TW202342439A - Actinic-ray-sensitive or radiation-sensitive resin composition, resist film, pattern forming method, and electronic device manufacturing method - Google Patents

Abstract

Provided are: an actinic-ray-sensitive or radiation-sensitive resin composition; a resist film; a pattern forming method; and an electronic device manufacturing method, wherein the resist film, the pattern forming method, and the electronic device manufacturing method use the actinic-ray-sensitive or radiation-sensitive resin composition. The actinic-ray-sensitive or radiation-sensitive resin composition comprises: a resin (A) that contains a repeating unit represented by general formula (N1) and a repeating unit represented by general formula (S1); a compound (B) that generates an acid upon exposure to actinic rays or radiation; and a compound (C) that is represented by general formula (Q1) and is different from the compound (B), wherein the content of the repeating unit represented by general formula (N1) is at least 55 mol% of the repeating units as a whole. The resist film, the pattern forming method, and the electronic device manufacturing method make it possible to suppress the occurrence of defects in ultrafine pattern formation.

Description

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

The present invention relates to photosensitive radiation or radiation-sensitive resin compositions, resist films, pattern forming methods, and manufacturing methods of electronic components. More specifically, the present invention relates to a manufacturing process that can be applied to ultra-LSI (Large Scale Integration, large-scale integrated circuit) and high-capacity microchips, a nanoimprint mold manufacturing process, and a manufacturing process of high-density information recording media, etc. Ultralithography process, as well as photosensitive radiation or radiation-sensitive resin compositions that can be preferably used in other photosensitive etching processes, resist films and patterns using the above-mentioned photosensitive radiation or radiation-sensitive compositions Formation method, and manufacturing method of electronic components.

In the past, in the manufacturing process of semiconductor components such as IC (Integrated Circuit) and LSI (Large Scale Integration), microfabrication was performed by photolithography using resist compositions. In recent years, with the high integration of integrated circuits, it is required to form ultra-fine patterns in the sub-micron area or the quarter-micron area. Along with this, the exposure wavelength has also shown a trend of shortening from g-rays to i-rays, and then to KrF excimer laser light. Currently, an exposure machine using ArF excimer laser with a wavelength of 193 nm as the light source has been developed. In addition, as a technology to further improve the resolution, the so-called liquid immersion method is being developed in which a high refractive index liquid (hereinafter also referred to as "immersion liquid") is filled between the projection lens and the sample.

In addition, in addition to excimer laser light, lithography using electron beam (EB), X-ray, extreme ultraviolet (EUV), etc. is also being developed. Along with this, resist compositions that can effectively sense various actinic rays or radiation have been developed.

Various compositions are known as photosensitive radiation or radiation-sensitive resin compositions. For example, Patent Document 1 and Patent Document 2 describe a resist composition containing a resin having a repeating unit containing a phenolic hydroxyl group and an acid-decomposable repeating unit containing an aromatic group. [Prior technical literature] [Patent Document]

Patent document 1: Japanese Patent Application Publication No. 2019-219470 Patent Document 2: Japanese Patent Application Publication No. 2021-130808

[Problem to be solved by the invention] However, the resist compositions described in Patent Documents 1 and 2 have a problem that defects (for example, bridge defects or residue defects) are easily generated when forming extremely fine patterns with a line width of 30 nm or less, for example.

An object of the present invention is to provide a photosensitive radiation or radiation-sensitive resin composition capable of suppressing the occurrence of defects when forming extremely fine patterns (for example, line widths of 30 nm or less). Furthermore, an object of the present invention is to provide a resist film, a pattern forming method, and an electronic component manufacturing method using the above-mentioned photosensitive radiation or radiation-sensitive resin composition. [Means to solve the problem]

The present inventors found that the above-mentioned problems can be solved by the following configuration.

[1] A photosensitive ray or radiation-sensitive resin composition, which contains a resin (A), a compound (B) that generates an acid by irradiation with actinic rays or radioactive rays, and a compound different from the above compound (B) ( C), where, The above-mentioned resin (A) contains a repeating unit represented by the following general formula (N1) and a repeating unit represented by the following general formula (S1), The content of the repeating unit represented by the following general formula (N1) in the above-mentioned resin (A) is 55 mol% or more relative to all the repeating units in the above-mentioned resin (A), The above-mentioned compound (C) is a compound represented by the following general formula (Q1).

[Chemical 1]

In the general formula (N1), R ^1N to R ^3N each independently represent a hydrogen atom, an alkyl group, a cycloalkyl group, a halogen atom, a cyano group, an alkoxy group or an alkoxycarbonyl group, and R ^4N represents a hydrogen atom or something other than a hydroxyl group. Substituent, R ^4N can be bonded to at least one of R ^1N ~ R ^3N . When there are plural R ^4Ns , the plural R ^4Ns can be the same or different, and the plural R ^4Ns can be bonded. k1 represents 0 or 1, When k1 represents 0, k2 represents an integer from 1 to 5, k3 represents 5-k2, when k1 represents 1, k2 represents an integer from 1 to 7, and k3 represents 7-k2.

[Chemicalization 2]

In the general formula (S1), R ^1S to R ^3S each independently represent a hydrogen atom, an alkyl group, a cycloalkyl group, a halogen atom, a cyano group, an alkoxy group or an alkoxycarbonyl group, and R ^4S represents a hydrogen atom or -COOR ^5S . ^{For substituents other than _ _ _} When a plurality of R ^5S is present in a group separated by the action of an acid, the plurality of R ^5S may be the same or different. m1 represents 0 or 1. When m1 represents 0, m2 represents an integer from 1 to 5, and m3 represents 5- When m2 and m1 represent 1, m2 represents an integer from 1 to 7, and m3 represents 7-m2.

[Chemical 3]

In the general formula (Q1), R ^1Z represents an organic group, and Mq ⁺ represents a cation. [2] The photosensitive radiation-sensitive or radiation-sensitive resin composition according to [1], wherein the repeating unit represented by the general formula (S1) is a repeating unit represented by the following general formula (S2).

[Chemical 4]

In the general formula (S2), R ^1S to R ^3S each independently represent a hydrogen atom, an alkyl group, a cycloalkyl group, a halogen atom, a cyano group, an alkoxy group or an alkoxycarbonyl group, R ^6S represents an organic group, and R ^7S represents - For substituents other than COOR ^5S , when there are multiple R ^7S , the plural R ^7S may be the same or different. R ^5S represents a group that is detached by the action of an acid. R ^8S represents a substituent, and there are multiple R ^8S . When , a plurality of R ^8S may be the same or different, and a plurality of R ^8S may be bonded. m4 represents an integer from 1 to 3, m5 represents an integer from 0 to 4, and m6 represents an integer from 0 to (2×m4+6). [3] The photosensitive radiation or radiation-sensitive resin composition according to [1] or [2], wherein the compound (B) is a compound represented by the following general formula (P1).

[Chemistry 5]

In the general formula (P1), R ^1P to R ^5P each independently represent a hydrogen atom, an alkyl group, a cycloalkyl group, an aryl group, a hydroxyl group, an alkoxy group or a cycloalkoxy group, and R ^1P to R ^5P do not contain a fluorine atom. Mp ⁺ represents a cation. [4] The photosensitive radiation-sensitive or radiation-sensitive resin composition according to any one of [1] to [3], wherein the compound (B) is generated by irradiation with actinic radiation or radiation. The ClogP value of the acid is 3.5 or less. [5] The photosensitive radiation-sensitive or radiation-sensitive resin composition according to any one of [1] to [4], wherein the compound (C) is a compound represented by the following general formula (Q2).

[Chemical 6]

In the general formula (Q2), R ^2Z to R ^6Z independently represent a hydrogen atom, an alkyl group, a cycloalkyl group, an aryl group, a hydroxyl group, an alkoxy group, a cycloalkoxy group, a fluorine atom or an iodine atom, and Mq ⁺ represents a cation. . [6] The photosensitive radiation-sensitive or radiation-sensitive resin composition according to any one of [1] to [5], wherein at least one of Mq ⁺ and Mp ⁺ is represented by the following general formula (KT- 1) represents the cation.

[Chemical 7]

In the general formula (KT-1), R ^KT1 , R ^KT2 and R ^KT3 independently represent an alkyl group, a cycloalkyl group, a halogen atom, a cyano group, an alkoxy group or an alkoxycarbonyl group, and there are multiple R ^KT1 , R When ^KT2 and R ^KT3 , a plurality of R ^KT1 , a plurality of R ^KT2 and a plurality of R ^KT3 may be the same or different respectively. w1, w2 and w3 respectively independently represent integers from 0 to 5, where among w1, w2 and w3 At least one of represents an integer above 1. [7] The photosensitive radiation-sensitive or radiation-sensitive resin composition according to any one of [1] to [6], wherein the repeating unit represented by the above general formula (N1) in the above-mentioned resin (A) The content is 65 mol% or more relative to all the repeating units in the above-mentioned resin (A). [8] The photosensitive radiation-sensitive or radiation-sensitive resin composition according to any one of [1] to [7], wherein the repeating unit represented by the above general formula (S1) in the above-mentioned resin (A) The content is 25 mol% or more relative to all the repeating units in the above-mentioned resin (A). [9] The photosensitive radiation-sensitive or radiation-sensitive resin composition according to any one of [1] to [8], wherein the repeating unit contained in the above-mentioned resin (A) is composed only of the above-mentioned general formula ( The repeating unit represented by N1) and the repeating unit represented by the above general formula (S1). [10] The photosensitive radiation-sensitive or radiation-sensitive resin composition according to any one of [1] to [9], wherein the weight average molecular weight of the resin (A) is 8,000 or less. [11] The photosensitive radiation or radiation-sensitive resin composition according to any one of [1] to [10], wherein the dispersion degree of the resin (A) is 1.7 or less. [12] The photosensitive radiation or radiation-sensitive resin composition according to any one of [1] to [11], wherein the compound (B) has an acid-decomposable group. [13] A resist film formed using the photosensitive radiation or radiation-sensitive resin composition described in any one of [1] to [12]. [14] A pattern forming method, which includes a process of forming a resist film on a substrate using the photosensitive radiation-sensitive or radiation-sensitive resin composition described in any one of [1] to [12]; The process of exposing the resist film; and the process of developing the exposed resist film using a developer. [15] A method of manufacturing electronic components, which includes the pattern forming method described in [14]. [Effects of the invention]

According to the present invention, it is possible to provide a photosensitive radiation-sensitive or radiation-sensitive resin composition capable of suppressing the occurrence of defects when forming an extremely fine pattern (for example, a line width of 30 nm or less). Furthermore, according to the present invention, it is possible to provide a resist film, a pattern forming method, and an electronic component manufacturing method using the above-mentioned photosensitive radiation or radiation-sensitive resin composition.

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.

In this specification, "actinic rays" or "radiation" means, for example, far ultraviolet rays, extreme ultraviolet rays (EUV: Extreme Ultraviolet), X-rays, soft X-rays and electron beams (EB: Electron Beam). In this specification, "light" means actinic rays or radiation. In this specification, the so-called "exposure", unless otherwise specified, includes not only exposure using far ultraviolet, extreme ultraviolet X-rays and EUV represented by the bright line spectrum of mercury lamps and excimer lasers, but also includes the use of electron beams and ion beams and other particle beams. In this specification, "～" is used in the sense that the numerical values described before and after it are included as the lower limit value and the upper limit value.

In this specification, (meth)acrylate means at least one of acrylate and methacrylate. Moreover, (meth)acrylic acid means at least one kind of acrylic acid and methacrylic acid.

In this specification, the weight average molecular weight (Mw), number average molecular weight (Mn) and dispersion (also called "molecular weight distribution") (Mw/Mn) of the resin are measured using GPC (Gel Permeation Chromatography). ) device (HLC-8120GPC manufactured by Tosoh Corporation) measured by GPC (solvent: tetrahydrofuran, flow rate (sample injection amount): 10 μL, column: TSK gel Multipore HXL-M manufactured by Tosoh Corporation, column temperature: 40℃, flow rate: 1.0mL/min, detector: differential refractive index detector (Refractive Index Detector)) and defined by the polystyrene conversion value.

Regarding the expressions of groups (atomic groups) in this specification, as long as they do not violate the gist of the present invention, those that do not describe substituted or unsubstituted include both groups without substituents and groups containing substituents. For example, the so-called "alkyl group" includes not only an alkyl group having no substituent (unsubstituted alkyl group) but also an alkyl group having a substituent (substituted alkyl group). In addition, the so-called "organic group" in this specification means a group containing at least one carbon atom. As the substituent, unless otherwise specified, a monovalent substituent is preferred. Examples of the substituent include monovalent non-metal atomic groups other than hydrogen atoms. For example, the substituent T can be selected from the following.

(Substituent T) Examples of the substituent T include halogen atoms such as fluorine atom, chlorine atom, bromine atom and iodine atom; alkoxy groups such as methoxy group, ethoxy group and tert-butoxy group; cycloalkoxy group; phenoxy group and Aryloxy groups such as p-tolyloxy; alkoxycarbonyl groups such as methoxycarbonyl and butoxycarbonyl; cycloalkoxycarbonyl; aryloxycarbonyl groups such as phenoxycarbonyl; acetyloxy, propyloxy and benzyl Carboxyl groups such as acyloxy group; acylyl groups such as acetyl group, benzyl group, isobutyl group, acryl group, methacryl group and methyl oxalyl group; sulfide group; methylthio group and tert-butyl sulfide group alkylthio groups such as alkylthio groups; arylthio groups such as phenylthio and p-tolylthio groups; alkyl groups; alkenyl groups; cycloalkyl groups; aryl groups; aromatic heterocyclic groups; hydroxyl groups; carboxyl groups; carboxyl groups; sulfo groups; cyanide groups. group; alkylaminocarbonyl group; arylaminocarbonyl group; sulfonamide group; silyl group; amine group; amine methane group, etc. Moreover, when these substituents may further have one or more substituents, as the further substituent, a group having one or more substituents selected from the above-mentioned substituents (for example, monoalkylamino group, dialkylamine group group, arylamine group, trifluoromethyl, etc.) are also included in the examples of the substituent T.

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

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

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

In this specification, pKa, as mentioned above, refers to a value obtained by calculation using the software package 1 based on the Hammett substituent constant and the value of the database of known literature values. However, it cannot be calculated using this method. For pKa, the value obtained by Gaussian16 based on DFT (density functional theory) is used. In this specification, pKa refers to "pKa in aqueous solution" as shown above. However, when the pKa in aqueous solution cannot be calculated, "pKa in dimethylstyrene (DMSO) solution" is used. ”.

In this specification, "solid content" means a component that forms a photosensitive radiation-sensitive film or a radiation-sensitive film, and does not contain a solvent. In addition, as long as it is a component that forms a photosensitive radiation or a radiation-sensitive film, it is regarded as a solid component even if its nature is liquid.

＜Photosensitive radiation or radiation-sensitive resin composition＞ The photosensitive radiation-sensitive or radiation-sensitive resin composition of the present invention (also referred to as the "composition of the present invention") contains at least a resin (A) and a compound (B) that generates acid upon irradiation with actinic rays or radiation. ), and a photosensitive radiation-sensitive or radiation-sensitive resin composition of a compound (C) different from compound (B), wherein the resin (A) contains a repeating unit represented by the general formula (N1) and a compound represented by the general formula (N1) S1), and the content of the repeating unit represented by the general formula (N1) in the resin (A) is 55 mol% or more relative to all the repeating units in the resin (A), and the compound (C) is A compound represented by general formula (Q1).

[Chemical 8]

In the general formula (N1), R ^1N to R ^3N each independently represent a hydrogen atom, an alkyl group, a cycloalkyl group, a halogen atom, a cyano group, an alkoxy group or an alkoxycarbonyl group. R ^4N represents a hydrogen atom or a substituent other than a hydroxyl group. R ^4N may be bonded to at least one of R ^1N to R ^3N . When there are a plurality of R ^4Ns , the plurality of R ^4Ns may be the same or different, and the plurality of R ^4Ns may be bonded. k1 means 0 or 1. When k1 represents 0, k2 represents an integer from 1 to 5, and k3 represents 5-k2. When k1 represents 1, k2 represents an integer from 1 to 7, and k3 represents 7-k2.

[Chemical 9]

In the general formula (S1), R ^1S to R ^3S each independently represent a hydrogen atom, an alkyl group, a cycloalkyl group, a halogen atom, a cyano group, an alkoxy group or an alkoxycarbonyl group. R ^4S represents a hydrogen atom or a substituent other than -COOR ^5S . R ^4S may be bonded to at least one of R ^1S to R ^3S . When there are a plurality of R ^4S , the plurality of R ^4S may be the same or different, and the plurality of R ^4S may be bonded. R ^5S represents a group separated by the action of an acid. When there are a plurality of R ^5S , the plurality of R ^5S may be the same or different. m1 means 0 or 1. When m1 represents 0, m2 represents an integer from 1 to 5, and m3 represents 5-m2. When m1 represents 1, m2 represents an integer from 1 to 7, and m3 represents 7-m2.

[Chemical 10]

In the general formula (Q1), R ^1Z represents an organic group, and Mq ⁺ represents a cation.

The reason why the composition of the present invention can suppress the occurrence of defects when forming an extremely fine pattern (for example, a line width of 30 nm or less) is not clear, but the inventors speculate as follows. The resin (A) contained in the composition of the present invention contains a repeating unit represented by the general formula (N1) and a repeating unit represented by the general formula (S1), and the content of the repeating unit represented by the general formula (N1) is relatively More than 55 mol% of all repeating units. The hydrophobicity of the resin (A) can be appropriately adjusted by setting the content of the repeating unit represented by the general formula (N1) to 55 mol% or more based on the total repeating units. In addition, the repeating unit represented by the general formula (S1) has an acid-decomposable group, and R ^5S is detached by exposure to generate a carboxyl group bonded to an aromatic ring. Therefore, the dissolution contrast can be improved. Furthermore, the compound (C) contained in the composition of the present invention has a structure represented by the general formula (Q1), and is considered to be able to suppress the generation of residues from the viewpoint of solubility in a developer. It is thought that the occurrence of defects can be suppressed by these reasons.

The composition of the present invention is typically a resist composition, and may be a positive resist composition or a negative resist composition. The resist composition of the present invention may be a resist composition for alkali development or a resist composition for organic solvent development. The resist composition of the present invention may be a chemically amplified resist composition or a non-chemically amplified resist composition. The composition of the present invention is typically a chemically amplified resist composition. A photosensitive radiation-sensitive or radiation-sensitive film can be formed using the composition of the present invention. The photosensitive radiation-sensitive or radiation-sensitive film formed using the composition of the present invention is typically a resist film. Below, various components of the composition of the present invention are first described in detail.

[Resin (A)] The resin (A) contains at least a repeating unit represented by the general formula (N1) and a repeating unit represented by the general formula (S1).

(Repeating unit represented by general formula (N1)) The repeating unit represented by general formula (N1) will be explained. R ^1N to R ^3N in the general formula (N1) each independently represent a hydrogen atom, an alkyl group, a cycloalkyl group, a halogen atom, a cyano group, an alkoxy group or an alkoxycarbonyl group. The alkyl groups of R ^1N to R ^3N may be either linear or branched. The number of carbon atoms in the alkyl group is not particularly limited, but is preferably 1 to 5, more preferably 1 to 3. The number of carbon atoms in the cycloalkyl group of R ^1N to R ^3N is not particularly limited, but is preferably 3 to 20, more preferably 5 to 15. The cycloalkyl groups of R ^1N to R ^3N may be monocyclic cycloalkyl groups such as cyclopentyl and cyclohexyl, or may be norbornyl, tetracyclodecyl, tetracyclododecyl, adamantyl, etc. Ring cycloalkyl. Examples of the halogen atom of R ^1N to R ^3N include a fluorine atom, a chlorine atom, a bromine atom, and an iodine atom, and a fluorine atom or an iodine atom is preferred. The alkyl group contained in the alkoxy group of R ^1N to R ^3N may be either linear or branched. The carbon number of the alkyl group contained in the alkoxy group is not particularly limited, but is preferably 1 to 5, more preferably 1 to 3. The alkyl group contained in the alkoxycarbonyl group of R ^1N to R ^3N may be either linear or branched. The number of carbon atoms of the alkyl group contained in the alkoxycarbonyl group is not particularly limited, but is preferably 1 to 5, more preferably 1 to 3. R ^1N to R ^3N preferably represent a hydrogen atom or a methyl group, more preferably a hydrogen atom.

k1 in the general formula (N1) represents 0 or 1. When k1 represents 0, the aromatic ring described in the general formula (N1) represents a benzene ring. When k1 represents 1, the aromatic ring described in the general formula (N1) represents a naphthalene ring. When k1 represents 0, k2 represents an integer from 1 to 5, and k3 represents 5-k2. When k1 represents 1, k2 represents an integer from 1 to 7, and k3 represents 7-k2. k1 preferably represents 0. k2 is preferably an integer representing 1 to 3, more preferably 1 or 2, and still more preferably 1.

R ^4N in the general formula (N1) represents a hydrogen atom or a substituent other than a hydroxyl group. The substituent represented by R ^4N is not particularly limited as long as it is a substituent other than a hydroxyl group. Examples thereof include a carboxyl group, a halogen atom (preferably a fluorine atom or an iodine atom), and an alkyl group (preferably a carbon number of 1 to 1). 5 alkyl group), alkenyl group (preferably an alkenyl group having 2 to 5 carbon atoms), alkoxy group (preferably an alkoxy group having 1 to 5 carbon atoms), etc. R ^4N preferably represents a hydrogen atom. When there are a plurality of R ^4Ns , the plurality of R ^4Ns may be the same or different, and the plurality of R ^4Ns may be bonded.

R ^4N may be bonded to at least one of R ^1N to R ^3N . For example, examples of the case where R ^4N and R ^3N are bonded include a repeating unit represented by the general formula (N1-2) and a repeating unit represented by the general formula (N1-3), which will be described later.

The repeating unit represented by the general formula (N1) is preferably a repeating unit represented by the following general formula (N1-1), a repeating unit represented by the following general formula (N1-2), or a repeating unit represented by the following general formula (N1-2) N1-3) represents the repeating unit.

[Chemical 11]

In the general formula (N1-1), R ^1N to R ^4N and k1 to k3 respectively have the same meanings as R ^1N to R ^4N and k1 to k3 in the general formula (N1), and the specific examples and preferred ranges are also the same.

[Chemical 12]

In the general formula (N1-2), R ^1N , R ^2N , R ^4N , and k1 respectively represent the same meanings as R ^1N , R ^2N , R ^4N , and k1 in the general formula (N1). Specific examples are preferred. The scope is also the same. L ^1N represents a single bond or an alkylene group. The alkylene group represented by L ^1N is preferably an alkylene group having 1 to 5 carbon atoms, more preferably an alkylene group having 1 to 3 carbon atoms. When k1 represents 0, k4 represents an integer from 1 to 4, and k5 represents 4-k4. When k1 represents 1, k4 represents an integer from 1 to 6, and k5 represents 6-k4. k4 is preferably an integer representing 1 to 3, more preferably 1 or 2, and still more preferably 1.

[Chemical 13]

In the general formula (N1-3), R ^1N , R ^2N , and R ^4N respectively have the same meanings as R ^1N , R ^2N , and R ^4N in the general formula (N1), and the specific examples and preferred ranges are also the same. k6 represents an integer from 1 to 6, and k7 represents 6-k6. k6 is preferably an integer representing 1 to 3, more preferably 1 or 2, and still more preferably 1.

The repeating unit represented by the general formula (N1) is particularly preferably a repeating unit represented by the above-mentioned general formula (N1-1), and most preferably is a repeating unit represented by the following general formula (N2).

[Chemical 14]

In the general formula (N2), R ^1N to R ^3N each have the same meaning as R ^1N to R ^3N in the general formula (N1), and the specific examples and preferred ranges are also the same. R ^6N represents a substituent other than hydroxyl group. k8 represents an integer from 1 to 5. k9 means 0~(5-k8). Examples of the substituent represented by R ^6N include a carboxyl group, a halogen atom (preferably a fluorine atom or an iodine atom), an alkyl group (preferably an alkyl group having 1 to 5 carbon atoms), and an alkenyl group (preferably a fluorine atom or an iodine atom). Alkenyl group having 2 to 5 carbon atoms), alkoxy group (preferably alkoxy group having 1 to 5 carbon atoms), etc. k8 is preferably an integer representing 1 to 3, more preferably 1 or 2, and still more preferably 1. k9 is preferably an integer representing 0 to 2, more preferably 0 or 1, and still more preferably 0.

Specific examples of the repeating unit represented by the general formula (N1) are shown below, but are not limited thereto.

[Chemical 15]

The number of repeating units represented by the general formula (N1) contained in the resin (A) may be one type, or two or more types.

The content of the repeating unit represented by the general formula (N1) in the resin (A) is 55 mol% or more, preferably 65 mol% or more, based on all the repeating units in the resin (A). Moreover, the content of the repeating unit represented by the general formula (N1) in the resin (A) is preferably 90 mol% or less, more preferably 80 mol% or less based on all the repeating units in the resin (A). , further preferably 75 mol% or less.

(Repeating unit represented by general formula (S1)) The resin (A) contains a repeating unit represented by general formula (S1). The repeating unit represented by the general formula (S1) is preferably a repeating unit different from the repeating unit represented by the general formula (N1). R ^1S to R ^3S in the general formula (S1) each independently represent a hydrogen atom, an alkyl group, a cycloalkyl group, a halogen atom, a cyano group or an alkoxycarbonyl group. The alkyl groups of R ^1S to R ^3S may be either linear or branched. The number of carbon atoms in the alkyl group is not particularly limited, but is preferably 1 to 5, more preferably 1 to 3. The number of carbon atoms in the cycloalkyl group of R ^1S to R ^3S is not particularly limited, but is preferably 3 to 20, more preferably 5 to 15. The cycloalkyl groups of R ^1S to R ^3S may be monocyclic cycloalkyl groups such as cyclopentyl and cyclohexyl, or may be norbornyl, tetracyclodecyl, tetracyclododecyl, adamantyl, etc. Ring cycloalkyl. Examples of the halogen atom of R ^1S to R ^3S include a fluorine atom, a chlorine atom, a bromine atom and an iodine atom, and a fluorine atom or an iodine atom is preferred. The alkyl group contained in the alkoxy group of R ^1S to R ^3S may be either linear or branched. The carbon number of the alkyl group contained in the alkoxy group is not particularly limited, but is preferably 1 to 5, more preferably 1 to 3. The alkyl group contained in the alkoxycarbonyl group of R ^1S to R ^3S may be either linear or branched. The number of carbon atoms of the alkyl group contained in the alkoxycarbonyl group is not particularly limited, but is preferably 1 to 5, more preferably 1 to 3. R ^1S to R ^3S preferably represent a hydrogen atom or a methyl group, more preferably a hydrogen atom.

m1 in the general formula (S1) represents 0 or 1. When m1 represents 0, the aromatic ring described in the general formula (S1) represents a benzene ring. When m1 represents 1, the aromatic ring described in the general formula (S1) represents a naphthalene ring. When m1 represents 0, m2 represents an integer from 1 to 5, and m3 represents 5-m2. When m1 represents 1, m2 represents an integer from 1 to 7, and m3 represents 7-m2. m1 preferably represents 0. m2 is preferably an integer representing 1 to 3, more preferably 1 or 2, and still more preferably 1.

R ^4S in the general formula (S1) represents a hydrogen atom or a substituent other than -COOR ^5S . The substituent represented by R ^4S is not particularly limited as long as it is a substituent other than -COOR ^5S . Examples include a halogen atom (preferably a fluorine atom or an iodine atom), an alkyl group (preferably a carbon number of 1 to 5 alkyl group), alkenyl group (preferably an alkenyl group having 2 to 5 carbon atoms), alkoxy group (preferably an alkoxy group having 1 to 5 carbon atoms), etc. R ^4S preferably represents a hydrogen atom. When there are a plurality of R ^4S , the plurality of R ^4S may be the same or different, and the plurality of R ^4S may be bonded.

R ^4S may be bonded to at least one of R ^1S to R ^3S . For example, examples of the case where R ^4S and R ^3S are bonded include a repeating unit represented by the general formula (S1-2) and a repeating unit represented by the general formula (S1-3), which will be described later.

-COOR ^5S is an acid-decomposable group. -COOR ^5S is decomposed by the action of acid (R ^5S is detached) to produce -COOH. Since the resin (A) contains a repeating unit represented by the general formula (S1), typically, the polarity increases by the action of an acid, thereby increasing the solubility in an alkali developer and decreasing the solubility in an organic solvent. . R ^5S represents a group (leaving group) that is released by the action of an acid. When there are a plurality of R ^5S , the plurality of R ^5S may be the same or different. R ^5S is preferably a group represented by formula (Y1). Formula (Y1): -C(Rx ₁ )(Rx ₂ )(Rx ₃ ) In the formula (Y1), Rx ₁ to Rx ₃ each independently represent an organic group. As the organic group, an alkyl group (linear or branched), a cycloalkyl group (monocyclic or polycyclic), an alkenyl group (linear or branched), or an aryl group (monocyclic or polycyclic) is preferred. ring). When all Rx ₁ to Rx ₃ are alkyl groups (linear or branched), at least two of Rx ₁ to Rx ₃ are preferably methyl groups. 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 single ring or a polycyclic ring. The alkyl groups of Rx ₁ to Rx ₃ are preferably alkyl groups having 1 to 5 carbon atoms such as methyl, ethyl, n-propyl, isopropyl, n-butyl, isobutyl and tert-butyl. The cycloalkyl groups of Rx ₁ to Rx ₃ may be monocyclic cycloalkyl groups such as cyclopentyl and cyclohexyl, norbornyl, tetracyclodecyl, tetracyclododecyl, adamantyl, etc. Ring cycloalkyl. 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. As the alkenyl group of Rx ₁ to Rx ₃ , vinyl group is preferred. The ring formed by two of Rx ₁ to Rx ₃ bonding is preferably a cycloalkyl group. The cycloalkyl group formed by bonding two of Rx ₁ to Rx ₃ is preferably a monocyclic cycloalkyl group such as cyclopentyl or cyclohexyl, or a norbornyl group, a tetracyclodecyl group, or a tetracyclododecanyl group. 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. A cycloalkyl group formed by bonding two of Rx ₁ to Rx ₃ , in which one of the methylene groups constituting the ring may be substituted by a heteroatom such as an oxygen atom, a heteroatom-containing group such as a carbonyl group, or a vinylidene group. In these cycloalkyl groups, one or more ethylene groups constituting the cycloalkane ring may be substituted with vinylidene groups. The group represented by the formula (Y1) 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 above-mentioned cycloalkyl group. When the composition of the present invention is, for example, a resist composition for EUV exposure, an alkyl group, a cycloalkyl group, an alkenyl group, an aryl group represented by Rx ₁ to Rx ₃ , and an alkyl group represented by Rx ₁ to Rx ₃ The ring formed by two bonds further preferably has a fluorine atom or an iodine atom as a substituent.

The repeating unit represented by the general formula (S1) is preferably a repeating unit represented by the following general formula (S1-1), a repeating unit represented by the following general formula (S1-2), or a repeating unit represented by the following general formula (S1-2) S1-3) represents the repeating unit.

[Chemical 16]

In the general formula (S1-1), R ^1S to R ^5S and m1 to m3 respectively have the same meanings as R ^1S to R ^5S and m1 to m3 in the general formula (S1), and the specific examples and preferred ranges are also the same.

[Chemical 17]

In the general formula (S1-2), R ^1S , R ^2S , R ^4S , R ^5S , and m1 respectively have the same meanings as R ^1S , R ^2S , R ^4S , R ^5S , and m1 in the general formula (S1). , the specific examples and preferred ranges are also the same. L ^1S represents a single bond or an alkylene group. The alkylene group represented by L ^1S is preferably an alkylene group having 1 to 5 carbon atoms, more preferably an alkylene group having 1 to 3 carbon atoms. When m1 represents 0, n1 represents an integer from 1 to 4, and n2 represents 4-n1. When m1 represents 1, n1 represents an integer from 1 to 6, and n2 represents 6-n1. n1 is preferably an integer representing 1 to 3, more preferably 1 or 2, and still more preferably 1.

[Chemical 18]

In the general formula (S1-3), R ^1S , R ^2S , R ^4S , and R ^5S respectively represent the same meanings as R ^1S , R ^2S , R ^4S , and R ^5S in the general formula (S1). Specific examples are as follows The preferred range is also the same. n3 represents an integer from 1 to 6, and n4 represents 6-n3. n3 is preferably an integer representing 1 to 3, more preferably 1 or 2, and still more preferably 1.

The repeating unit represented by the general formula (S1) is particularly preferably a repeating unit represented by the above-mentioned general formula (S1-1), and most preferably is a repeating unit represented by the following general formula (S2). The repeating unit represented by the following general formula (S2) has a large difference in dissolution rate before and after deprotection, so it has high solubility after deprotection and is less likely to leave residues.

[Chemical 19]

In the general formula (S2), R ^1S to R ^3S each independently represent a hydrogen atom, an alkyl group, a cycloalkyl group, a halogen atom, a cyano group, an alkoxy group or an alkoxycarbonyl group. R ^6S represents an organic group. R ^7S represents a substituent other than -COOR ^5S . When there are a plurality of R ^7S , the plurality of R ^7S may be the same or different. R ^5S represents a group separated by the action of an acid. R ^8S represents a substituent. When there are a plurality of R ^8S , the plurality of R ^8S may be the same or different, and the plurality of R ^8S may be bonded. m4 represents an integer from 1 to 3. m5 represents an integer from 0 to 4. m6 represents an integer from 0 to (2×m4+6).

In the general formula (S2), R ^1S to R ^3S each have the same meaning as R ^1S to R ^3S in the general formula (S1), and the specific examples and preferred ranges are also the same. R ^6S represents an organic group and may be linear or branched. The organic group of R ^6S is preferably a hydrocarbon group having 1 to 6 carbon atoms, more preferably a hydrocarbon group having 1 to 5 carbon atoms, and even more preferably a hydrocarbon group having 1 to 4 carbon atoms. As the organic group, an alkyl group (linear or branched) or alkenyl group (linear or branched) is preferred.

R ^7S in the general formula (S2) represents a substituent other than -COOR ^5S . R ^5S has the same meaning as R ^5S in the general formula (S1), and the specific examples and preferred ranges are also the same. Examples of the substituent represented by R ^7S include a halogen atom (preferably a fluorine atom or an iodine atom), an alkyl group (preferably an alkyl group having 1 to 5 carbon atoms), and an alkenyl group (preferably a carbon atom). Alkenyl group with 2 to 5 carbon atoms), alkoxy group (preferably alkoxy group with 1 to 5 carbon atoms), etc.

R ^8S in the general formula (S2) represents a substituent. Examples of the substituent represented by R ^8S include a halogen atom (preferably a fluorine atom or an iodine atom), an alkyl group (preferably an alkyl group having 1 to 5 carbon atoms), and an alkenyl group (preferably a carbon atom). Alkenyl group with 2 to 5 carbon atoms), alkoxy group (preferably alkoxy group with 1 to 5 carbon atoms), etc.

m4 represents an integer from 1 to 3, preferably 1 or 2. m5 represents an integer of 0 to 4, preferably an integer of 0 to 2, more preferably 0 or 1, and still more preferably 0. m6 represents an integer from 0 to (2×m4+6), preferably an integer from 0 to 4, more preferably 0 or 1, and still more preferably 0.

Specific examples of the repeating unit represented by general formula (S1) are shown below, but are not limited thereto.

[Chemistry 20]

The number of repeating units represented by the general formula (S1) contained in the resin (A) may be one type, or two or more types.

The content of the repeating unit represented by the general formula (S1) in the resin (A) is preferably 20 mol% or more, more preferably 25 mol%, based on all the repeating units in the resin (A). Moreover, the content of the repeating unit represented by the general formula (A2) in the resin (A) is preferably 45 mol% or less, more preferably 40 mol% or less based on all the repeating units in the resin (A). , further preferably 35 mol% or less.

The resin (A) may further contain other repeating units in addition to the repeating unit represented by the general formula (N1) and the repeating unit represented by the general formula (S1). The content of other repeating units is preferably 0 to 40 mol%, more preferably 0 to 20 mol%, and further preferably 0 to 10 mol% based on all the repeating units in the resin (A). The repeating units contained in the resin (A) are preferably only the repeating units represented by the general formula (N1) and the repeating units represented by the general formula (S1) (that is, the resin (A) does not contain other repeating units) .

The resin (A) may contain at least one repeating unit selected from the group consisting of the following group A and/or at least one repeating unit selected from the group consisting of the following group B. Group A: A group consisting of the following repeating units (20) to (25). (20) Repeating unit having an acid group described below (21) A repeating unit having no acid-decomposable group or acid group but having a fluorine atom, a bromine atom or an iodine atom, as described below (22) Repeating unit having a lactone group, a sultone group or a carbonate group described below (23) Repeating unit having a photoacid generating group described below (24) Repeating unit represented by formula (V-1) or the following formula (V-2) described below (25) Repeating units used to reduce the mobility of the main chain In addition, the repeating units represented by the formulas (A) to (E) described below correspond to (25) the repeating units for reducing the mobility of the main chain. Group B: A group consisting of the following repeating units (30) to (32). (30) A repeating unit having at least one group selected from the group consisting of a lactone group, a sultone group, a carbonate group, a hydroxyl group, a cyano group, and an alkali-soluble group, as described below (31) A repeating unit described below that has an alicyclic hydrocarbon structure and does not show acid decomposability (32) The repeating unit represented by formula (III) described below and having neither a hydroxyl group nor a cyano group

(Repeating unit having an acid group) The resin (A) may further have a repeating unit containing an acid group in addition to the repeating unit represented by the general formula (N1) and the repeating unit represented by the general formula (S1). As the acid group, an acid group having a pKa of 13 or less is preferred. The acid dissociation constant of the acid group is preferably 13 or less, more preferably 3 to 13, and still more preferably 5 to 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 in many cases it is 0.2 to 6.0 mmol/g. Among them, 0.8 to 6.0 mmol/g is preferred, 1.2 to 5.0 mmol/g is more preferred, and 1.6 to 4.0 mmol/g is further preferred. If the content of the acid group is within the above range, development will proceed favorably, the shape of the formed pattern will be excellent, and the resolution will also be excellent. As the acid group, for example, a carboxyl 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-mentioned hexafluoroisopropanol group, one or more (preferably 1 to 2) fluorine atoms may be substituted with groups other than fluorine atoms (alkoxycarbonyl group, etc.). As the acid group, -C(CF ₃ )(OH)-CF ₂ - thus formed is also preferred. Furthermore, one or more fluorine atoms may be substituted with 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 a repeating unit having a structure in which a polar group is protected by a group detached by the action of the above-mentioned acid, and a lactone group, a sultone group or a carbonate group described below. repeating units that are different from each other. The repeating unit having an acid group may have a fluorine atom or an iodine atom.

Examples of the repeating unit having an acid group include the following repeating units.

[Chemistry 21]

(A repeating unit that does not have either an acid-decomposable group or an acid group, but has a fluorine atom, a bromine atom, or an iodine atom) The resin (A) may further have either a non-acid-decomposable group or an acid group, in addition to the repeating unit represented by the general formula (N1) and the repeating unit represented by the general formula (S1), And it has a repeating unit containing a fluorine atom, a bromine atom, or an iodine atom (hereinafter, also referred to as unit X.). The "repeating unit which does not have either an acid-decomposable group or an acid group but has a fluorine atom, a bromine atom or an iodine atom" mentioned here is preferably the same as the <has a lactone group or a sulfonate group which will be described later. Other types of repeating units belonging to group A such as the repeating unit of an ester group or a carbonate group and the <repeating unit having a photoacid generating group> are different.

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

[Chemistry 22]

L ₅ represents a single bond or 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 which may have a fluorine atom or an iodine atom, a cycloalkyl group which may have a fluorine atom or an iodine atom, an aryl group which may have a fluorine atom or an iodine atom, or a group combining these .

Hereinafter, repeating units having a fluorine atom or an iodine atom are exemplified.

[Chemistry 23]

(Repeating unit with lactone group, sultone group or carbonate group) The resin (A) may further have, in addition to the repeating unit represented by the general formula (N1) and the repeating unit represented by the general formula (S1), a lactone group, a sultone group, and a carbonate group selected from the group consisting of At least one repeating unit in the group (hereinafter, also referred to as "unit Y".). It is also preferable that unit Y does not have acidic groups such as hydroxyl group and hexafluoropropanol group. travel

As the lactone group or the sultone group, any one having a lactone structure or a sultone structure may be used. The lactone structure or sultone structure is preferably a 5- to 7-membered ring lactone structure or a 5- to 7-membered ring sultone structure. Among them, more preferred ones are those in which the 5- to 7-membered ring lactone structure has other ring structures condensed to form a bicyclic structure or a spirocyclic structure, or a 5- to 7-membered ring lactone structure in the form of a bicyclic structure or a spirocyclic structure. There are other ring structures in the condensed ring of sultone structure. Resin (A) may have a repeating unit containing a lactone group or a sultone group, and the lactone group or sultone group is one of the following formulas (LC1-1) to (LC1-21) or a sultone structure represented by any of the following formulas (SL1-1) to (SL1-3), which is formed by removing one or more hydrogen atoms from the ring member atoms, or it can be internalized The ester group or sultone group is directly bonded to the main chain. For example, the ring member atoms of the lactone group or the sultone group may also constitute the main chain of the resin (A).

[Chemistry 24]

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

As having a lactone structure represented by any one of formulas (LC1-1) to (LC1-21) or a sultone structure represented by any one of formulas (SL1-1) to (SL1-3) Examples of the repeating unit of the group include repeating units represented by the following formula (AI).

[Chemical 25]

In the formula (AI), Rb ₀ represents a hydrogen atom, a halogen atom, or an alkyl group having 1 to 4 carbon atoms. Preferable substituents that the alkyl group of Rb ₀ may have include hydroxyl groups and halogen atoms. 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 bivalent linking group having a monocyclic or polycyclic alicyclic hydrocarbon structure, an ether group, an ester group, a carbonyl group, a carboxyl group, or a bivalent linkage 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 cycloalkyl group, preferably a methyl group, an ethyl group, a cyclohexyl group, an adamantyl group or an norbornene group. 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 by the formula (SL1-1) A group formed by removing one hydrogen atom from the ring member atom of the sultone structure represented by any one 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. In addition, one optical isomer may be used alone, or a plurality of optical isomers may be mixed and used. When mainly using one optical isomer, its optical purity (ee) is preferably 90 or more, more preferably 95 or more.

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 preferred.

[Chemical 26]

In 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 above 0. R _A ² represents a substituent. When n is 2 or more, there are a plurality of _RA ² 's, which may be the same or different. A represents a single bond or a divalent linking group. The bivalent connecting group is preferably an alkylene group, a bivalent connecting 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. into a bivalent linking base. Z represents an atomic group forming a monocyclic or polycyclic ring together with the group represented by -O-CO-O- in the formula.

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

[Chemical 27]

[Chemical 28]

(Repeating unit with photoacid generating group) The resin (A), in addition to the repeating unit represented by the general formula (N1) and the repeating unit represented by the general formula (S1), may further contain a group that generates an acid by irradiation with actinic rays or radioactive rays. A repeating unit of a group (hereinafter also referred to as "photoacid generating group"). Examples of the repeating unit containing the photoacid generating group include the repeating unit represented by formula (4).

[Chemical 29]

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 bivalent linking group. R ⁴⁰ represents a structural site that is decomposed by irradiation with actinic rays or radioactive rays to produce an acid in the side chain. Hereinafter, repeating units having a photoacid generating group are exemplified, but are not limited thereto.

[Chemical 30]

Examples of the repeating unit represented by formula (4) include the repeating units described in paragraphs [0094] to [0105] of Japanese Patent Application Laid-Open No. 2014-041327, and International Publication No. 2018/193954. Repeating units described in paragraph [0094] of the publication.

(Repeating unit represented by formula (V-1) or the following formula (V-2)) The resin (A) may further have the following formula (V-1) or the following formula (V) in addition to the repeating unit represented by the general formula (N1) and the repeating unit represented by the general formula (S1). -2) represents the repeating unit. 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 31]

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

(repeating unit used to reduce the mobility of the main chain) 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 development. The Tg is preferably greater than 90°C, more preferably greater than 100°C, further preferably greater than 110°C, and particularly preferably greater than 125°C. In addition, from the viewpoint of having a good dissolution rate in a developer, Tg is preferably 400°C or lower, more preferably 350°C or lower. In addition, in this specification, the glass transition temperature (Tg) (hereinafter also referred to as "Tg of the repeating unit") of polymers such as resin (A) is calculated by the following method. First, the Tg of the homopolymer consisting only of each repeating unit contained in the polymer was calculated by the Bicerano method. Next, the mass ratio (%) of each repeating unit relative to all repeating units in the polymer is calculated. Next, the Tg at each mass ratio was calculated using Fox's formula (described in Materials Letters 62 (2008) 3152, etc.), and the sum was calculated as the Tg (°C) of the polymer. The Bicerano method is described in Prediction of polymer properties, Marcel Dekker Inc, New York (1993). When calculating Tg using the Bicerano method, the polymer physical property evaluation software MDL Polymer (MDL Information Systems, Inc.) can be used for calculation.

In order to increase the Tg of the resin (A) (preferably, the Tg exceeds 90° C.), it is preferable to reduce the mobility of the main chain of the resin (A). Methods for reducing the mobility of the main chain of 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 inducing interaction between resins (A) near the main chain (d) Forming a main chain in a ring structure (e) Connect the cyclic structure to the main chain Moreover, it is preferable that resin (A) has a repeating unit whose Tg of a homopolymer shows 130 degreeC or more. In addition, the type of the repeating unit whose Tg of the homopolymer shows 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, the repeating units represented by formulas (A) to (E) to be described later correspond to repeating units whose Tg of the homopolymer shows 130° C. or higher depending on the type of functional groups therein.

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

[Chemical 32]

In formula (A), R _A represents a group containing a polycyclic structure. R _x represents a hydrogen atom, methyl group or ethyl group. The so-called 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 formula (A) include the repeating units described in paragraphs [0107] to [0119] of International Publication No. 2018/193954.

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

[Chemical 33]

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

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

[Chemical 34]

In the 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 atom with hydrogen bonding properties 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 properties within 2 atoms (closer to the main chain side) are preferred. Specific examples of the repeating unit represented by formula (C) include the repeating units described in paragraphs [0119] to [0121] of International Publication No. 2018/193954.

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

[Chemical 35]

In formula (D), "Cyclic" represents a group forming 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 formula (D) include the repeating units described in paragraphs [0126] to [0127] of International Publication No. 2018/193954.

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

[Chemical 36]

In formula (E), Re each independently represents a hydrogen atom or an organic group. Examples of the organic group include an alkyl group, a cycloalkyl group, an aryl group, an aralkyl group and an alkenyl group which may have a substituent. "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 formula (E) include the 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 containing 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 containing a lactone group, a sultone group or a carbonate group that the resin (A) has include those described in the above <Repeating unit containing a lactone group, a sultone group or a carbonate group> of repeating units. The preferred content is also the content described in the above <Repeating unit containing lactone group, sultone group or carbonate group>.

The resin (A) may have repeating units containing a hydroxyl group or a cyano group. This can improve substrate adhesion and developer affinity. The repeating unit having a hydroxyl group or a cyano group is preferably a repeating unit having an alicyclic hydrocarbon structure substituted with a hydroxyl group or a cyano group. The repeating unit having a hydroxyl group or a cyano group preferably does not have an acid-decomposable group. Examples of the repeating unit having a hydroxyl group or a cyano group include the repeating units described in paragraphs [0081] to [0084] of Japanese Patent Application Laid-Open No. 2014-098921.

The resin (A) may have a repeating unit containing an alkali-soluble group. Examples of the alkali-soluble group include a carboxyl group, a sulfonamide group, a sulfonimide group, a disulfonimide group, and an aliphatic alcohol group substituted at the α-position with an electron-withdrawing group (for example, hexafluoroisopropanol group), preferably carboxyl group. By the resin (A) containing repeating units having alkali-soluble groups, the resolution in contact hole applications can be increased. Examples of the repeating unit having an alkali-soluble group include the repeating units described in paragraphs [0085] and [0086] of Japanese Patent Application Laid-Open No. 2014-098921.

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

(Repeating unit represented by formula (III) and having neither a hydroxyl group nor a cyano group) The resin (A) may have a repeating unit represented by the formula (III) and having neither a hydroxyl group nor a cyano group.

[Chemical 37]

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 a hydroxyl group. Examples of the repeating unit represented by formula (III) and having neither a hydroxyl group nor a cyano group include the repeating units described in paragraphs [0087] to [0094] of Japanese Patent Application Laid-Open No. 2014-098921 .

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

[Chemical 38]

In addition to the above-mentioned repeating structural units, resin (A) may also have various repeats in order to adjust dry etching resistance, standard developer adaptability, substrate adhesion, resist profile, resolution, heat resistance, sensitivity, etc. structural unit.

Resin (A) can be synthesized according to conventional methods (such as free radical polymerization). The weight average molecular weight (Mw) of the resin (A) is preferably 30,000 or less, more preferably 10,000 or less, in terms of polystyrene conversion value using the GPC method, and further preferably 8,000 or less from the viewpoint of reducing defects. Moreover, the weight average molecular weight (Mw) of the resin (A) is preferably 1,000 or more, more preferably 3,000 or more. The dispersion degree (molecular weight distribution, Pd, Mw/Mn) of the resin (A) is preferably 3.0 or less, more preferably 2.0 or less, and from the viewpoint of reducing defects, it is further more preferably 1.7 or less. Moreover, the dispersion degree of resin (A) may be 1.0 or more, and may be 1.2 or more.

The resin (A) contained in the composition of the present invention may be one type, or two or more types.

In the resist composition of the present invention, the content of the resin (A) is preferably 40.0 to 99.9 mass %, more preferably 60.0 to 90.0 mass % with respect to the total solid content of the resist composition of the present invention.

[Compounds (B) that generate acids by exposure to actinic rays or radioactive rays] The composition of the present invention contains a compound (B) that generates acid upon irradiation with actinic rays or radioactive rays. Compound (B) may be in the form of a low molecular compound or may be incorporated into a part of a polymer. Moreover, a form of a low molecular compound and a form of being incorporated into a part of the polymer may be used together. When compound (B) is in the form of a low molecular compound, the molecular weight of compound (B) is preferably 3,000 or less, more preferably 2,000 or less, and still more preferably 1,000 or less. The lower limit is not particularly limited, but is preferably 100 or more. When the compound (B) is incorporated into a part of the polymer, the compound (B) may be incorporated into a part of the resin (A) or may be incorporated into a resin different from the resin (A). Compound (B) is preferably in the form of a low molecular compound.

The ClogP value of the acid generated (acid generated) from compound (B) by irradiation with actinic rays or radioactive rays is preferably 7.5 or less, more preferably 4.5 or less. Since defects can be further reduced, it is even more preferred. is below 3.5. Furthermore, the ClogP value of the acid generated from compound (B) may be 2.5 or more, or may be 3.0 or more. The so-called ClogP value refers to a value obtained by calculating the common logarithm logP of the distribution coefficient P between 1-octanol and water. Regarding the method and software for calculating the ClogP value, well-known programs can be used. Unless otherwise specified, the present invention uses the ClogP program incorporated into ChemBioDraw Ultra 12.0 of Cambridge Soft. Furthermore, when the acid-generating acid-generating group of the compound (B) has an acid-decomposable group, the ClogP value of the structure after the acid-generating acid-decomposable group is decomposed by an acid is preferably within the above range.

In order to further reduce defects, compound (B) preferably has an acid-decomposable group. An acid-decomposable group is a group that decomposes by the action of an acid to generate a polar group. The acid-decomposable group preferably has a structure that protects the polar group with a group (leaving group) that is released by the action of an acid. The polar group is preferably an alkali-soluble group, and examples thereof include carboxyl group, phenolic hydroxyl group, fluorinated alcohol group, sulfonic acid group, phosphate group, sulfonamide group, sulfonimide group, (alkyl sulfonyl group base) (alkylcarbonyl) methylmide group, (alkylsulfonyl) (alkylcarbonyl) amide group, bis (alkylcarbonyl) methyl methylene group, bis (alkylcarbonyl) imine group, bis ( Acidic groups such as alkylsulfonyl)methylmide, bis(alkylsulfonyl)imide, tris(alkylcarbonyl)methylmethylene and tris(alkylsulfonyl)methylmethylene, as well as alcohols Sexual hydroxyl. Among these, the polar group is preferably a carboxyl group, a phenolic hydroxyl group, a fluorinated alcohol group (preferably a hexafluoroisopropanol group), or a sulfonic acid group.

Examples of groups that are detached by the action of 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 each independently represent an alkyl group (linear or branched), cycloalkyl (monocyclic or polycyclic), or alkenyl (linear or branched). branched chain), or aryl (monocyclic or polycyclic). Furthermore, when all 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, Rx ₁ to Rx ₃ each independently preferably represent a linear or branched alkyl group, and 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 single ring or a polycyclic ring. The alkyl groups of Rx ₁ to Rx ₃ are preferably alkyl groups having 1 to 5 carbon atoms such as methyl, ethyl, n-propyl, isopropyl, n-butyl, isobutyl and tert-butyl. As the cycloalkyl group of Rx ₁ to Rx ₃ , preferred are monocyclic cycloalkyl groups such as cyclopentyl and cyclohexyl, norbornyl, tetracyclodecyl, tetracyclododecyl, adamantyl and the like. Ring cycloalkyl. 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. As the alkenyl group of Rx ₁ to Rx ₃ , vinyl group is preferred. The ring formed by two of Rx ₁ to Rx ₃ bonding is preferably a cycloalkyl group. The cycloalkyl group formed by bonding two of Rx ₁ to Rx ₃ is preferably a monocyclic cycloalkyl group such as cyclopentyl or cyclohexyl, or a norbornyl group, a tetracyclodecyl group, or a tetracyclododecanyl group. 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. A cycloalkyl group formed by bonding two of Rx ₁ to Rx ₃ , in which one of the methylene groups constituting the ring may be substituted by a heteroatom such as an oxygen atom, a heteroatom-containing group such as a carbonyl group, or a vinylidene group. In these cycloalkyl groups, one or more ethylene groups constituting the cycloalkane ring may be substituted with vinylidene groups. The group represented by formula (Y1) or formula (Y2) is preferably one in which, for example, Rx ₁ is a methyl group or an ethyl group, and Rx ₂ and Rx ₃ are bonded to form the above-mentioned cycloalkyl group.

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. Examples of the monovalent organic group include an alkyl group, a cycloalkyl group, an aryl group, an aralkyl group, and an alkenyl group. R ₃₆ is preferably a hydrogen atom. In addition, the above-mentioned alkyl group, cycloalkyl group, aryl group and aralkyl group may contain heteroatoms such as oxygen atoms and/or groups containing heteroatoms such as carbonyl groups. For example, in the above-mentioned alkyl group, cycloalkyl group, aryl group and aralkyl group, one or more methylene groups may be substituted by a heteroatom such as an oxygen atom and/or a group containing a heteroatom such as a carbonyl group. R ₃₈ may be bonded to another substituent on the main chain of the repeating unit to form a ring. The group formed by bonding R ₃₈ to another substituent on the main chain of the repeating unit is preferably an alkylene group such as a methyl group.

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

[Chemical 39]

Here, L ₁ and L ₂ each independently represent a hydrogen atom, an alkyl group, a cycloalkyl group, an aryl group, or a group combining these (for example, a group combining an alkyl group and an aryl group). ). M represents a single bond or a divalent linking group. Q represents an alkyl group that may contain a heteroatom, a cycloalkyl group that may contain a heteroatom, an aryl group that may contain a heteroatom, an amine group, an ammonium group, a mercapto group, a cyano group, an aldehyde group, or a combination thereof. group (for example, a group combining an alkyl group and a cycloalkyl group). For alkyl and cycloalkyl groups, for example, one of the methylene groups may be substituted by 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 ₁ can be bonded to form a ring (preferably a 5-membered or 6-membered ring).

In formula (Y4), Ar represents an aromatic ring group. Rn represents an alkyl group, a cycloalkyl group or an aryl group. Rn and Ar can bond with each other to form a non-aromatic ring. Ar is preferably an aryl group.

Examples of the photoacid generator (B) include compounds (onium salts) represented by "M ⁺ X ^- ", and preferably are compounds that generate organic acids upon exposure. Examples of the organic acid include sulfonic acid (aliphatic sulfonic acid, aromatic sulfonic acid, camphorsulfonic acid, etc.), carboxylic acid (aliphatic carboxylic acid, aromatic carboxylic acid, aralkyl carboxylic acid, etc.) ), carbonyl sulfonyl imide acid, bis(alkyl sulfonyl) amide acid, and ginseng (alkyl sulfonyl) methylated acid.

In the compound represented by "M ⁺ X ^- ", M ⁺ represents a cation, preferably an organic cation. The organic cation represented by M ⁺ is not particularly limited. The valence of the cation may be monovalent or bivalent or higher. The cation is preferably a cation represented by formula (ZaI) (hereinafter also referred to as "cation (ZaI)") or a cation represented by formula (ZaII) (hereinafter also referred to as "cation (ZaII)"). M ⁺ preferably represents the sulfonium cation.

[Chemical 40]

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

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

First, the cation (ZaI-1) will be explained. The cation (ZaI-1) is an arylsulfonium cation in which at least one of R ²⁰¹ to R ²⁰³ of the above formula (ZaI) is an aryl group. The aryl sulfonium cation can be an aryl group in which R ²⁰¹ to R ²⁰³ are all aryl groups, or a part of R ²⁰¹ to R ²⁰³ can be an aryl group, and the rest can be an alkyl group or a cycloalkyl group. One of R ²⁰¹ to R ²⁰³ can be an aryl group, and the remaining two bonds between R ²⁰¹ to R ²⁰³ can form a ring structure, or the ring can contain oxygen atoms, sulfur atoms, ester groups, and amide groups. or carbonyl. Examples of the group formed by bonding two of R ²⁰¹ to R ²⁰³ include an alkylene group (for example, butylene group, pentylene group, and -CH ₂ -CH ₂ -O-CH ₂ - CH ₂ -), wherein more than one methylene group may be substituted by an oxygen atom, a sulfur atom, an ester group, a amide group and/or a carbonyl group. Examples of aryl sulfonium cations include triarylsulfonium cations, diarylalkylsulfonium cations, aryldialkylsulfonium cations, diarylcycloalkylsulfonium cations, and arylbicycloalkylsulfonium cations.

The aryl group contained in the arylsulfonium cation is preferably a phenyl group or a naphthyl group, and more preferably a phenyl group. The aryl group may be an aryl group having a heterocyclic structure containing an oxygen atom, a nitrogen atom, a sulfur atom, or the like. Examples of the heterocyclic structure include a pyrrole residue, a furan residue, a thiophene residue, an indole residue, a benzofuran residue, and a benzothiophene residue. When the arylsulfonium cation has two or more aryl groups, the two or more aryl groups may be the same or different. The alkyl group or cycloalkyl group that the arylsulfonium cation has if necessary is preferably a linear alkyl group having 1 to 15 carbon atoms, a branched alkyl group having 3 to 15 carbon atoms, or an alkyl group having 3 to 15 carbon atoms. Cycloalkyl, more preferably methyl, ethyl, propyl, n-butyl, sec-butyl, tert-butyl, cyclopropyl, cyclobutyl or cyclohexyl.

As the substituent that the aryl group, alkyl group and cycloalkyl group of R ²⁰¹ to R ²⁰³ may have, an alkyl group (for example, carbon number 1 to 15), cycloalkyl group (for example, carbon number 3 to 15), Aryl group (for example, carbon number 6 to 14), alkoxy group (for example, carbon number 1 to 15), cycloalkylalkoxy group (for example, carbon number 1 to 15), halogen atom (for example, fluorine and iodine) , hydroxyl group, carboxyl group, ester group, sulfinyl group, sulfonyl group, alkylthio group, or phenylthio group. The above-mentioned substituent may further have a substituent if possible, and it is also preferred that the above-mentioned alkyl group has a halogen atom as a substituent and is a haloalkyl group such as trifluoromethyl. It is also preferred that the above substituents form an acid-decomposable group by arbitrary combinations.

Next, the cation (ZaI-2) will be described. R ²⁰¹ to R ²⁰³ in the cation (ZaI-2) formula (ZaI) each independently represent a cation having an organic group that does not have an aromatic ring. The so-called aromatic ring also includes aromatic rings containing heteroatoms. The carbon number of the organic group that does not have an aromatic ring as R ²⁰¹ to R ²⁰³ is preferably 1 to 30, more preferably 1 to 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 group. The cycloalkyl group or the alkoxycarbonylmethyl group is more preferably a linear or branched 2-oxoalkyl group.

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

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

[Chemical 41]

In the formula (ZaI-3b), R _1c to R _5c each independently represent a hydrogen atom, an alkyl group, a cycloalkyl group, an aryl group, an alkoxy group, an aryloxy group, an alkoxycarbonyl group, a fluorinated alcohol group, or a ring fluorinated group. Alcohol 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 (for example, tert-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. The substituents of R _1c to R _7c and R _x and R _y are each independently, and it is preferable that an acid-decomposable group is formed by any combination of substituents.

Any two or more of R _1c to R _5c , R _5c and R _6c , R _6c and R _7c , R _5c and R _x , and R _x and R _y may be bonded to each other to form a ring, and the rings may be independent of each other. Ground contains oxygen atoms, sulfur atoms, ketone groups, ester bonds or amide bonds. Examples of the ring include an aromatic or non-aromatic hydrocarbon ring, an aromatic or non-aromatic heterocyclic ring, and a polycyclic condensed ring in which two or more of these rings are combined. Examples of the ring include a 3- to 10-membered ring, preferably a 4- to 8-membered ring, and more preferably a 5- or 6-membered ring.

Examples of the group 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 group and pentylene group. The methyl group in the alkylene group may be substituted by a heteroatom such as an oxygen atom. The group formed by bonding R _5c and R _6c and R _5c and R _x is preferably a single bond or an alkylene group. As an alkylene group, a methyl group, an ethylene group, etc. are mentioned.

R _1c to R _5c , R _6c , R _7c , R _x , R _y , and any two or more of R 1c to R _{5c , R 5c and} R _6c , R _6c and _{R 7c ,} R _5c and R _x , and The ring formed by each of R _x and R _y being bonded to each other may have a substituent.

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

[Chemical 42]

In the formula (ZaI-4b), l represents an integer from 0 to 2, and r represents an integer from 0 to 8. R ₁₃ represents a hydrogen atom, a halogen atom (for example, a fluorine atom, an iodine atom, etc.), a hydroxyl group, an alkyl group, a haloalkyl group, an alkoxy group, a carboxyl group, an alkoxycarbonyl group, or a group containing a cycloalkyl group (which may be a cycloalkyl group). The group itself may also be a group partially containing a cycloalkyl group). These groups may have substituents. R ₁₄ represents a hydroxyl group, a halogen atom (for example, a fluorine atom and an iodine atom, etc.), 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 the cycloalkyl group itself or a group partially containing a cycloalkyl group). These groups may have substituents. When there are plural R _14s , each independently represents the above-mentioned group such as hydroxyl group. R ₁₅ each independently represents an alkyl group, a cycloalkyl group or a naphthyl group. Two R _15's may bond to each other to form a ring. When two R _15's are bonded to each other to form a ring, the ring skeleton may contain heteroatoms such as oxygen atoms or nitrogen atoms. In one aspect, it is preferable that two R ₁₅ are alkylene groups and are bonded to each other to form a ring structure. In addition, the above-mentioned alkyl group, the above-mentioned cycloalkyl group, the above-mentioned naphthyl group, and the ring formed by two R _15s bonded to each other may have a substituent.

In the 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 to 10. The alkyl group is preferably methyl, ethyl, n-butyl or tert-butyl. Each substituent of R ₁₃ to R ₁₅ , and R _x and R _y is each independently, and it is preferable that an acid-decomposable group is formed by any combination of substituents.

Next, equation (ZaII) will be explained. In formula (ZaII), R ²⁰⁴ and R ²⁰⁵ each independently represent an aryl group, an alkyl group or a cycloalkyl group. As the aryl group of R ²⁰⁴ and R ²⁰⁵ , a phenyl group or a naphthyl group is preferable, and a phenyl group is more preferable. 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, a sulfur atom, or the like. Examples of the skeleton of the aryl group having a heterocyclic ring include pyrrole, furan, thiophene, indole, benzofuran and benzothiophene. As the alkyl group and cycloalkyl group of R ²⁰⁴ and R ²⁰⁵ , a linear alkyl group having 1 to 10 carbon atoms or a branched alkyl group having 3 to 10 carbon atoms (for example, methyl, ethyl, propyl) is preferred. group, butyl or pentyl), or a cycloalkyl group with 3 to 10 carbon atoms (for example, cyclopentyl, cyclohexyl or norbornyl).

The aryl group, alkyl group and cycloalkyl group of R ²⁰⁴ and R ²⁰⁵ may each independently have a substituent. Examples of substituents that the aryl group, alkyl group and cycloalkyl group of R ²⁰⁴ and R ²⁰⁵ may have include an alkyl group (for example, having 1 to 15 carbon atoms) and a cycloalkyl group (for example, having 3 to 15 carbon atoms). ), an aryl group (for example, having 6 to 15 carbon atoms), an alkoxy group (for example, having 1 to 15 carbon atoms), a halogen atom, a hydroxyl group, and a phenylthio group. Furthermore, it is preferable that the substituents of R ²⁰⁴ and R ²⁰⁵ form an acid-decomposable group independently of each other or by any combination of the substituents.

Specific examples of the cation represented by M ⁺ are shown below, but they are not limited thereto.

[Chemical 43]

[Chemical 44]

[Chemical 45]

In the compound represented by "M ⁺ X ^- ", X ^- represents an anion, preferably an organic anion. The organic anion is not particularly limited, and examples thereof include organic anions having a valence of 1, 2 or higher. As the organic anion, an anion having a very low ability to cause a nucleophilic reaction is preferred, and a non-nucleophilic anion is more preferred.

Examples of non-nucleophilic anions include sulfonic acid anions (aliphatic sulfonic acid anions, aromatic sulfonic acid anions, camphorsulfonic acid anions, etc.), carboxylic acid anions (aliphatic carboxylic acid anions, aromatic carboxylic acid anions, etc.) anions, and aralkylcarboxylic acid anions, etc.), sulfonimide anions, bis(alkylsulfonyl)imide anions, and ginseng(alkylsulfonyl)methide anions.

The aliphatic moiety in the aliphatic sulfonic acid anion and aliphatic carboxylic acid anion can be a linear or branched alkyl group, or a cycloalkyl group, preferably a linear or branched chain having 1 to 30 carbon atoms. Chain alkyl group or cycloalkyl group having 3 to 30 carbon atoms. The alkyl group may be, for example, a fluoroalkyl group (which may have a substituent other than a fluorine atom. It may also be a perfluoroalkyl group).

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

The alkyl group, cycloalkyl group, and aryl group listed above may have a substituent. The substituent is not particularly limited, and examples thereof include nitro groups, halogen atoms such as fluorine atoms and chlorine atoms, carboxyl groups, hydroxyl groups, amino groups, cyano groups, alkoxy groups (preferably having 1 to 15 carbon atoms), and alkyl groups. group (preferably carbon number 1 to 10), cycloalkyl group (preferably carbon number 3 to 15), aryl group (preferably carbon number 6 to 14), alkoxycarbonyl group (preferably carbon number 2 to 15) 7), acyl group (preferably having 2 to 12 carbon atoms), alkoxycarbonyloxy group (preferably having 2 to 7 carbon atoms), alkylthio group (preferably having 1 to 15 carbon atoms), alkyl sulfonate acyl group (preferably having 1 to 15 carbon atoms), alkyl iminosulfonyl group (preferably having 1 to 15 carbon atoms), and aryloxysulfonyl group (preferably having 6 to 20 carbon atoms).

The aralkyl group in the aralkylcarboxylic acid 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, phenethyl, naphthylmethyl, naphthylethyl, and naphthyl butyl.

Examples of sulfonimide anions include saccharin anions.

As the alkyl group in the bis(alkylsulfonyl)imide anion and the alkyl(alkylsulfonyl)methide anion, an alkyl group having 1 to 5 carbon atoms is preferred. Examples of substituents for such alkyl groups include halogen atoms, alkyl groups substituted by halogen atoms, alkoxy groups, alkylthio groups, alkoxysulfonyl groups, aryloxysulfonyl groups, and cycloalkylaryl groups. The oxysulfonyl group is preferably a fluorine atom or an alkyl group substituted by a fluorine atom. In addition, the alkyl groups in the bis(alkylsulfonyl)imide anion may be bonded to each other to form a ring structure. By this, the acid strength can be increased.

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

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

[Chemical 46]

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 amine group, and a hydrocarbon-substituted amide group. As the non-electron-withdrawing group, 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, Monovalent linear or branched hydrocarbon groups such as propynyl and butynyl and other alkynyl groups; cyclopropyl, cyclobutyl, cyclopentyl, cyclohexyl, norbornyl, and adamantyl and other rings Alkyl; monovalent alicyclic hydrocarbon groups such as cyclopropenyl, cyclobutenyl, cyclopentenyl, norbornenyl and other cycloalkenyl groups; phenyl, tolyl, xylyl, mesityl, naphthyl , methylnaphthyl, anthracenyl, and methylanthracenyl and other aryl groups; benzyl, phenethyl, phenylpropyl, naphthylmethyl, anthracenyl and other aralkyl and other monovalent aromatic hydrocarbon groups. Among them, R ¹ and R ² are each independently preferably a hydrocarbon group (preferably a cycloalkyl group) or a hydrogen atom.

L represents a bivalent linking group. When there are multiple L's, L's may be the same or different. Examples of the divalent linking group include -O-CO-O-, -COO-, -CONH-, -CO-, -O-, -S-, -SO-, -SO ₂ -, Alkyl group (preferably having 1 to 6 carbon atoms), cycloalkyl group (preferably having 3 to 15 carbon atoms), alkenylene group (preferably having 2 to 6 carbon atoms), and a combination of a plurality of these into a bivalent linking base. Among them, as the divalent linking group, -O-CO-O-, -COO-, -CONH-, -CO-, -O-, -SO ₂ -, -O-CO-O-alkane is preferred. -, -COO-alkylene-, or -CONH-alkylene-, more preferably -O-CO-O-, -O-CO-O-alkylene-, -COO-, -CONH- , -SO ₂ -, or -COO-alkylene-.

As L, for example, a group represented by the following formula (AN1-1) is preferred. * ^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 formula (AN1). X and Y each independently represent an integer from 0 to 10, preferably an integer from 0 to 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 may be the same or different. When Y is 1 or more, R ^2b in CR ^2b ₂ directly bonded to -C(R ¹ )(R ² )- in formula (AN1) is other than a fluorine atom. Q represents * ^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 . Among them, when X+Y in the formula (AN1-1) is 1 or more, and R ^2a and R ^2b in the formula (AN1-1) are both hydrogen atoms, Q represents * ^A -O-CO-O- * ^B , * ^A -CO-* ^B , * ^A -O-CO-* ^B , * ^A -O-* ^B , * ^A -S-* ^B , or * ^A - _SO2- * ^B . * ^A represents the bonding position on the R ³ side in the formula (AN1), * ^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 one or more carbon atoms, and may be a linear group (for example, a linear alkyl group) or a branched group (for example, a tertiary butyl group, etc. branched alkyl group) or a cyclic group. The above organic group may or may not have a substituent. The above-mentioned organic group may have heteroatoms (oxygen atom, sulfur atom and/or nitrogen atom, etc.), or may not have heteroatoms.

Among them, R ³ is preferably an organic group having a cyclic structure. The above-mentioned cyclic structure may be a monocyclic ring or a polycyclic ring, or may have a substituent. The ring in the organic group containing a cyclic structure is preferably directly bonded to L in formula (AN1). The organic group having the above-mentioned cyclic structure may, for example, have heteroatoms (oxygen atom, sulfur atom, and/or nitrogen atom, etc.), or may not have heteroatoms. Heteroatoms can replace more than one carbon atom forming a cyclic structure. The organic group having the above-mentioned cyclic structure is, for example, preferably a hydrocarbon group, a lactone ring group, and a sultone ring group with a cyclic structure. Among them, the organic group having the above-mentioned cyclic structure is preferably a hydrocarbon group having a cyclic structure. The hydrocarbon group with 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 to 12. Examples of the lactone group and the sultone group include the structures represented by the above formulas (LC1-1) to (LC1-21) and the structures represented by the formulas (SL1-1) to (SL1-3). In either structure, a group obtained by removing one hydrogen atom from a ring member atom constituting the lactone structure or sultone structure is preferred.

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

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

[Chemical 47]

In formula (AN2), o represents an integer from 1 to 3. p represents an integer from 0 to 10. q represents an integer from 0 to 10.

Xf represents a hydrogen atom, a fluorine atom, an alkyl group substituted with at least one fluorine atom, or an organic group having no fluorine atom. The number of carbon atoms in the alkyl group is preferably 1 to 10, more preferably 1 to 4. As the alkyl group substituted by at least one fluorine atom, a perfluoroalkyl group is preferred. Xf is preferably a fluorine atom or a perfluoroalkyl group having 1 to 4 carbon atoms, more preferably a fluorine atom or CF ₃ , and further preferably both 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 respectively. The alkyl group represented by R ⁴ and R ⁵ preferably has 1 to 4 carbon atoms. The above-mentioned alkyl group may have a substituent. R ⁴ and R ⁵ are preferably hydrogen atoms.

L represents a bivalent linking group. The definition of L is synonymous with L in formula (AN1).

W represents an organic group containing a cyclic structure. Among them, a cyclic organic group is preferred. Examples of the cyclic organic group include an alicyclic group, an aryl group and a heterocyclic group. The alicyclic group may be monocyclic or polycyclic. Examples of the monocyclic alicyclic group include 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, tricyclodecyl, tetracyclodecyl, tetracyclododecyl, and adamantyl, are preferred.

Aryl groups can be monocyclic or polycyclic. Examples of the aryl group include phenyl, naphthyl, phenanthrenyl, and anthracenyl. Heterocyclyl groups may be monocyclic or polycyclic. Among them, when it is a polycyclic heterocyclic group, the diffusion of acid can be further suppressed. The heterocyclic group may or may not be aromatic. Examples of the aromatic heterocyclic ring include a furan ring, a thiophene ring, a benzofuran ring, a benzothiophene ring, a dibenzofuran ring, a dibenzothiophene ring, and a pyridine ring. Examples of the nonaromatic heterocyclic ring include a tetrahydropyran ring, a lactone ring, a sultone ring, and a decahydroisoquinoline ring. As the heterocyclic ring in the heterocyclic group, a furan ring, a thiophene ring, a pyridine ring, or a decahydroisoquinoline ring is preferred.

The above-mentioned cyclic organic group may have a substituent. Examples of the substituent include an alkyl group (which may be linear or branched, preferably having 1 to 12 carbon atoms), a cycloalkyl group (which may be monocyclic, polycyclic, or and spiro ring, preferably carbon number 3 to 20), aryl group (preferably carbon number 6 to 14), hydroxyl group, alkoxy group, ester group, amide group, carbamate group group, urea group, thioether group, sulfonamide group, and sulfonate group. In addition, the carbon constituting the cyclic organic group (carbon that contributes to ring formation) may be a carbonyl carbon.

As the anion represented by the formula (AN2), preferred are SO ₃ ^- -CF ₂ -CH ₂ -OCO-(L) _q' -W, SO ₃ ^- -CF ₂ -CHF-CH ₂ -OCO-(L) _q' -W, SO ₃ ^- -CF ₂ -COO-(L) _q' -W, SO ₃ ^- -CF ₂ -CF ₂ -CH ₂ -CH ₂ -(L) _q -W, or SO ₃ ^- - CF ₂ -CH(CF ₃ )-OCO-(L) _q' -W. Here, L, q and W are the same as Formula (AN2). q' represents an integer from 0 to 10.

As the non-nucleophilic anion, an aromatic sulfonic acid anion represented by the following formula (AN3) is also preferred.

[Chemical 48]

In formula (AN3), Ar represents an aryl group (such as a phenyl group), and may further have a substituent other than a sulfonate anion and a -(D-B) group. Examples of substituents that may further include a fluorine atom and a hydroxyl group. n represents an integer above 0. As n, 1 to 4 are preferable, 2 to 3 are more preferable, and 3 is still more preferable.

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

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

As the non-nucleophilic anion, disulfonamide anion is also preferred. For example, the disulfonamide anion is an anion represented by N ^- (SO ₂ -R ^q ) ₂ . Here, R ^q represents an alkyl group which may have a substituent, and is preferably a fluoroalkyl group, more preferably a perfluoroalkyl group. Two R ^q can bond to each other to form a ring. The group formed by two R ^q's bonded 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 above-mentioned alkylene group is preferably 2 to 4.

Compound (B) is preferably a compound represented by the following general formula (P1).

[Chemical 49]

In the general formula (P1), R ^1P to R ^5P each independently represent a hydrogen atom, an alkyl group, a cycloalkyl group, an aryl group, a hydroxyl group, an alkoxy group or a cycloalkoxy group, and R ^1P to R ^5P do not contain a fluorine atom. Mp ⁺ represents a cation.

The alkyl groups of R ^1P to R ^5P may be either linear or branched. The number of carbon atoms in the alkyl group is not particularly limited, but is preferably 1 to 5, more preferably 1 to 3. The number of carbon atoms in the cycloalkyl group of R ^1P to R ^5P is not particularly limited, but is preferably 3 to 20, more preferably 5 to 15. The cycloalkyl groups of R ^1P to R ^5P may be monocyclic cycloalkyl groups such as cyclopentyl and cyclohexyl, or may be norbornyl, tetracyclodecyl, tetracyclododecyl, adamantyl, etc. Ring cycloalkyl. The number of carbon atoms in the aryl group of R ^1P to R ^5P is not particularly limited, but is preferably 6 to 20, more preferably 6 to 15. The aryl group of R ^1P to R ^5P is preferably a phenyl group. The alkoxy groups of R ^1P to R ^5P may be either linear or branched. The number of carbon atoms in the alkoxy group is not particularly limited, but is preferably 1 to 5, more preferably 1 to 3. The number of carbon atoms in the cycloalkoxy group of R ^1P to R ^5P is not particularly limited, but is preferably 3 to 20, more preferably 5 to 15. The cycloalkoxy groups of R ^1P to R ^5P may be monocyclic cycloalkoxy groups or polycyclic cycloalkoxy groups.

When R ^1P to R ^5P represent an alkyl group, a cycloalkyl group, an aryl group, an alkoxy group or a cycloalkoxy group, these may further have a substituent. Among them, R ^1P to R ^5P do not contain fluorine atoms. That is, the alkyl group, cycloalkyl group, aryl group, alkoxy group and cycloalkoxy group mentioned above do not have a fluorine atom as a substituent. Since R ^1P to R ^5P do not contain fluorine atoms, the hydrophobicity of the compound (B) can be reduced and defects can be further reduced, which is preferable.

Mp ⁺ in the general formula (P1) represents a cation, and specific examples and preferred ranges are the same as M ⁺ mentioned above.

Compound (B) is also preferably at least one selected from the group consisting of compounds (I) to (II).

(Compound (I)) Compound (I) is a compound having one or more structural parts X and one or more structural parts Y described below, and is produced by irradiation with actinic rays or radioactive rays, including those derived from the following structural parts A compound of an acid derived from the following first acidic site of X and the following second acidic site of structural site Y below. _Structural ^site _{_} ^_ _{_ _} ^- and the cationic site M ₂ ⁺ , and the structural site forming a second acidic site 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 replacing 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 a The acid _{dissociation constant a1 of the acidic site represented by HA 1} ⁱⁿ _which the above-mentioned cationic site M ₁ ⁺ in the above ^- mentioned structural site The acid dissociation constant a2 of the acidic site represented by HA ₂ formed by H ⁺ is greater than the acid dissociation constant a1.

Condition I will be explained in more detail below. When compound (I), for example, is a compound producing an acid having the above-mentioned first acidic site derived from the above-mentioned structural site X and the above-mentioned second acidic site derived from the above-mentioned structural site Y, the compound PI is equivalent to "having Compounds of HA ₁ and HA ₂ ". The acid dissociation constant a1 and the acid dissociation constant a2 of the compound PI are, more specifically, when the acid dissociation constant of the compound PI is determined and the compound PI becomes a "compound having A ₁ ^- and HA ₂ " pKa is the acid dissociation constant a1, and the pKa when the above "compound having A ₁ ^- and HA ₂ " becomes "the compound having A ₁ ^- and A ₂ ^- " is the acid dissociation constant a2.

When compound (I), for example, is a compound generating an acid having two above-mentioned first acidic sites derived from above-mentioned structural site X and one above-mentioned second acidic site derived from above-mentioned structural site Y, compound PI corresponds to " Compounds with two HA ₁ and one HA ₂ ". When the acid dissociation constant of compound PI is found, the acid dissociation constant of compound PI becomes "a compound having one A ₁ ^- , one HA ₁ and one HA ₂ " and "it has one A ₁ ^- and one HA ₁ The acid dissociation constant when "a compound having two A ₁ ^- and one HA ₂ " becomes "a compound having two A 1 - and one HA ₂ " is equivalent to the above-mentioned acid dissociation constant a1. The acid dissociation constant when "a compound having two A ₁ ^- and one HA ₂ " becomes "a compound having two A ₁ ^- and A ₂ ^- " is equivalent to the acid dissociation constant a2. That is, in the case of compound PI, when there are multiple acid dissociation constants of the acidic site represented by HA ₁ derived from the cationic site M ₁ ⁺ in the structural site X substituted with H ⁺ , the acid dissociation The value of constant a2 is greater than the maximum value among the plurality of acid dissociation constants a1. In addition, when compound PI is "a compound having one A ₁ ^- , one HA ₁ and one HA ₂ ", the acid dissociation constant is aa, and "a compound having one A ₁ ^- , one HA ₁ and one HA _2" When the acid dissociation constant when "compound" becomes "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 can be determined by the above-described acid dissociation constant measuring method. The above compound PI corresponds to an acid generated when compound (I) is irradiated with actinic rays or radioactive rays. When the compound (I) has two or more structural parts X, the structural parts X may be the same or different. In addition, two or more of the above-mentioned A ₁ ^- and two or more of the above-mentioned M ₁ ⁺ may be the same or different. In the compound (I), 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, but the above-mentioned A ₁ ^- and the above-mentioned A ₂ ^- are preferably different.

In the above-mentioned compound PI, the difference (absolute value) between the acid dissociation constant a1 (the maximum value when there are multiple acid dissociation constants a1) and the acid dissociation constant a2 is preferably 0.1 or more, more preferably 0.5 or more, and still more preferably is above 1.0. In addition, 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, but is, for example, 16 or less.

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

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

The anionic site A ₁ ^- and the anionic site A ₂ ^- are structural sites containing negatively charged atoms or atomic groups. Examples thereof include the following formulas (AA-1) to (AA-3) and formula ( Structural parts in the group composed of BB-1) ~ (BB-6). The anionic site A ₁ ^- is preferably one that can form 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-3) is more preferred. Any one of AA-1) and (AA-3). Furthermore, the anionic site A ₂ ^- is preferably one capable of forming an acidic site with a larger acid dissociation constant than the anionic site A ₁ ^- , and is more preferably any one of the formulas (BB-1) to (BB-6). More preferred is either 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 50]

[Chemistry 51]

The cationic site M ₁ ⁺ and the cationic site M ₂ ⁺ are structural sites containing positively charged atoms or atomic groups. Examples thereof include organic cations with a single charge. Examples of organic cations include the organic cations described as the cation represented by the above-mentioned M ⁺ .

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

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

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

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

In the 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 bivalent linking group. M ₁₁ ⁺ and M ₁₂ ⁺ may be the same or different respectively. A ₁₁ ^- and A ₁₂ ^- may be the same or different, respectively, but are preferably different from each other. Among them, in the compound PIa (HA 11 -L 1 -A 12 H) in which the cations represented by M ₁₁ ⁺ and M ₁₂ ⁺ are substituted with H ⁺ in the above formula (Ia-1), the compound PIa (HA ₁₁ -L ₁ -A ₁₂ H) is derived from A ₁₂ The acid dissociation constant a2 of the acidic site represented by H is greater than the acid dissociation constant a1 derived from the acidic site represented by HA ₁₁ . In addition, preferred values of the acid dissociation constant a1 and the acid dissociation constant a2 are as described above. Compound PIa is the same acid produced from the compound represented by formula (Ia-1) by irradiation with actinic rays or radiation. Moreover, at least one of M ₁₁ ⁺ , M ₁₂ ⁺ , A ₁₁ ^- , A ₁₂ ^- and L ₁ may have an acid-decomposable group as a substituent.

In the formula (Ia-1), the organic cations represented by M ₁₁ ⁺ and M ₁₂ ⁺ are the same as the organic cations described as the cation represented by M ⁺ mentioned above.

The monovalent anionic functional group represented by A ₁₁ ^- means a monovalent group containing the above-mentioned anionic site A ₁ ^- . In addition, the monovalent anionic functional group represented by A ₁₂ ^- means a monovalent group including the above-mentioned anionic site A ₂ ^- . The monovalent anionic functional group represented by A ₁₁ ^- and A ₁₂ ^- is preferably included in the above formulas (AA-1) to (AA-3) and formulas (BB-1) to (BB-6). The monovalent anionic functional group in any of the anionic sites is 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 in the group. As the monovalent anionic functional group represented by A ₁₁ ^- , among them, a monovalent anionic functional group represented by any one of formulas (AX-1) to (AX-3) is preferred. As the monovalent anionic functional group represented by A ₁₂ ^- , among them, a monovalent anionic functional group represented by any one of the formulas (BX-1) to (BX-7) is preferred, and more preferred It is a monovalent anionic functional group represented by any one of (BX-1) to (BX-6).

[Chemistry 52]

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

As the monovalent organic group represented by R ^A2 , a linear, branched or cyclic alkyl group or an aryl group is preferred. The number of carbon atoms in the alkyl group is preferably 1 to 15, more preferably 1 to 10, and still more preferably 1 to 6. The above-mentioned alkyl group may have a substituent. As the substituent, a fluorine atom or a cyano group is preferred, and a fluorine atom is more preferred. When the alkyl group has a fluorine atom as a substituent, it may be a perfluoroalkyl group.

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

In formulas (BX-1) to (BX-4) and formula (BX-6), R ^B represents a monovalent organic group. *Indicates bonding position. As the monovalent organic group represented by ^RB , a linear, branched, or cyclic alkyl group or an aryl group is preferred. The number of carbon atoms in the alkyl group is preferably 1 to 15, more preferably 1 to 10, and still more preferably 1 to 6. The above-mentioned alkyl group may have a substituent. The substituent is not particularly limited. The substituent is preferably a fluorine atom or a cyano group, and more preferably a fluorine atom. When the alkyl group has a fluorine atom as a substituent, it may be a perfluoroalkyl group. Furthermore, when the carbon atom serving as a 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 carbon atom that serves as a bonding position in the alkyl group, for example, in the case of formulas (BX-1) and (BX-4), corresponds to -CO- specified in the formula in the alkyl group. The directly bonded carbon atom, in the case of formulas (BX-2) and (BX-3), is equivalent to the directly bonded carbon atom with -SO ₂ - shown in the formula in the alkyl group, in the formula ((BX-2) and (BX-3)). In the case of BX-6), it corresponds to the carbon atom directly bonded to ^N- specified in the formula in the alkyl group. The carbon atoms of the above-mentioned alkyl groups may be substituted by carbonyl carbons.

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

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

Among these, the bivalent coupling group represented by L ₁ is preferably a bivalent coupling group represented by formula (L1).

[Chemistry 53]

In formula (L1), L ₁₁₁ represents a single bond or a bivalent connecting group. The bivalent linking group represented by L ₁₁₁ is not particularly limited, and examples thereof include -CO-, -NH-, -O-, -SO-, -SO ₂ -, or alkanes which may have a substituent. group (preferably, more preferably 1 to 6 carbon atoms. It may be linear or branched), a cycloalkyl group (preferably, 3 to 15 carbon atoms) which may have a substituent, An aryl group having a substituent (preferably having 6 to 10 carbon atoms), and a bivalent linking group formed by combining a plurality of these groups. The substituent is not particularly limited, and examples thereof include halogen atoms. p represents an integer of 0 to 3, preferably an integer of 1 to 3. v represents an integer of 0 or 1. Xf ₁ each independently represents a fluorine atom or an alkyl group substituted by at least one fluorine atom. The number of carbon atoms in the alkyl group is preferably 1 to 10, more preferably 1 to 4. As the alkyl group substituted by at least one fluorine atom, a perfluoroalkyl group is preferred. Xf ₂ each independently represents a hydrogen atom, an alkyl group which may have a fluorine atom as a substituent, or a fluorine atom. The number of carbon atoms in the alkyl group is preferably 1 to 10, more preferably 1 to 4. Among them, Xf ₂ preferably represents a fluorine atom or an alkyl group substituted with at least one fluorine atom, and 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 carbon atoms, and 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 bonding position. When L ₁ in formula (Ia-1) represents a bivalent linking group represented by formula (L1), the bonding bond (*) on the L ₁₁₁ side in formula (L1) is preferably the same as formula (Ia-1) ) in the A ₁₂ ^-bond .

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

[Chemistry 54]

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 ^- means a monovalent group including the above-mentioned anionic site A ₁ ^- . The monovalent anionic functional group represented by A _21a ^- and A _21b ^- is not particularly limited, and examples thereof include those selected from the group consisting of the above formulas (AX-1) to (AX-3). A monovalent anionic functional group. A ₂₂ ^- represents a divalent anionic functional group. Here, the bivalent anionic functional group represented by A ₂₂ ^- means a bivalent connecting group including the above-mentioned anionic 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 55]

M _21a ⁺ , M _21b ⁺ and M ₂₂ ⁺ each independently represent an organic cation. The organic cations represented by M _21a ⁺ , M _21b ⁺ and M ₂₂ ⁺ are synonymous with the above-mentioned M ₁ ⁺ , and preferred aspects are also the same. L ₂₁ and L ₂₂ each independently represent a divalent organic group.

In the above formula (Ia-2), in the compound PIa-2 in which the organic cations represented by M _21a ⁺ , M _21b ⁺ and M ₂₂ ⁺ are substituted with H ⁺ , the ions derived from the acidic site represented by A ₂₂ H The acid dissociation constant a2 is larger than the acid dissociation constant a1-1 derived from A _21a H and the acid dissociation constant a1-2 derived from the acidic site represented by A _21b H. In addition, the acid dissociation constant a1-1 and the acid dissociation constant a1-2 correspond to the 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 synonymous with 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 site A ₂ ^- . The monovalent anionic functional group represented by A ₃₂ ^- is not particularly limited, and examples thereof include monovalent anionic functional groups selected from the group consisting of the above formulas (BX-1) to (BX-7). Anionic functional group. A _31b ^- represents a divalent anionic functional group. Here, the bivalent anionic functional group represented by A _31b ^- means a bivalent connecting group including the above-mentioned anionic site A ₁ ^- . Examples of the divalent anionic functional group represented by A _31b ^- include a divalent anionic functional group represented by the following formula (AX-4).

[Chemical 56]

M _31a ⁺ , M _31b ⁺ and M ₃₂ ⁺ each independently represent a monovalent organic cation. The organic cations represented by M _31a ⁺ , M _31b ⁺ and M ₃₂ ⁺ are synonymous with M ₁ ⁺ mentioned above, and preferred aspects are also the same. L ₃₁ and L ₃₂ each independently represent a divalent organic group.

In the above formula (Ia-3), in the compound PIa-3 in which the organic cations represented by M _31a ⁺ , M _31b ⁺ and M ₃₂ ⁺ are substituted with H ⁺ , the ions derived from the acidic site represented by A ₃₂ H The acid dissociation constant a2 is larger than the acid dissociation constant a1-3 derived from the acidic site represented by A _31a H and the acid dissociation constant a1-4 derived from the acidic 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. In addition, 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 definitions of the monovalent anionic functional groups represented by A _41a ^- and A _41b ^- are synonymous with A _21a ^- and A _21b ^- in the above formula (Ia-2). The definition of the monovalent anionic functional group represented by A ₄₂ ^- is synonymous with that of A ₃₂ ^- in the above formula (Ia-3), and the preferred embodiments 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 PIa-4 in which the organic cations represented by M _41a ⁺ , M _41b ⁺ and M ₄₂ ⁺ are substituted with H ⁺ , the ions derived from the acidic site represented by A ₄₂ H The acid dissociation constant a2 is larger than the acid dissociation constant a1-5 derived from the acidic site represented by A _41a H and the acid dissociation constant a1-6 derived from the acidic site represented by A _41b H. In addition, the acid dissociation constant a1-5 and the acid dissociation constant a1-6 correspond to the 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. In addition, 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 group represented by L ₂₁ and L ₂₂ in the formula (Ia-2) and L ₃₁ and L ₃₂ in the formula (Ia-3) is not particularly limited, and examples thereof include -CO- , -NR-, -O-, -S-, -SO-, -SO ₂ -, alkylene group (preferably carbon number 1 to 6, can be linear or branched), ring extension group Alkyl group (preferably having 3 to 15 carbon atoms), alkenyl group (preferably having 2 to 6 carbon atoms), divalent aliphatic heterocyclic group (preferably having at least one N atom, O in the ring structure atom, S atom or Se atom, a 5- to 10-membered ring, more preferably a 5- to 7-membered ring, further preferably a 5- to 6-membered ring.), a divalent aromatic heterocyclic group (preferably an in-ring structure A 5- to 10-membered ring having at least one N atom, O atom, S atom or Se atom, more preferably a 5- to 7-membered ring, further preferably a 5- to 6-membered ring.), a divalent aromatic hydrocarbon ring group (preferably a 6- to 10-membered ring, more preferably a 6-membered ring.), and a bivalent organic group formed by combining a plurality of these. Examples of R in -NR- mentioned above include a hydrogen atom or a monovalent organic group. The monovalent organic group is not particularly limited, but for example, an alkyl group (preferably having 1 to 6 carbon atoms) is preferred. The alkylene group, the cycloalkylene group, the alkenylene group, the divalent aliphatic heterocyclic group, the divalent aromatic heterocyclic group, and the divalent aromatic hydrocarbon ring group may have a substituent. Examples of the substituent include a halogen atom (preferably a fluorine atom).

As the divalent organic group represented by L ₂₁ and L ₂₂ in the formula (Ia-2) and L ₃₁ and L ₃₂ in the formula (Ia-3), for example, the following formula (L2 ) represents a divalent organic radical.

[Chemistry 57]

In formula (L2), q represents an integer from 1 to 3. *Indicates bonding position. Xf each independently represents a fluorine atom or an alkyl group substituted by at least one fluorine atom. The number of carbon atoms in the alkyl group is preferably 1 to 10, more preferably 1 to 4. As the alkyl group substituted by at least one fluorine atom, a perfluoroalkyl group is preferred. Xf is preferably a fluorine atom or a perfluoroalkyl group having 1 to 4 carbon atoms, more preferably a fluorine atom or CF ₃ . In particular, it is more preferred that Xf in both of them is a fluorine atom.

L _A represents a single bond or a divalent linking group. The bivalent linking group represented by L _A is not particularly limited, and examples thereof include -CO-, -O-, -SO-, -SO ₂ -, and an alkylene group (preferably having 1 to 6 carbon atoms). . It may be linear or branched), cycloalkyl group (preferably carbon number 3 to 15), divalent aromatic hydrocarbon ring group (preferably 6 to 10 membered ring, more preferably (a 6-membered ring), and a bivalent linking base formed by combining a plurality of these. The above-mentioned alkylene group, the above-mentioned cycloalkylene group, and the divalent aromatic hydrocarbon ring group may have a substituent. Examples of the substituent include a halogen atom (preferably a fluorine atom).

Examples of the divalent organic group represented by formula (L2) include *-CF ₂ -*, *-CF ₂ -CF ₂ -*, *-CF ₂ -CF ₂ -CF ₂ -*, * -Ph-O-SO ₂ -CF ₂ -*,*-Ph-O-SO ₂ -CF ₂ -CF ₂ -*,*-Ph-O-SO ₂ -CF ₂ -CF ₂ -CF ₂ -*and *-Ph-OCO-CF ₂ -*. In addition, the Ph-based phenylene group which may have a substituent is preferably a 1,4-phenylene group. The substituent is not particularly limited, but is preferably an alkyl group (for example, preferably with a carbon number of 1 to 10, more preferably with a carbon number of 1 to 6), an alkoxy group (for example, preferably with a carbon number of 1 to 6 10, more preferably 1 to 6 carbon atoms), or an alkoxycarbonyl group (for example, preferably 2 to 10 carbon atoms, more preferably 2 to 6 carbon atoms). When L ₂₁ and L ₂₂ in the formula (Ia-2) represent a divalent organic group represented by the formula (L2), the bonding bond (*) on the L _A side in the formula (L2) is preferably the same as the formula A _21a ^- and A _21b ^- bonds in (Ia-2). When L ₃₁ and L ₃₂ in the formula (Ia-3) represent a divalent organic group represented by the formula (L2), the bonding bond (*) on the L _A side in the formula (L2) is preferably the same as the formula A _31a ^- and ^A ₃₂ -bonds in (Ia-3).

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

[Chemical 58]

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

M _51a ⁺ , M _51b ⁺ , M _51c ⁺ , M _52a ⁺ and M _52b ⁺ each independently represent an organic cation. The organic cations represented by M _51a ⁺ , M _51b ⁺ , M _51c ⁺ , M _52a ⁺ and M _52b ⁺ are synonymous with the above-mentioned M ₁ ⁺ , and preferred aspects are also the same. L ₅₁ and L ₅₃ each independently represent a divalent organic group. The divalent organic groups represented by L ₅₁ and L ₅₃ are synonymous with L ₂₁ and L ₂₂ in the above formula (Ia-2), and 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 L ₄₁ in the above formula (Ia-4), and the preferred aspects are also the same.

In the above formula (Ia-5), in the compound PIa-5 in which the organic cations represented by M _51a ⁺ , M _51b ⁺ , M _51c ⁺ , M _52a ⁺ and M _52b ⁺ are substituted with H ⁺ , the compound PIa-5 is derived from The acid dissociation constant a2-1 of the acidic site represented by A _52a H and the acid dissociation constant a2-2 derived from the acidic site represented by A _52b H are larger than the acid dissociation constant a1-1 derived from A _51a H and derived from A _51b H The acid dissociation constant a1-2 of the acidic site represented by A _51c H and the acid dissociation constant a1-3 derived from the acidic 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. In addition, 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 (II)) Compound (II) is a compound having two or more of the above-mentioned structural parts X and one or more of the following structural parts Z, and is a compound containing two or more structural parts derived from the above-mentioned structural parts X produced by irradiation with actinic rays or radiation. The first acidic site and the above-mentioned structural site Z acid compound. Structural part Z: a non-ionic part that can neutralize acid.

^In the compound (II), the definition of the structural part X and the definitions of A ₁ ^- and M ₁ ⁺ are synonymous with _the ^definitions of _the structural part The same goes for good looks.

In the compound (II), the compound PII in which the cationic site M ₁ ⁺ in the structural site X is substituted with H ⁺ is derived from the substitution of the cationic site M ₁ ⁺ in the structural site X with The preferable range of the acid dissociation constant a1 of the acidic site represented by HA ₁ formed by H ⁺ is the same as the acid dissociation constant a1 of the above-mentioned compound PI. Furthermore, for example, when compound (II) is a compound that generates an acid having two first acidic sites derived from the above structural site X and the above structural site Z, the compound PII is equivalent to "a compound having two HA ₁ " . When the acid dissociation constant of compound PII is found, the acid dissociation constant when compound PII becomes "a compound having one A ₁ ^- and one HA ₁ " and "a compound having one A ₁ ^- and one HA ₁ " The acid dissociation constant when it becomes a "compound having two A ₁ ^- " is equivalent to the acid dissociation constant a1.

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

The nonionic moiety capable of neutralizing the acid in the structural moiety Z is not particularly limited. For example, a moiety containing a group capable of electrostatically interacting with protons or a functional group having electrons is preferred. Examples of the group capable of electrostatic interaction with protons or the functional group having electrons include functional groups having a macrocyclic structure such as cyclic polyethers or nitrogen containing non-shared electron pairs that do not contribute to π conjugation. functional groups of atoms. The nitrogen atom having a non-shared electron pair that does not contribute to π conjugation means, for example, a nitrogen atom having a partial structure represented by the following formula.

[Chemistry 59]

Examples of the partial structure of a group capable of electrostatically interacting with a proton or a functional group having electrons include a crown ether structure, an azacrown ether structure, a primary to tertiary amine structure, a pyridine structure, an imidazole structure, and a pyrazine. structure, among which the 1st to 3rd level amine structure is preferred.

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

[Chemical 60]

In the above formula (IIa-1), A _61a ^- and A _61b ^- are respectively synonymous with A ₁₁ ^- in the above formula (Ia-1), and the preferred aspects are also the same. In addition, M _61a ⁺ and M _61b ⁺ are each synonymous with M ₁₁ ⁺ in the above formula (Ia-1), and preferred aspects are also the same. In the above formula (IIa-1), L ₆₁ and L ₆₂ are respectively synonymous with L ₁ in the above formula (Ia-1), and the preferred aspects are also the same.

In formula (IIa-1), R _2X represents a monovalent organic group. The monovalent organic group represented by R _2X is not particularly limited, and examples thereof include an alkyl group (preferably a carbon number of 1 to 10, which may be linear or branched), and a cycloalkyl group (preferably C3-15) or alkenyl (preferably C2-6). -CH ₂ - included 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-, - Replace with one or a combination of two or more of the group consisting of SO-, and -SO ₂ -. The above-mentioned alkylene group, the above-mentioned cycloalkylene group, and the above-mentioned alkenylene group may have a substituent. The substituent is not particularly limited, and examples thereof include a halogen atom (preferably a fluorine atom).

In the above formula (IIa-1), in the compound PIIa-1 in which the organic cations represented by M _61a ⁺ and M _61b ⁺ are substituted with H ⁺ , the 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 acidic site represented by A _61b H correspond to the above-mentioned acid dissociation constant a1. In addition, ^the compound PIIa-1 obtained by substituting the above-mentioned cationic _sites M _61a ⁺ and M _61b ⁺ _in the above-mentioned structural site _2X )-L ₆₂ -A _61b H. In addition, compound PIIa-1 is the same as the acid generated from the compound represented by formula (IIa-1) by irradiation with actinic rays or radioactive rays. 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 ^- are respectively synonymous with A ₁₁ ^- in the above formula (Ia-1), and the preferred aspects are also the same. M _71a ⁺ , M _71b ⁺ and M _71c ⁺ are respectively synonymous with M ₁₁ ⁺ in the above formula (Ia-1), and the preferred aspects are also the same. In the above formula (IIa-2), L ₇₁ , L ₇₂ and L ₇₃ are respectively synonymous with L ₁ in the above formula (Ia-1), and preferred aspects are also the same.

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

Examples of possible sites other than cations that compound (I) and compound (II) may have.

[Chemical 61]

[Chemical 62]

Specific examples of compound (B) are shown below, but are not limited thereto.

[Chemical 63]

The content of compound (B) in the composition of the present invention is not particularly limited, but it is preferably 0.5 mass% or more, more preferably 1.0 mass% or more based on the total solid content of the composition of the present invention. The content of compound (B) in the composition of the present invention is preferably 50.0 mass% or less, more preferably 30.0 mass% or less, and still more preferably 25.0 mass% or less based on the total solid content of the composition of the present invention. Compound (B) may be used individually by 1 type, or in 2 or more types.

[Compound (C)] The composition of the present invention contains a compound (C) different from the above-mentioned compound (B). Compound (C) is a compound represented by the following general formula (Q1).

[Chemical 64]

In the general formula (Q1), R ^1Z represents an organic group. Mq ⁺ represents a cation.

The organic group represented by R ^1Z in the general formula (Q1) is preferably an alkyl group (linear or branched), a cycloalkyl group (monocyclic or polycyclic), or an alkenyl group (linear or branched). Chain) or aryl group (monocyclic or polycyclic), more preferably aryl group, further preferably phenyl group. The alkyl group of R ^1Z is preferably an alkyl group having 1 to 5 carbon atoms such as methyl, ethyl, n-propyl, isopropyl, n-butyl, isobutyl and tert-butyl. Examples of the cycloalkyl group of R ^1Z include cycloalkyl groups having 3 to 20 carbon atoms, preferably monocyclic cycloalkyl groups such as cyclopentyl and cyclohexyl, norbornyl, tetracyclodecyl, and tetracycloalkyl groups. Polycyclic cycloalkyl groups such as dodecyl and adamantyl. The aryl group of R ^1Z is preferably an aryl group having 6 to 20 carbon atoms. Examples thereof include phenyl, naphthyl, anthracenyl, and the like, and phenyl is particularly preferred. The alkenyl group of R ^1Z is preferably an alkenyl group having 2 to 5 carbon atoms such as vinyl. The alkyl group, the cycloalkyl group, the alkenyl group and the aryl group may further have a substituent. Examples of the substituent include the aforementioned substituent T, and in particular, an alkyl group, a cycloalkyl group, an aryl group, an alkoxy group, a cycloalkoxy group, a hydroxyl group and a halogen atom are preferred.

Mq ⁺ in the general formula (Q1) represents a cation, and specific examples and preferred ranges are the same as the aforementioned M ⁺ .

Compound (C) is preferably a compound represented by the following general formula (Q2). The compound represented by the following general formula (Q2) can have both volatility resistance and solubility as a carboxylic acid after cation decomposition.

[Chemical 65]

In the general formula (Q2), R ^2Z to R ^6Z each independently represent a hydrogen atom, an alkyl group, a cycloalkyl group, an aryl group, a hydroxyl group, an alkoxy group, a cycloalkoxy group, a fluorine atom or an iodine atom. Mq ⁺ represents a cation.

The alkyl group of R ^2Z to R ^6Z is preferably an alkyl group having 1 to 5 carbon atoms such as methyl, ethyl, n-propyl, isopropyl, n-butyl, isobutyl and tert-butyl. Examples of the cycloalkyl group of R ^2Z to R ^6Z include cycloalkyl groups having 3 to 20 carbon atoms, preferably monocyclic cycloalkyl groups such as cyclopentyl and cyclohexyl, norbornyl and tetracyclodecyl. , tetracyclododecyl and adamantyl and other polycyclic cycloalkyl groups. The aryl group of R ^2Z to R ^6Z is preferably an aryl group having 6 to 20 carbon atoms. Examples thereof include phenyl, naphthyl, anthracenyl, and the like, and phenyl is particularly preferred. As the alkenyl group of R ^2Z to R ^6Z , an alkenyl group having 2 to 5 carbon atoms such as vinyl is preferred. The alkoxy group of R ^2Z to R ^6Z is preferably an alkoxy group having 1 to 5 carbon atoms. The cycloalkoxy group of R ^2Z to R ^6Z is preferably a monocyclic or polycyclic cycloalkoxy group having 3 to 20 carbon atoms.

Mq ⁺ in the general formula (Q2) represents a cation, and specific examples and preferred ranges are the same as the aforementioned M ⁺ .

The compound (C) is preferably a compound whose acidity is relatively weak relative to the acid generated from the compound (B) by irradiation with actinic rays or radioactive rays. The compound (C) functions as a quencher that captures the acid generated by the compound (B) and the like during exposure and suppresses the reaction of the resin (A) in the unexposed portion due to the excess generation of acid.

Specific examples of the compound (C) are shown below, but are not limited thereto.

[Chemical 66]

The content of compound (C) in the composition of the present invention is preferably 0.1 to 20.0 mass%, more preferably 1.0 to 20.0 mass%, based on the total solid content of the composition of the present invention. In the composition of the present invention, one type of compound (C) may be used alone, or two or more types may be used in combination.

At least one of Mq ⁺ in the general formula (Q1) or (Q2) and Mp ⁺ in the general formula (P1) is preferably a cation represented by the following general formula (KT-1).

[Chemical 67]

In the general formula (KT-1), R ^KT1 , R ^KT2 and R ^KT3 each independently represent an alkyl group, a cycloalkyl group, a halogen atom, a cyano group, an alkoxy group or an alkoxycarbonyl group. When there are plural R ^KT1 , R ^KT2 and R ^KT3 , the plural R ^KT1 , the plural R ^KT2 and the plural R ^KT3 may be the same or different respectively. w1, w2, and w3 each independently represent an integer from 0 to 5. Among them, at least one of w1, w2 and w3 represents an integer of 1 or more.

The alkyl groups of R ^KT1 , R ^KT2 and R ^KT3 may be either linear or branched. The number of carbon atoms in the alkyl group is not particularly limited, but is preferably 1 to 5, more preferably 1 to 3. The number of carbon atoms in the cycloalkyl group of R ^KT1 , R ^KT2 and R ^KT3 is not particularly limited, but is preferably 3 to 20, more preferably 5 to 15. The cycloalkyl groups of R ^KT1 , R ^KT2 and R ^KT3 can be monocyclic cycloalkyl groups such as cyclopentyl and cyclohexyl, or can also be norbornyl, tetracyclodecyl, tetracyclododecyl and adamantane. polycyclic cycloalkyl groups. Examples of the halogen atom represented by R ^KT1 , R ^KT2 and R ^KT3 include a fluorine atom, a chlorine atom, a bromine atom and an iodine atom, and a fluorine atom or an iodine atom is preferred. The alkyl group contained in the alkoxy group of R ^KT1 , R ^KT2 , and R ^KT3 may be either linear or branched. The carbon number of the alkyl group contained in the alkoxy group is not particularly limited, but is preferably 1 to 5, more preferably 1 to 3. The alkyl group contained in the alkoxycarbonyl group of R ^KT1 , R ^KT2 , and R ^KT3 may be either linear or branched. The number of carbon atoms of the alkyl group contained in the alkoxycarbonyl group is not particularly limited, but is preferably 1 to 5, more preferably 1 to 3.

w1, w2, and w3 each independently represent an integer from 0 to 5, preferably an integer from 0 to 4, and more preferably an integer from 1 to 3. Among them, at least one of w1, w2 and w3 represents an integer of 1 or more.

[Hydrophobic resin] The composition of the present invention may further contain a hydrophobic resin (also referred to as "hydrophobic resin (D)") that is different from resin (A). Hydrophobic resin (D) is preferably designed to be preferentially present on the surface of the resist film, but unlike surfactants, it does not necessarily have a hydrophilic group in its molecule, and it may not be helpful for polar and non-polar substances. of even mixing. Examples of effects brought about by adding the hydrophobic resin (D) include controlling the static and dynamic contact angles of the resist film surface with respect to water and suppressing outgassing.

From the viewpoint of localizing the film surface layer, the hydrophobic resin (D) preferably has at least one of a fluorine atom, a silicon atom, and a CH ₃ partial structure included in the side chain part of the resin, and more preferably has Two or more types. The hydrophobic resin preferably has a hydrocarbon group having 5 or more carbon atoms. These groups may exist in the main chain of the resin or may be substituted on the side chain. Examples of the hydrophobic resin (D) include compounds described in paragraphs [0275] to [0279] of International Publication No. 2020/004306.

When the composition of the present invention contains the hydrophobic resin (D), the content of the hydrophobic resin (D) is preferably 0.01 to 20.0% by mass, more preferably 0.1 to 20.0% by mass relative to the total solid content of the composition of the present invention. 15.0% by mass.

[Surfactant] The composition of the present invention may contain surfactants. When a surfactant is contained, a pattern with better adhesion and fewer development defects can be formed. The surfactant is preferably a fluorine-based and/or silicone-based surfactant. Examples of the fluorine-based and/or silicone-based surfactants include those disclosed in paragraphs [0218] and [0219] of International Publication No. 2018/193954.

One type of these surfactants may be used alone, or two or more types of surfactants may be used.

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

[Solvent] The composition of the present invention preferably contains a solvent. The solvent preferably contains at least one of (M1) and (M2), where (M1) is propylene glycol monoalkyl ether carboxylate, and (M2) is selected from the group consisting of propylene glycol monoalkyl ether, lactic acid ester, and ethyl ether. At least one of the group consisting of acid esters, alkoxypropionate esters, chain ketones, cyclic ketones, lactones and alkylene carbonates. In addition, the above-mentioned solvent may further contain components other than components (M1) and (M2).

From the viewpoint of improving the coatability of the composition of the present invention and reducing the number of development defects of the pattern, it is preferable to combine the above-mentioned solvent and the above-mentioned resin. Since the resin has a good balance of solubility, boiling point, and viscosity, the solvent can suppress uneven film thickness of the resist film and the generation of precipitates during spin coating. 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 into this specification.

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

The content of the solvent in the composition of the present invention is preferably set so that the solid content concentration becomes 0.5 to 30% by mass, more preferably 1 to 20% by mass. In this way, the coatability of the composition of the present invention can be further improved.

[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 alicyclic or aliphatic compounds containing carboxyl groups).

The above-mentioned "dissolution-inhibiting compound" refers to a compound with a molecular weight of 3000 or less that is decomposed by the action of an acid and has a reduced solubility in an organic-based developer.

The composition of the present invention is suitable for use as a photosensitive composition for EUV exposure. The wavelength of EUV light is 13.5nm. Compared with ArF (wavelength 193nm) light, etc., its wavelength is shorter, so the number of incident photons when exposed to the same sensitivity is smaller. Therefore, "photon shot noise" with a deviation in the number of photons in probability has a greater impact, leading to deterioration of line edge roughness (LER) and bridging defects. In order to reduce photon shot noise, there is a method of increasing exposure to increase the number of incident photons, but this is weighed against the requirement for high sensitivity.

When the A value calculated from the following formula (1) is high, the absorption efficiency of EUV light and electron beams of the resist film formed of the resist composition becomes high, and photon shot noise can be effectively reduced. The A value represents the absorption efficiency of EUV light and electron beam relative to the mass ratio of the resist 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 0.120 or more. The upper limit is not particularly limited, but if the A value is too large, the EUV light and electron beam transmittance of the resist film will decrease, and the optical image profile in the resist film will deteriorate. As a result, it will be difficult to obtain a good pattern shape, so it is relatively Preferably, it is 0.240 or less, and more preferably, it is 0.220 or less.

In the formula (1), [H] represents the molar ratio of hydrogen atoms derived from the total solid content of the photosensitive radiation or radiation-sensitive resin composition to all atoms of the total solid content, and [C] represents The molar ratio of carbon atoms derived from the total solid content of the photosensitive radiation-sensitive or radiation-sensitive resin composition to all atoms in the total solid content, [N] represents the molar ratio derived from the photosensitive radiation-sensitive or radiation-sensitive resin composition The molar ratio of nitrogen atoms in the total solid content in the composition to all atoms in the total solid content, [O] represents the molar ratio of oxygen atoms derived from the total solid content in the photosensitive radiation or radiation-sensitive resin composition to the total The molar ratio of all atoms in the solid content, [F], represents the molar ratio of fluorine atoms derived from the total solid content in the photosensitive radiation or radiation-sensitive resin composition to all the atoms in the total solid content, [S ] represents the molar ratio of sulfur atoms derived from the photosensitive radiation or the total solid content in the radiation-sensitive resin composition to all atoms in the total solid content, and [I] represents the molar ratio derived from the photosensitive radiation or radiation sensitivity. The molar ratio of iodine atoms in the total solid content in the resin composition to all atoms in the total solid content. For example, when the resist composition contains an acid-decomposable resin, a photoacid generator, an acid diffusion control agent, and a solvent, the acid-decomposable resin, the photoacid generator, and the acid diffusion control agent correspond to the solid content. That is, all atoms of the total solid content correspond to the sum of all atoms derived from the resin, all atoms derived from the photoacid generator, and all atoms derived from the acid diffusion control agent. For example, [H] represents the molar ratio of hydrogen atoms derived from the total solid content to all atoms in the total solid content. Based on the above example, [H] represents the hydrogen atoms derived from the acid-decomposable resin, The sum of the hydrogen atoms derived from the photoacid generator and the hydrogen atoms derived from the acid diffusion control agent is relative to all the atoms derived from the acid-decomposable resin, all the atoms derived from the photoacid generator, and The molar ratio derived from the sum of all atoms of the above acid diffusion control agent.

The A value can be calculated by calculating the ratio of the number of atoms contained in the resist composition when the structure and content of the constituent components of the total solid content in the resist composition are known. Furthermore, even when the constituent components are unknown, the constituent atomic number ratio of the resist film obtained by evaporating the solvent component of the resist composition can be calculated by an analysis method such as elemental analysis.

＜Photosensitive radiation or radiation-sensitive film and pattern forming method＞ The present invention also relates to a photosensitive radiation-sensitive or radiation-sensitive film formed from the composition of the present invention. The photosensitive radiation or radiation-sensitive film of the present invention is preferably a resist film. The sequence of the pattern forming method using the composition of the present invention is not particularly limited, but preferably includes the following processes. Process 1: A process of forming a resist film on a substrate using the composition of the present invention. Process 2: The process of exposing the resist film. Process 3: The process of developing the exposed resist film using a developer. Below, the steps of each of the above processes will be described in detail.

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

An example of a method of forming a resist film on a substrate using the composition of the present invention is a method of applying the composition of the present invention onto a substrate. In addition, it is preferable to filter the composition of the present invention with a filter if necessary 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 coated onto a substrate (eg, silicon, silicon dioxide coating) used for manufacturing integrated circuit components by a suitable coating method such as a spinner or a coater. The coating method is preferably spin coating using a spinner. The rotation speed when using a spinner for spin coating is preferably 1000 to 3000 rpm (rotation per minute). After coating the composition of the present invention, the substrate can be dried and a resist film can be formed. In addition, if necessary, various base films (inorganic films, organic films, anti-reflection films) can be formed on the lower layer of the resist film.

An example of the drying method is a method of drying by heating. Heating can be implemented by devices provided with a common exposure machine and/or developing machine, or by using a hot plate or the like. The heating temperature is preferably 80 to 150°C, more preferably 80 to 140°C, and further preferably 80 to 130°C. The heating time is preferably 30 to 1000 seconds, more preferably 60 to 800 seconds, and further preferably 60 to 600 seconds.

The film thickness of the resist film is not particularly limited, but from the viewpoint of forming a fine pattern with higher precision, it is preferably 10 to 120 nm. Among them, in the case of EUV exposure, the film thickness of the resist film is more preferably 10 to 65 nm, further preferably 15 to 50 nm. In the case of ArF immersion exposure, the film thickness of the resist film is more preferably 10 to 120 nm, further preferably 15 to 90 nm.

In addition, a top coat composition may be used to form a top coat layer on the upper layer of the resist film. The top coating composition is preferably not mixed with the resist film and can be uniformly applied to the upper layer of the resist film. The top coat layer is not particularly limited, and a previously known top coat layer can be formed by a previously known method. For example, it can be formed according to the descriptions in paragraphs [0072] to [0082] of Japanese Patent Application Laid-Open No. 2014-059543. Top coat. For example, it is preferable to form a top coat layer including a basic compound such as that described in Japanese Patent Application Laid-Open No. 2013-61648 on the resist film. Specific examples of the basic compounds that can be contained in the top coat include basic compounds that can be contained in the composition of the present invention. It is also preferred that the top coat layer contains a compound containing 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 resist film. An example of the exposure method is a method of irradiating the formed resist film with actinic rays or radiation through a predetermined mask. Examples of actinic rays or radiation include infrared light, visible light, ultraviolet light, far ultraviolet light, extreme ultraviolet light, X-rays, and electron beams. The ray is preferably 250 nm or less, more preferably 220 nm or less, and particularly preferably 1 to 10 nm. Far ultraviolet light with a wavelength of 200nm, specifically, KrF excimer laser (248nm), ArF excimer laser (193nm), F ₂ excimer laser (157nm), EUV (13.5nm), X-rays, and electron beam.

It is preferable to bake (heat) after exposure and before development. Baking can promote the reaction of the exposed part, thereby improving the sensitivity and pattern shape. The heating temperature is preferably 80 to 150°C, more preferably 80 to 140°C, and further preferably 80 to 130°C. The heating time is preferably 10 to 1000 seconds, more preferably 10 to 180 seconds, and further preferably 30 to 120 seconds. Heating can be performed by devices provided with a common exposure machine and/or developing machine, or by using a hot plate or the like. This process is also called post-exposure bake.

(Process 3: Development process) Process 3 is a process in which a developer is used to develop the exposed resist film to form a pattern. The developer may be an alkali developer or a developer containing an organic solvent (hereinafter also referred to as an organic developer).

Examples of the development method include a method in which the substrate is immersed in a tank filled with a developer for a certain period of time (immersion method), and a method in which the developer is deposited on the surface of the substrate by surface tension and left to stand for a certain period of time to develop. (puddle method), a method of spraying a developer onto a substrate surface (spray method), and a method of continuously spraying a developer from a nozzle while scanning at a certain speed on a substrate rotating at a certain speed (spray method) dynamic allocation method). In addition, after performing the development process, it is also possible to perform a process of stopping the development while replacing it with another solvent. The development time is not particularly limited as long as the resin in the unexposed portion is fully dissolved, but it is preferably 10 to 300 seconds, more preferably 20 to 120 seconds. The temperature of the developer is preferably 0 to 50°C, more preferably 15 to 35°C.

As an alkali developer, an alkali aqueous solution containing an alkali is preferably used. The type of alkali aqueous solution is not particularly limited, and examples thereof include quaternary ammonium salts represented by tetramethylammonium hydroxide, inorganic bases, primary amines, secondary amines, tertiary amines, alcoholamines, or cyclic Alkaline aqueous solutions of amines, etc. Among them, the alkali developer is preferably an aqueous solution of a quaternary ammonium salt represented by tetramethylammonium hydroxide (TMAH). An appropriate amount of alcohols, surfactants, etc. can be added to the alkali developer. The alkali concentration of the alkali developer is usually preferably 0.1 to 20% by mass. The pH of an alkali developer is generally preferably 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.

A plurality of types of the above-mentioned solvents may be mixed, and they may be mixed with solvents other than those mentioned above or water. The moisture content of the entire 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 contains substantially no water. The content of the organic solvent relative to the organic developer is preferably 50 mass% or more and 100 mass% or less, more preferably 80 mass% or more and 100 mass% or less, and further preferably 90 mass% relative to the total amount of the developer. It is 95 mass % or more and 100 mass % or less, especially preferably 95 mass % or more and 100 mass % or less.

(Other processes) The above pattern forming method preferably includes a process of cleaning with a rinse liquid after process 3.

Examples of the rinse liquid used in the rinse process after the development process with an alkali developer include pure water. In addition, an appropriate amount of surfactant can be added to pure water. An appropriate amount of surfactant can also be added to the rinse solution.

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

The method of the rinsing process is not particularly limited. Examples include a method of continuously spraying a rinsing liquid onto a substrate rotating at a certain speed (spin coating method), and a method of immersing the substrate in a tank filled with a rinsing liquid for a certain period of time ( dipping method), and the method of spraying rinsing liquid on the surface of the substrate (spraying method). In addition, the pattern forming method may include a heating process (Post Bake) after the rinse process. Through this process, the developer and rinse fluid remaining between and inside the patterns are removed by baking. In addition, this process also has the effect of annealing the resist 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 10 seconds to 3 minutes (preferably 30 seconds to 120 seconds).

Furthermore, the formed pattern can be used as a mask to perform etching of the substrate. That is, the pattern formed in process 3 can be used as a mask to process the substrate (or the underlying film and the 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, but it is preferable to use the pattern formed in process 3 as a mask and dry-etch the substrate (or the underlying film and the substrate) to form a pattern on the substrate. method of forming patterns. Dry etching is preferably oxygen plasma etching.

Various materials used in the composition and pattern forming method of the present invention (for example, solvents, developers, rinse solutions, antireflection film forming compositions, top coat forming compositions, etc.) are preferably free of metal, etc. Impurities. The impurity content contained in these materials is preferably 1 mass ppm (parts per million, one part per million) or less, more preferably 10 mass ppb (parts per billion, one part per billion) or less, still more preferably It is less than 100 ppt by mass, the best is less than 10 ppt by mass, and the best is less than 1 ppt by mass. 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.

An example of a method for removing impurities such as metals from various materials is filtration using a filter. Details of filtering using a filter are described in paragraph [0321] of International Publication No. 2020/004306.

Examples of methods for reducing impurities such as metals contained in various materials include selecting raw materials with low metal content as the raw materials constituting the various materials, filtering the raw materials constituting the various materials with a filter, and using TEFLON (Registered Trademark) A method of distilling under conditions that suppress contamination as much as possible by forming a lining in the device, etc.

In addition to filter filtration, adsorbent materials can also be used to remove impurities, or a combination of filter filtration and adsorbent materials can be used. As the adsorbent material, known adsorbent materials can be used. For example, inorganic adsorbent materials such as silica gel and zeolite, and organic adsorbent materials such as activated carbon can be used. In order to reduce metal and other impurities contained in the various materials mentioned above, it is necessary to prevent the mixing of metal impurities during the manufacturing process. Whether metal impurities have been sufficiently removed from the manufacturing equipment can be confirmed by measuring the content of metal components contained in the cleaning liquid used to clean the manufacturing equipment. The content of the metal component contained in the cleaning solution after use is preferably 100 ppt by mass (parts per trillion, one part per trillion) or less, more preferably 10 ppt by mass or less, and still more 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 fluids such as flushing fluids to prevent breakdown of chemical piping and various components (filters, O-rings, tubes, etc.) caused by electrostatic charging and subsequent electrostatic discharge. The conductive compound is not particularly limited, and examples thereof include methanol. The addition amount is not particularly limited, but from the viewpoint of maintaining better development characteristics or flushing characteristics, it is preferably 10 mass% or less, and more preferably 5 mass% or less. The lower limit is not particularly limited, but is preferably 0.01 mass% or more. As the chemical liquid piping, for example, SUS (stainless steel) or various piping coated with polyethylene, polypropylene, or fluororesin (polytetrafluoroethylene, perfluoroalkoxy resin, etc.) that has been subjected to antistatic treatment can be used. Similarly, for filters and O-rings, polyethylene, polypropylene, or fluororesin (polytetrafluoroethylene, perfluoroalkoxy resin, etc.) that has been treated with antistatic treatment can be used.

＜Manufacturing method of electronic components＞ This specification also relates to a manufacturing method of an electronic component including the above pattern forming method, and an electronic component manufactured by the manufacturing method. A preferable aspect of the electronic component described in this specification is one that is mounted on electrical and electronic equipment (home appliances, OA (Office Automation), media-related equipment, optical equipment, communication equipment, etc.). [Example]

The present invention will be described in more detail below based on examples. The materials, usage amounts, ratios, processing contents, processing steps, etc. shown in the following examples can be appropriately changed as long as they do not deviate from the gist of the present invention. Therefore, the scope of the present invention should not be construed restrictively by the embodiments shown below.

Various components used in the resist compositions of Examples and Comparative Examples are shown below.

<Resin (A)> As the resin (A), AP-1 to AP-18 were used. Moreover, in Comparative Examples 1 and 3, AX-2 and AX-1 were used as resins other than resin (A). For convenience, AX-1 and AX-2 are also listed in the resin (A) column in Table 2 below. The structures of AP-1 to AP-18, AX-1, and AX-2 are shown below. The content ratio of the following repeating units (relative to the content of all repeating units in the resin) is molar ratio (mol%). In addition, the weight average molecular weight (Mw) and dispersion (Pd=Mw/Mn) of AP-1 to AP-18, AX-1 and AX-2 are also shown below. The Mw and Pd of the resin were measured by GPC (carrier: tetrahydrofuran (THF)) (in terms of polystyrene). In addition, the content of repeating units is measured by ¹³ C-NMR (nuclear magnetic resonance, nuclear magnetic resonance).

[Chemical 68]

[Chemical 69]

[Chemical 70]

[Chemical 71]

＜Compound (B)＞ As compound (B), B-1 to B-5 were used.

[Chemical 72]

Tables 1 and 2 below describe the ClogP value of acid generated (acid generated) from compound (B) by irradiation with actinic rays or radioactive rays. Regarding B-1 and B-5, the ClogP value of a structure in which an acid-decomposable group that generates an acid is decomposed by an acid is described. When two compounds (B) are used, record the ClogP value separated by "/". For example, in the resist composition R-20 of Example 20, B-1 and B-2 are used, and the column of "Compound (B) generates acid ClogP" in Table 2 is written as "3.1/7.2". This means that the acid-generating ClogP value of B-1 (a structure in which an acid-decomposable group is decomposed by an acid) is 3.1, and the acid-generating ClogP value of B-2 is 7.2.

＜Compound (C)＞ As compound (C), C-1 to C-4 were used. Moreover, in Comparative Example 2, CX-1 was used as a compound other than compound (C). For convenience, CX-1 is also listed in the compound (C) column in Table 2 below.

[Chemical 73]

＜Solvent＞ The solvents used are shown below. PGMEA: propylene glycol monomethyl ether acetate PGME: propylene glycol monomethyl ether EL: Ethyl lactate

＜Surface active agent＞ As the surfactant, D-1 was used. 20 in the following structural formula represents the number of repeating units.

[Chemical 74]

<Preparation of resist composition> The components shown in Tables 1 and 2 were dissolved in the solvents shown in Tables 1 and 2 at the contents (mass %) shown in Tables 1 and 2, to prepare solid components shown in Tables 1 and 2 concentration (mass %) and filtered through a polyethylene filter with a pore size of 0.02 μm, thereby obtaining resist compositions R-1 to R-32 and RX-1 to RX-3. Regarding the solvent, the types and mass ratios of the compounds used are described in Tables 1 and 2. The content of components other than the solvent is a mass ratio relative to the total solid content of the resist composition. When more than two types of each ingredient are used, each type and content are separated by "/". For example, "C-1/C-2" in the resist composition R-21 means that two types of C-1 and C-2 are used as the compound (C), and "7.00/7.00" means that the content of C-1 is 7.00% by mass, and the content of C-2 is 7.00% by mass.

[Table 1]

[Table 2]

＜Coating of resist composition＞ The prepared resist composition was coated on a 6-inch Si (silicon) wafer previously treated with hexamethyldisilazane (HMDS) using a spin coater Mark8 manufactured by Tokyo Electron, and It was dried on a hot plate at 130° C. for 300 seconds to form a resist film with a film thickness shown in Table 3. In addition, the same results can be obtained by replacing the above-mentioned Si wafer with a chromium substrate.

<Examples 1 to 14, 16 to 32, Comparative Examples 1 to 3; EB exposure, alkali development (positive type)> The wafer coated with the resist film obtained above was pattern-irradiated using an electron beam drawing apparatus (manufactured by Advantest Co., Ltd.; F7000S, acceleration voltage 50keV). At this time, drawing was performed so as to form a 1:1 line and space with a line width of 30 nm. After electron beam drawing, it was heated on a hot plate at 130° C. for 300 seconds, immersed in a 2.38 mass% tetramethylammonium hydroxide (TMAHaq) aqueous solution for 60 seconds, rinsed with water for 45 seconds, and dried. Then, the wafer was rotated at 4000 rpm for 30 seconds, and then baked at 90° C. for 60 seconds to dry. This forms a pattern.

<Example 15; EB exposure, organic solvent development (negative type)> The wafer coated with the resist film obtained above was pattern-irradiated using an electron beam drawing apparatus (manufactured by Advantest Co., Ltd.; F7000S, acceleration voltage 50keV). At this time, drawing was performed so as to form a 1:1 line and space with a line width of 30 nm. After electron beam drawing, it was heated on a hot plate at 130°C for 300 seconds, developed with n-butyl acetate (nBA) for 30 seconds, and spin-dried to obtain a negative pattern. Then, the wafer was rotated at 4000 rpm for 30 seconds, and then baked at 90° C. for 60 seconds to dry. This forms a pattern.

[evaluation] The formed pattern was evaluated for defects using a defect evaluation device (KLA2360; manufactured by KLA-Tencor Corporation). The re-inspection image is obtained by Review SEM (SEMVision G3E FIB; manufactured by AMAT), and the number of defects is calculated. The results are shown in Table 3 below.

[table 3]

It can be seen from the results in Table 3 that the resist compositions used in Examples 1 to 32 can suppress the occurrence of defects when forming extremely fine patterns compared to the resist compositions used in Comparative Examples 1 to 3. [Industrial availability]

According to the present invention, it is possible to provide a photosensitive radiation-sensitive or radiation-sensitive resin composition capable of suppressing the occurrence of defects when forming an extremely fine pattern (for example, a line width of 30 nm or less). Furthermore, according to the present invention, it is possible to provide a resist film, a pattern forming method, and an electronic component manufacturing method using the above-mentioned photosensitive radiation or radiation-sensitive resin composition.

Although the present invention has been described in detail with reference to specific embodiments, it is obvious to those skilled in the art that various changes and modifications can be made without departing from the spirit and scope of the present invention. This application is a patent application based on the Japanese patent application (Japanese Patent Application No. 2022-030343) filed on February 28, 2022, the contents of which are incorporated into this specification by reference.

Claims (15)

A photosensitive radiation-sensitive or radiation-sensitive resin composition, which contains a resin (A), a compound (B) that generates an acid by irradiation with actinic rays or radiation, and a compound different from the compound (B) (C), wherein the resin (A) contains a repeating unit represented by the following general formula (N1) and a repeating unit represented by the following general formula (S1), and the resin (A) is represented by the following The content of the repeating unit represented by the general formula (N1) is 55 mol% or more relative to all the repeating units in the resin (A), and the compound (C) is a compound represented by the following general formula (Q1) , In the general formula (N1), R ^1N to R ^3N each independently represent a hydrogen atom, an alkyl group, a cycloalkyl group, a halogen atom, a cyano group, an alkoxy group or an alkoxycarbonyl group, and R ^4N represents a hydrogen atom or something other than a hydroxyl group. Substituent, R ^4N can be bonded to at least one of R ^1N ~ R ^3N . When there are plural R ^4Ns , the plural R ^4Ns can be the same or different, and the plural R ^4Ns can be bonded. k1 represents 0 or 1, When k1 represents 0, k2 represents an integer from 1 to 5, k3 represents 5-k2, when k1 represents 1, k2 represents an integer from 1 to 7, k3 represents 7-k2, In the general formula (S1), R ^1S to R ^3S each independently represent a hydrogen atom, an alkyl group, a cycloalkyl group, a halogen atom, a cyano group, an alkoxy group or an alkoxycarbonyl group, and R ^4S represents a hydrogen atom or -COOR ^5S . ^{For substituents other than _ _ _} When a plurality of R ^5S is present in a group separated by the action of an acid, the plurality of R ^5S may be the same or different. m1 represents 0 or 1. When m1 represents 0, m2 represents an integer from 1 to 5, and m3 represents 5- m2, when m1 represents 1, m2 represents an integer from 1 to 7, m3 represents 7-m2, In the general formula (Q1), R ^1Z represents an organic group, and Mq ⁺ represents a cation. The photosensitive radiation or radiation-sensitive resin composition according to claim 1, wherein the repeating unit represented by the general formula (S1) is a repeating unit represented by the following general formula (S2), In the general formula (S2), R ^1S to R ^3S each independently represent a hydrogen atom, an alkyl group, a cycloalkyl group, a halogen atom, a cyano group, an alkoxy group or an alkoxycarbonyl group, R ^6S represents an organic group, and R ^7S represents - For substituents other than COOR ^5S , when there are multiple R ^7S , the plural R ^7S may be the same or different. R ^5S represents a group that is detached by the action of an acid. R ^8S represents a substituent, and there are multiple R ^8S . When , a plurality of R ^8S may be the same or different, and a plurality of R ^8S may be bonded. m4 represents an integer from 1 to 3, m5 represents an integer from 0 to 4, and m6 represents an integer from 0 to (2×m4+6). The photosensitive radiation or radiation-sensitive resin composition according to claim 1, wherein the compound (B) is a compound represented by the following general formula (P1), In the general formula (P1), R ^1P to R ^5P each independently represent a hydrogen atom, an alkyl group, a cycloalkyl group, an aryl group, a hydroxyl group, an alkoxy group or a cycloalkoxy group, and R ^1P to R ^5P do not contain a fluorine atom. Mp ⁺ represents a cation. The photosensitive radiation-sensitive or radiation-sensitive resin composition according to claim 1, wherein the ClogP value of the acid generated from the compound (B) by irradiation with actinic rays or radiation is 3.5 or less. The photosensitive radiation or radiation-sensitive resin composition according to claim 1, wherein the compound (C) is a compound represented by the following general formula (Q2), In the general formula (Q2), R ^2Z to R ^6Z independently represent a hydrogen atom, an alkyl group, a cycloalkyl group, an aryl group, a hydroxyl group, an alkoxy group, a cycloalkoxy group, a fluorine atom or an iodine atom, and Mq ⁺ represents a cation. . The photosensitive radiation or radiation-sensitive resin composition according to claim 3, wherein at least one of Mq ⁺ and Mp ⁺ is a cation represented by the following general formula (KT-1), In the general formula (KT-1), R ^KT1 , R ^KT2 and R ^KT3 independently represent an alkyl group, a cycloalkyl group, a halogen atom, a cyano group, an alkoxy group or an alkoxycarbonyl group, and there are multiple R ^KT1 , R When ^KT2 and R ^KT3 , a plurality of R ^KT1 , a plurality of R ^KT2 and a plurality of R ^KT3 may be the same or different respectively. w1, w2 and w3 respectively independently represent integers from 0 to 5, where among w1, w2 and w3 At least one of represents an integer above 1. The photosensitive radiation or radiation-sensitive resin composition according to claim 1, wherein the content of the repeating unit represented by the general formula (N1) in the resin (A) is relative to the resin (A). All repeating units in A) are above 65 mol%. The photosensitive radiation-sensitive or radiation-sensitive resin composition according to claim 1, wherein the content of the repeating unit represented by the general formula (S1) in the resin (A) is relative to the resin (A). All repeating units in A) are above 25 mol%. The photosensitive radiation or radiation-sensitive resin composition according to claim 1, wherein the repeating units contained in the resin (A) are only the repeating units represented by the general formula (N1) and the repeating units represented by the general formula (N1). The repeating unit represented by the general formula (S1) is shown below. The photosensitive radiation or radiation-sensitive resin composition according to claim 1, wherein the weight average molecular weight of the resin (A) is 8,000 or less. The photosensitive radiation or radiation-sensitive resin composition according to claim 1, wherein the dispersion degree of the resin (A) is 1.7 or less. The photosensitive radiation or radiation-sensitive resin composition according to claim 1, wherein the compound (B) has an acid-decomposable group. A resist film formed using the photosensitive radiation or radiation-sensitive resin composition according to any one of claims 1 to 12. A pattern forming method having: A process for forming a resist film on a substrate using the photosensitive radiation-sensitive or radiation-sensitive resin composition as described in any one of claims 1 to 12; A process for exposing the resist film; and A process of developing the exposed resist film using a developing solution. A manufacturing method of electronic components, which includes the pattern forming method as described in claim 14.