form an underlayer film with a film thickness of 20 nm. The photoresist composition shown in Table 6 was coated on the lower layer, and baked at 100° C. for 60 seconds to form a photoresist film with a film thickness of 30 nm. The silicon wafer having the obtained photoresist film was subjected to pattern irradiation using an EUV exposure apparatus (manufactured by Exitech, Micro Exposure Tool, NA0.3, Quadrupole, outer sigma 0.68, inner sigma 0.36). As the reticle, a mask with line size=14 nm and line:space=1:1 was used. The exposed photoresist film was baked at 90° C. for 60 seconds, developed with n-butyl acetate for 30 seconds, and then spin-dried to obtain a negative pattern.

[Evaluation of pattern shape (EUV exposure, organic solvent development)] Observe the cross-sectional shape of a line pattern with an average line width of 14 nm, and measure the pattern line width Lb at the bottom of the resist pattern and the pattern line width at the top of the resist pattern using a length-measuring scanning electron microscope (SEM Co., Ltd., Hitachi, Ltd. S-9380II) La, When 0.98＜(La/Lb)≤1.03, the evaluation is "A", When 1.03＜(La/Lb)≤1.06, the evaluation is "B", When 1.06＜(La/Lb)≤1.10, the evaluation is "C", When 1.10<(La/Lb)≤1.14, the evaluation is "D", When (La/Lb)>1.14, the evaluation was "E".

[Table 6]

From the results in Table 5 and Table 6, it can be seen that the photoresist composition of the example can form a pattern excellent in the pattern shape in the ultrafine pattern formation. [Industrial availability]

According to the present invention, it is possible to provide a method for producing an actinic radiation-sensitive or radiation-sensitive resin composition capable of forming an extremely fine pattern (for example, a 1:1 line and space pattern with a line width of 14 nm or less, etc.) A pattern with excellent pattern shape. Furthermore, according to the present invention, there can be provided a photoresist film using the above-mentioned actinic radiation-sensitive or radiation-sensitive resin composition, a method for forming a pattern, and a method for manufacturing an electronic device.

Although the present invention has been described in detail with reference to specific embodiments, it is obvious for those skilled in the art that various changes and modifications can be made without departing from the spirit and scope of the present invention. This application is based on Japanese Patent Application (Japanese Patent Application No. 2021-160154) filed on September 29, 2021, the contents of which are incorporated herein by reference.

Claims (14)

An actinic radiation-sensitive or radiation-sensitive resin composition comprising: at least one selected from the group consisting of cations represented by the following general formula (N1) and cations represented by the following general formula (N2) compound (N); and a resin (A) whose polarity is increased by decomposition by the action of an acid,

In the general formula (N1) and the general formula (N2), Ar ^N1 and Ar ^N3 independently represent aromatic rings having at least one substituent represented by the following general formula (N3) bonded to at least one carbon atom constituting the aromatic ring. Ar ^N2 represents an aromatic group having at least one substituent selected from the group consisting of organic groups and halogen atoms, wherein Ar ^N2 is a group different from Ar ^N1 , and R ^N1 and R ^N2 are respectively independently represents an organic group, k1+k2+k3 is 3, k1 represents an integer of 1 to 3, k2 represents an integer of 0 to 2, k3 represents 0 or 1, wherein, when k1 represents 1, k2 represents 1 or 2, At least two of Ar ^N1 , Ar ^N2 , and R ^N1 can form a ring through a single bond or a linking group. When there are multiple Ar ^N1 , the multiple Ar ^N1 can be the same or different. There are multiple Ar ^N2 When there are multiple Ar ^N2 , the multiple Ar N2 can be the same or different, k4+k5 is 2, k4 means 1 or 2, k5 means 0 or 1, when there are multiple Ar ^N3 , the multiple Ar ^N3 can be the same or different, Ar ^N3 and R ^N2 , or two Ar ^N3 can be bonded by a single bond or a linking group to form a ring,

In the general formula (N3), Y ^N1 represents an oxygen atom or a sulfur atom, Z ^N1 represents a group represented by the following general formula (N4) or (N5), * represents a bonding position,

In the general formula (N4), R ^N3 and R ^N4 independently represent a hydrogen atom, a fluorine atom, a fluorinated alkyl group or an alkyl group, and at least one -CH ₂ - contained in the alkyl group may be substituted by -CO-, ＊Indicates the bonding position,

In the general formula (N5), Rf ^N1 represents a perfluoroalkyl group, R ^N5 represents a fluorinated alkyl or alkyl group, at least one -CH ₂ - contained in the alkyl group can be replaced by -CO-, R ^N6 represents hydrogen atom, fluorinated alkyl group or alkyl group, at least one -CH ₂ - contained in the alkyl group may be substituted by -CO-, * indicates the bonding position. The actinic radiation-sensitive or radiation-sensitive resin composition according to Claim 1, wherein R ^N3 in the general formula (N4) represents a fluorine atom or a fluorinated alkyl group. The actinic radiation-sensitive or radiation-sensitive resin composition according to claim 1, wherein R ^N5 in the general formula (N5) represents a fluorinated alkyl group. The actinic radiation-sensitive or radiation-sensitive resin composition according to claim 1 or 2, wherein Z ^N1 in the general formula (N3) represents a group represented by the general formula (N4). The actinic radiation-sensitive or radiation-sensitive resin composition as described in any one of Claims 1 to 3, wherein Ar ^N2 in the general formula (N1) represents an organic group selected from halogen atoms and halogen atoms At least one aromatic group as a substituent in the group formed. The actinic radiation-sensitive or radiation-sensitive resin composition as described in any one of claims 1 to 3, wherein Ar ^N2 in the general formula (N1) represents an organic group selected from fluorine atoms and fluorine atoms At least one aromatic group as a substituent in the group formed. The actinic radiation-sensitive or radiation-sensitive resin composition according to any one of Claims 1 to 3, wherein the compound (N) contains at least one cation represented by the general formula (N1). The actinic radiation-sensitive or radiation-sensitive resin composition as described in any one of Claims 1 to 3, wherein Ar ^N1 and Ar ^N3 in the general formulas (N1) and (N2) are independently represented by the following The group represented by the general formula (N6),

In the general formula (N6), R ^N7 to R ^N11 independently represent a hydrogen atom, a halogen atom, an alkyl group, an alkoxy group or a substituent represented by the general formula (N3), wherein, in R ^N7 to R ^N11 At least one represents a substituent represented by the general formula (N3), and * represents a bonding position. The actinic radiation-sensitive or radiation-sensitive resin composition according to any one of Claims 1 to 3, wherein the compound (N) has a group selected from the group represented by the following general formula (N7), *-SO ₃ ^- and *-CO ₂ ^-at least one of the group consisting of,

L ^N1 and L ^N2 each independently represent -SO ₂ - or -CO-, and * represents a bonding position. The actinic radiation-sensitive or radiation-sensitive resin composition according to any one of claims 1 to 3, wherein the actinic radiation-sensitive or radiation-sensitive resin composition further contains a solvent and has a solid content concentration of 0.5 to 14.0 quality%. A photoresist film formed using the actinic radiation-sensitive or radiation-sensitive resin composition described in any one of Claims 1 to 10. A pattern forming method, comprising: A process for forming a photoresist film on a substrate using the actinic radiation-sensitive or radiation-sensitive resin composition described in any one of Claims 1 to 10; the process of exposing the photoresist film; and A process of developing the exposed photoresist film with a developer. The pattern forming method according to claim 12, wherein the process of exposing the photoresist film is a process of exposing the photoresist film by EUV. A method of manufacturing an electronic device, which includes the pattern forming method described in claim 12 or 13.