WO2023162762A1

WO2023162762A1 - Actinic-ray-sensitive or radiation-sensitive resin composition, resist film, pattern forming method, and electronic device manufacturing method

Info

Publication number: WO2023162762A1
Application number: PCT/JP2023/004863
Authority: WO
Inventors: 文博吉野; 知昭吉岡; 英治福▲崎▼
Original assignee: 富士フイルム株式会社
Priority date: 2022-02-28
Filing date: 2023-02-13
Publication date: 2023-08-31
Also published as: TW202342439A

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

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

The present invention relates to an actinic ray-sensitive or radiation-sensitive resin composition, a resist film, a pattern forming method, and an electronic device manufacturing method. More specifically, the present invention provides an ultra-microlithography process applicable to ultra LSI (Large Scale Integration) and high-capacity microchip manufacturing processes, nanoimprint mold manufacturing processes, high-density information recording medium manufacturing processes, and the like. The present invention relates to an actinic ray- or radiation-sensitive resin composition, an actinic ray- or radiation-sensitive film, a pattern forming method, and an electronic device manufacturing method that can be suitably used in other photofabrication processes.

Conventionally, in the manufacturing process of semiconductor devices such as ICs (Integrated Circuits) and LSIs (Large Scale Integration), microfabrication is performed by lithography using resist compositions. 2. Description of the Related Art In recent years, as integrated circuits have become more highly integrated, there has been a demand for ultra-fine pattern formation in the submicron region or quarter micron region. Along with this, there is a tendency for the exposure wavelength to become shorter, from the g-line to the i-line and then to the KrF excimer laser light. At present, an exposure machine using an ArF excimer laser with a wavelength of 193 nm as a light source has been developed. ing. Further, as a technique for further improving the resolution, the so-called liquid immersion method, in which the space between the projection lens and the sample is filled with a liquid with a high refractive index (hereinafter also referred to as "immersion liquid"), has been developed.

In addition to excimer laser light, lithography using electron beams (EB), X-rays, extreme ultraviolet rays (EUV), etc. is currently under development. Along with this, resist compositions that are effectively sensitive to various actinic rays or radiation have been developed.

Various compositions are known as actinic ray-sensitive or radiation-sensitive resin compositions. For example, Patent Literature 1 and Patent Literature 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.

Japanese Patent Application Laid-Open No. 2019-219470 Japanese Patent Application Laid-Open No. 2021-130808

However, the resist compositions described in Patent Documents 1 and 2 have the problem that defects (eg, bridge defects and residue defects) are likely to occur in ultrafine pattern formation with a line width of 30 nm or less, for example.

An object of the present invention is to provide an actinic ray-sensitive or radiation-sensitive resin composition that can suppress the occurrence of defects in ultrafine (for example, line width of 30 nm or less) pattern formation. Another object of the present invention is to provide a resist film, a pattern forming method, and an electronic device manufacturing method using the actinic ray-sensitive or radiation-sensitive resin composition.

The inventors have found that the above problems can be solved by the following configuration.

[1]
An actinic ray-sensitive or radiation-sensitive resin composition comprising a resin (A), a compound (B) that generates an acid upon exposure to actinic rays or radiation, and a compound (C) different from the compound (B), ,
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),
The content of the repeating unit represented by the following general formula (N1) in the resin (A) is 55 mol% or more with respect to the total repeating units in the resin (A),
The compound (C) is a compound represented by the following general formula (Q1),
Actinic ray-sensitive or radiation-sensitive resin composition.

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.
^R4N represents a hydrogen atom or a substituent other than a hydroxy group. R ^4N may be combined with at least one of R ^1N to R ^3N . When multiple ^R4Ns are present, the multiple ^R4Ns may be the same or different, and multiple ^R4Ns may be bonded.
k1 represents 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.

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 bound to at least one of R ^1S to R ^3S . When multiple R ^4S are present, the multiple R ^4S may be the same or different, and multiple R ^4S may be combined.
^R5S represents a group that leaves under the action of an acid. When multiple R ^5S are present, the multiple 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, and m3 represents 7-m2.

In general formula (Q1), R ^1Z represents an organic group. Mq ⁺ represents a cation.
[2]
The actinic ray-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).

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.
^R6S represents an organic group.
R ^7S represents a substituent other than —COOR ^5S . When multiple ^R7S are present, the multiple ^R7S may be the same or different. ^R5S represents a group that leaves under the action of an acid.
^R8S represents a substituent. When multiple R ^8S are present, the multiple R ^8S may be the same or different, and multiple R ^8S may be combined.
m4 represents an integer of 1-3.
m5 represents an integer of 0-4.
m6 represents an integer from 0 to (2×m4+6).
[3]
The actinic ray-sensitive or radiation-sensitive resin composition according to [1] or [2], 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 hydroxy group, an alkoxy group, or a cycloalkyloxy group. R ^1P to R ^5P do not contain fluorine atoms.
Mp ⁺ represents a cation.
[4]
Actinic ray-sensitive or radiation-sensitive according to any one of [1] to [3], wherein the ClogP value of the acid generated from the compound (B) upon exposure to actinic rays or radiation is 3.5 or less. Resin composition.
[5]
The actinic ray-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).

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 hydroxy group, an alkoxy group, a cycloalkyloxy group, a fluorine atom or an iodine atom.
Mq ⁺ represents a cation.
[6]
The actinic ray-sensitive or radiation-sensitive resin composition according to any one of [1] to [5], wherein at least one of Mq ⁺ and Mp ⁺ is a cation represented by the following general formula (KT-1) thing.

In 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 a plurality of ^RKT1 , ^RKT2 and ^RKT3 , the plurality of ^RKT1 , the plurality of ^RKT2 and the plurality of ^RKT3 may be the same or different. w1, w2 and w3 each independently represents an integer of 0 to 5; However, at least one of w1, w2 and w3 represents an integer of 1 or more.
[7]
[1] to [6, wherein the content of the repeating unit represented by the general formula (N1) in the resin (A) is 65 mol% or more with respect to the total repeating units in the resin (A) ] The actinic ray-sensitive or radiation-sensitive resin composition according to any one of .
[8]
[1] to [7, wherein the content of the repeating unit represented by the general formula (S1) in the resin (A) is 25 mol% or more relative to the total repeating units in the resin (A). ] The actinic ray-sensitive or radiation-sensitive resin composition according to any one of .
[9]
[1] to [8], wherein the repeating units contained in the resin (A) are only repeating units represented by the general formula (N1) and repeating units represented by the general formula (S1). Actinic ray-sensitive or radiation-sensitive resin composition according to any one of the above.
[10]
The actinic ray-sensitive or radiation-sensitive resin composition according to any one of [1] to [9], wherein the resin (A) has a weight average molecular weight of 8000 or less.
[11]
The actinic ray-sensitive or radiation-sensitive resin composition according to any one of [1] to [10], wherein the resin (A) has a dispersion degree of 1.7 or less.
[12]
The actinic ray-sensitive 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 actinic ray-sensitive or radiation-sensitive resin composition according to any one of [1] to [12].
[14]
forming a resist film on a substrate using the actinic ray-sensitive or radiation-sensitive resin composition according to any one of [1] to [12]; exposing the resist film; and developing the exposed resist film with a developer.
[15]
A method for manufacturing an electronic device, including the pattern forming method according to [14].

According to the present invention, it is possible to provide an actinic ray-sensitive or radiation-sensitive resin composition that can suppress the occurrence of defects in the formation of extremely fine (for example, line width of 30 nm or less) patterns. Moreover, the present invention can provide a resist film, a pattern forming method, and an electronic device manufacturing method using the actinic ray-sensitive or radiation-sensitive resin composition.

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

As used herein, "actinic ray" or "radiation" means, for example, the emission line spectrum of a mercury lamp, far ultraviolet rays represented by excimer lasers, extreme ultraviolet rays (EUV: Extreme Ultraviolet), X-rays, soft X-rays, and electron It means a line (EB: Electron Beam) or the like.
As used herein, "light" means actinic rays or radiation.
In the present specification, the term "exposure" means, unless otherwise specified, not only exposure by the emission line spectrum of mercury lamps, far ultraviolet rays represented by excimer lasers, extreme ultraviolet rays, X-rays, and EUV, but also electron beams and ion beams. It also includes drawing with particle beams such as beams.
In the present specification, the term "~" is used to include the numerical values before and after it as lower and upper limits.

In this specification, (meth)acrylate represents at least one of acrylate and methacrylate. (Meth)acrylic acid represents at least one of acrylic acid and methacrylic acid.

In this specification, the weight average molecular weight (Mw), number average molecular weight (Mn), and dispersity (also referred to as molecular weight distribution) (Mw/Mn) of the resin are measured by GPC (Gel Permeation Chromatography) equipment (HLC manufactured by Tosoh Corporation). -8120 GPC) by GPC measurement (solvent: tetrahydrofuran, flow rate (sample injection volume): 10 μL, column: TSK gel Multipore HXL-M manufactured by Tosoh Corporation, column temperature: 40 ° C., flow rate: 1.0 mL / min, detector: It is defined as a polystyrene conversion value by a differential refractive index detector (Refractive Index Detector).

Regarding the notation of a group (atomic group) in the present specification, as long as it does not contradict the spirit of the present invention, the notation that does not describe substituted or unsubstituted includes groups containing substituents as well as groups that do not have substituents. do. For example, an "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). Also, the term "organic group" as used herein refers to a group containing at least one carbon atom.
As a substituent, a monovalent substituent is preferable unless otherwise specified. Examples of substituents include monovalent nonmetallic atomic groups excluding hydrogen atoms, and can be selected from the following substituents T, for example.

(substituent T)
The substituent T includes halogen atoms such as fluorine, chlorine, bromine and iodine atoms; alkoxy groups such as methoxy, ethoxy and tert-butoxy; cycloalkyloxy; phenoxy and p-tolyloxy; alkoxycarbonyl groups such as methoxycarbonyl and butoxycarbonyl groups; cycloalkyloxycarbonyl groups; aryloxycarbonyl groups such as phenoxycarbonyl groups; acyloxy groups such as acetoxy groups, propionyloxy groups and benzoyloxy groups; benzoyl group, isobutyryl group, acryloyl group, methacryloyl group and methoxalyl group; sulfanyl group; alkylsulfanyl group such as methylsulfanyl group and tert-butylsulfanyl group; phenylsulfanyl group and p-tolylsulfanyl group Arylsulfanyl group; Alkyl group; Alkenyl group; Cycloalkyl group; Aryl group; Aromatic heterocyclic group; Hydroxy group; amide group; silyl group; amino group; carbamoyl group; In addition, when these substituents can further have one or more substituents, a group having one or more substituents selected from the substituents described above as the further substituents (e.g., monoalkylamino group , a dialkylamino group, an arylamino group, a trifluoromethyl group, etc.) are also included in examples of the substituent T.

In this specification, the bonding direction of the divalent groups indicated is not limited unless otherwise specified. For example, in the compound represented by the formula "XYZ", when Y is -COO-, Y may be -CO-O- or -O-CO- good too. The compound may be "X—CO—O—Z" or "X—O—CO—Z."

As used herein, the acid dissociation constant (pKa) represents the pKa in an aqueous solution. is a calculated value. All pKa values described herein are calculated using this software package.
Software Package 1: Advanced Chemistry Development (ACD/Labs) Software V8.14 for Solaris (1994-2007 ACD/Labs).

pKa can also be determined by molecular orbital calculation. As a specific method for this, there is a method of calculating the H 2 ⁺ dissociation free energy in an aqueous solution based on the thermodynamic cycle. H ⁺ dissociation free energy can be calculated by, for example, DFT (density functional theory), but various other methods have been reported in literature, etc., and are not limited to this. . Note that there are a plurality of software that can implement DFT, and Gaussian16 is an example.

In the present specification, pKa refers to a value obtained by calculating a value based on Hammett's substituent constant and a database of known literature values using software package 1, as described above. If it cannot be calculated, a value obtained by Gaussian 16 based on DFT (density functional theory) is adopted.
In this specification, pKa refers to "pKa in aqueous solution" as described above, but when pKa in aqueous solution cannot be calculated, "pKa in dimethyl sulfoxide (DMSO) solution" is adopted. and

As used herein, the term "solid content" means a component that forms an actinic ray-sensitive or radiation-sensitive film, and does not include a solvent. In addition, as long as it is a component that forms an actinic ray-sensitive or radiation-sensitive film, it is regarded as a solid content even if the property is liquid.

<Actinic ray-sensitive or radiation-sensitive resin composition>
The actinic ray-sensitive or radiation-sensitive resin composition of the present invention (also referred to as "the composition of the present invention") comprises at least a resin (A) and a compound (B) that generates an acid upon exposure to actinic rays or radiation. , and an actinic ray-sensitive or radiation-sensitive resin composition containing a compound (C) different from the compound (B), wherein the resin (A) is a repeating unit represented by the general formula (N1), and the general formula Including the repeating unit represented by (S1), the content of the repeating unit represented by general formula (N1) in the resin (A) is 55 mol% or more with respect to the total repeating units in the resin (A). and the compound (C) is an actinic ray-sensitive or radiation-sensitive resin composition represented by the general formula (Q1).

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

The reason why the composition of the present invention can suppress the occurrence of defects in the formation of extremely fine patterns (for example, a line width of 30 nm or less) is not necessarily clear, but the present inventors presume 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 is represented by the general formula (N1) content of the repeating unit is 55 mol % or more based on the total repeating units. When the content of the repeating unit represented by formula (N1) is 55 mol% or more based on the total repeating units, the hydrophobicity of the resin (A) can be appropriately adjusted. In addition, the repeating unit represented by the general formula (S1) has an acid-decomposable group, and R ^5S is eliminated by exposure to generate a carboxyl group bonded to the aromatic ring, so that the dissolution contrast can be increased. can be done.
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. be done.
It is considered that the occurrence of defects can be suppressed by these.

The composition of the present invention is typically a resist composition, and may be a positive resist composition or a negative resist composition. The composition of the present invention may be a resist composition for alkali development or a resist composition for organic solvent development.
The composition of the present invention may be 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.
Actinic ray-sensitive or radiation-sensitive films can be formed using the composition of the present invention. The actinic ray-sensitive or radiation-sensitive film formed using the composition of the present invention is typically a resist film.
In the following, first, various components of the composition of the present invention are described in detail.

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

(Repeating unit represented by general formula (N1))
The repeating unit represented by formula (N1) will be described.
R ^1N to R ^3N in 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 linear or branched. Although the number of carbon atoms in the alkyl group is not particularly limited, it is preferably 1-5, more preferably 1-3.
The number of carbon atoms in the cycloalkyl group of R ^1N to R ^3N is not particularly limited, but is preferably 3-20, more preferably 5-15. The cycloalkyl groups of R ^1N to R ^3N may be monocyclic cycloalkyl groups such as cyclopentyl group and cyclohexyl group, or polycyclic groups such as norbornyl group, tetracyclodecanyl group, tetracyclododecanyl group and adamantyl group. It may be a cyclic cycloalkyl group.
The halogen atoms of R ^1N to R ^3N include fluorine, chlorine, bromine and iodine atoms, preferably fluorine or iodine.
The alkyl groups contained in the alkoxy groups of R ^1N to R ^3N may be linear or branched. Although the number of carbon atoms in the alkyl group contained in the alkoxy group is not particularly limited, it is preferably 1-5, more preferably 1-3.
The alkyl groups contained in the alkoxycarbonyl groups of R ^1N to R ^3N may be linear or branched. Although the number of carbon atoms in the alkyl group contained in the alkoxycarbonyl group is not particularly limited, it is preferably 1-5, more preferably 1-3.
R ^1N to R ^3N preferably represent a hydrogen atom or a methyl group, and more preferably represent a hydrogen atom.

k1 in general formula (N1) represents 0 or 1; When k1 represents 0, the aromatic ring described in general formula (N1) represents a benzene ring. When k1 represents 1, the aromatic ring described in 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 zero.
k2 preferably represents an integer of 1 to 3, more preferably 1 or 2, even more preferably 1.

^R4N in general formula (N1) represents a hydrogen atom or a substituent other than a hydroxy group.
The substituent represented by ^R4N is not particularly limited as long as it is a substituent other than a hydroxy group. Examples include a carboxyl group, a halogen atom (preferably a fluorine atom or an iodine atom), an alkyl group (preferably an alkyl group), alkenyl groups (preferably alkenyl groups having 2 to 5 carbon atoms), alkoxy groups (preferably alkoxy groups having 1 to 5 carbon atoms), and the like.
^R4N preferably represents a hydrogen atom.
When multiple ^R4Ns are present, the multiple ^R4Ns may be the same or different, and multiple ^R4Ns may be bonded.

R ^4N may be combined with 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 general formula (N1-2) and a repeating unit represented by general formula (N1-3) described below. .

The repeating unit represented by the general formula (N1) is 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- It is preferably a repeating unit represented by 3).

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

In general formula (N1-2), R ^1N , R ^2N , R ^4N , and k1 each have the same meaning as R ^1N , R ^2N , R ^4N , and k1 in general formula (N1), and specific examples and The preferred range 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 preferably represents an integer of 1 to 3, more preferably 1 or 2, even more preferably 1.

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

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

In general formula (N2), R ^1N to R ^3N each have the same meaning as R ^1N to R ^3N in general formula (N1), and specific examples and preferred ranges are also the same.
^R6N represents a substituent other than a hydroxy group.
k8 represents an integer of 1-5.
k9 represents 0 to (5-k8).
Examples of substituents 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), an alkenyl group (preferably having 2 to 5 alkenyl groups), alkoxy groups (preferably alkoxy groups having 1 to 5 carbon atoms), and the like.
k8 preferably represents an integer of 1 to 3, more preferably 1 or 2, even more preferably 1.
k9 preferably represents an integer of 0 to 2, more preferably 0 or 1, even more preferably 0.

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

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

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 the total repeating units in the resin (A). . Further, 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, relative to the total repeating units in the resin (A). is more preferably 75 mol % or less.

(Repeating unit represented by general formula (S1))
Resin (A) contains a repeating unit represented by general formula (S1). The repeating unit represented by formula (S1) is preferably a repeating unit different from the repeating unit represented by formula (N1).
R ^1S to R ^3S in 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 linear or branched. Although the number of carbon atoms in the alkyl group is not particularly limited, it is preferably 1-5, more preferably 1-3.
The number of carbon atoms in the cycloalkyl group of R ^1S to R ^3S is not particularly limited, but is preferably 3-20, more preferably 5-15. The cycloalkyl groups of R ^1S to R ^3S may be monocyclic cycloalkyl groups such as cyclopentyl group and cyclohexyl group, and polycyclic groups such as norbornyl group, tetracyclodecanyl group, tetracyclododecanyl group and adamantyl group. may be a cycloalkyl group of
The halogen atoms of R ^1S to R ^3S include fluorine, chlorine, bromine and iodine atoms, preferably fluorine or iodine.
The alkyl groups contained in the alkoxy groups of R ^1S to R ^3S may be linear or branched. Although the number of carbon atoms in the alkyl group contained in the alkoxy group is not particularly limited, it is preferably 1-5, more preferably 1-3.
The alkyl groups contained in the alkoxycarbonyl groups of R ^1S to R ^3S may be linear or branched. Although the number of carbon atoms in the alkyl group contained in the alkoxycarbonyl group is not particularly limited, it is preferably 1-5, more preferably 1-3.
R ^1S to R ^3S preferably represent a hydrogen atom or a methyl group, and more preferably represent a hydrogen atom.

m1 in the general formula (S1) represents 0 or 1; When m1 represents 0, the aromatic ring described in general formula (S1) represents a benzene ring. When m1 represents 1, the aromatic ring described in 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 preferably represents an integer of 1 to 3, more preferably 1 or 2, even more preferably 1.

R ^4S in 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 an alkyl group having 1 to 5 carbon atoms). , an alkenyl group (preferably an alkenyl group having 2 to 5 carbon atoms), an alkoxy group (preferably an alkoxy group having 1 to 5 carbon atoms), and the like.
^R4S preferably represents a hydrogen atom.
When multiple R ^4S are present, the multiple R ^4S may be the same or different, and multiple R ^4S may be combined.

R ^4S may be bound 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 general formula (S1-2) and a repeating unit represented by general formula (S1-3) described below. .

-COOR ^5S is an acid-labile group. -COOR ^5S is decomposed by the action of acid (R ^5S is eliminated) to produce -COOH. Since the resin (A) contains the repeating unit represented by the general formula (S1), typically, the action of an acid increases the polarity, increases the solubility in an alkaline developer, and decreases the solubility in an organic solvent. .
^R5S represents a group that leaves by the action of an acid (leaving group). When multiple R ^5S are present, the multiple 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 formula (Y1), Rx ₁ to Rx ₃ each independently represent an organic group. Examples of organic groups include alkyl groups (linear or branched), cycloalkyl groups (monocyclic or polycyclic), alkenyl groups (linear or branched), or aryl groups (monocyclic or polycyclic). ) is preferred. When all of Rx ₁ to Rx ₃ are alkyl groups (linear or branched), at least two of Rx ₁ to Rx ₃ are preferably methyl groups.
Rx ₁ to Rx ₃ preferably each independently represent a linear or branched alkyl group, and more preferably Rx ₁ to Rx ₃ each independently represent a linear alkyl group. .
Two of Rx ₁ to Rx ₃ may combine to form a monocyclic or polycyclic ring.
The alkyl groups of Rx ₁ to Rx ₃ are alkyl groups having 1 to 5 carbon atoms such as methyl group, ethyl group, n-propyl group, isopropyl group, n-butyl group, isobutyl group and t-butyl group. preferable.
The cycloalkyl groups of Rx ₁ to Rx ₃ may be monocyclic cycloalkyl groups such as cyclopentyl group and cyclohexyl group, norbornyl group, tetracyclodecanyl group, tetracyclododecanyl group and adamantyl group. It may be a polycyclic cycloalkyl group.
The aryl group represented by Rx ₁ to Rx ₃ is preferably an aryl group having 6 to 10 carbon atoms, such as phenyl group, naphthyl group and anthryl group.
A vinyl group is preferable as the alkenyl group for Rx ₁ to Rx ₃ .
The ring formed by combining two of Rx ₁ to Rx ₃ is preferably a cycloalkyl group. The cycloalkyl group formed by combining two of Rx ₁ to Rx ₃ includes a monocyclic cycloalkyl group such as a cyclopentyl group or a cyclohexyl group, a norbornyl group, a tetracyclodecanyl group, and a tetracyclododeca. A polycyclic cycloalkyl group such as a nyl group or an adamantyl group is preferable, and a monocyclic cycloalkyl group having 5 to 6 carbon atoms is more preferable.
In the cycloalkyl group formed by combining two of Rx ₁ to Rx ₃ , one of the methylene groups constituting the ring is a group containing a heteroatom such as an oxygen atom, a heteroatom such as a carbonyl group, or a vinylidene group. may be replaced with In these cycloalkyl groups, one or more ethylene groups constituting the cycloalkane ring may be replaced with a vinylene group.
In the group represented by the formula (Y1), for example, it is preferable that Rx ₁ is a methyl group or an ethyl group, and Rx ₂ and Rx ₃ combine to form the above-described cycloalkyl group.
For example, when the composition of the present invention is 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 2 of Rx ₁ to Rx ₃ It is also preferred that the ring formed by combining two atoms further has a fluorine atom or an iodine atom as a substituent.

The repeating unit represented by the general formula (S1) is 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- It is preferably a repeating unit represented by 3).

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

In general formula (S1-2), R ^1S , R ^2S , R ^4S , R ^5S and m1 have the same meanings as R ^1S , R ^2S , R ^4S , R ^5S and m1 in general formula (S1). and 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 preferably represents an integer of 1 to 3, more preferably 1 or 2, even more preferably 1.

In general formula (S1-3), R ^1S , R ^2S , R ^4S , and R ^5S each have the same meaning as R ^1S , R ^2S , R ^4S , and R ^5S in general formula (S1). Examples and preferred ranges are also the same.
n3 represents an integer of 1 to 6, and n4 represents 6-n3.
n3 preferably represents an integer of 1 to 3, more preferably 1 or 2, even more preferably 1.

The repeating unit represented by the general formula (S1) is particularly preferably a repeating unit represented by the above general formula (S1-1), and is preferably a repeating unit represented by the following general formula (S2). Most preferred. Since the repeating unit represented by the following general formula (S2) has a large difference in dissolution rate before and after deprotection, it is highly soluble after deprotection and hardly leaves a residue.

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.
^R6S represents an organic group.
R ^7S represents a substituent other than —COOR ^5S . When multiple ^R7S are present, the multiple ^R7S may be the same or different. ^R5S represents a group that leaves under the action of an acid.
^R8S represents a substituent. When multiple R ^8S are present, the multiple R ^8S may be the same or different, and multiple R ^8S may be combined.
m4 represents an integer of 1-3.
m5 represents an integer of 0-4.
m6 represents an integer from 0 to (2×m4+6).

In general formula (S2), R ^1S to R ^3S each have the same meaning as R ^1S to R ^3S in general formula (S1), and specific examples and preferred ranges are also the same.
^R6S represents an organic group, which may be linear, branched or cyclic. The organic group of R ^6S preferably represents a hydrocarbon group having 1 to 6 carbon atoms, more preferably represents a hydrocarbon group having 1 to 5 carbon atoms, and represents a hydrocarbon group having 1 to 4 carbon atoms. is more preferred. The organic group is preferably an alkyl group (linear or branched) or an alkenyl group (linear or branched).

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

^R8S in general formula (S2) represents a substituent.
Examples of substituents represented by R ^8S include halogen atoms (preferably fluorine atoms or iodine atoms), alkyl groups (preferably alkyl groups having 1 to 5 carbon atoms), alkenyl groups (preferably alkenyl groups having 2 to 5 carbon atoms group), an alkoxy group (preferably an alkoxy group having 1 to 5 carbon atoms), and the like.

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

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

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

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% or more, based on the total repeating units in the resin (A). is more preferable. Further, the content of the repeating unit represented by the general formula (S1) in the resin (A) is preferably 45 mol% or less, more preferably 40 mol% or less, relative to the total repeating units in the resin (A). is more preferably 35 mol % or less.

The resin (A) may further contain other repeating units in addition to the repeating units represented by the general formula (N1) and the repeating units represented by the general formula (S1).
The content of the other repeating units is preferably 0 to 40 mol%, more preferably 0 to 20 mol%, and 0 to 10 mol% based on the total repeating units in the resin (A). It is even more preferable to have
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 (S1) (that is, the resin (A) contains other repeating units ) is preferred.

The resin (A) may contain at least one repeating unit selected from the group consisting of Group A below and/or at least one repeating unit selected from the group consisting of Group B below. good.
Group A: A group consisting of the following repeating units (20) to (25).
(20) a repeating unit having an acid group, which will be described later; (21) a repeating unit, which has neither an acid-decomposable group nor an acid group, and has a fluorine atom, a bromine atom, or an iodine atom, as described later; a repeating unit having a lactone group, a sultone group, or a carbonate group; (23) a repeating unit having a photoacid-generating group, which will be described later; (25) a repeating unit for reducing the mobility of the main chain The repeating units represented by formulas (A) to (E), which will be described later, are (25) reducing the mobility of the main chain corresponds to a repeating unit for
Group B: A group consisting of the following repeating units (30) to (32).
(30) a repeating unit having at least one group selected from a lactone group, a sultone group, a carbonate group, a hydroxyl group, a cyano group, and an alkali-soluble group, which will be described later; (31) a repeating unit having an alicyclic hydrocarbon structure, which will be described later; (32) a repeating unit represented by the formula (III) having neither a hydroxyl group nor a cyano group, which will be described later

(Repeating unit having an acid group)
Resin (A) may further have a repeating unit having an acid group in addition to the repeating unit represented by general formula (N1) and the repeating unit represented by general formula (S1).
As the acid group, an acid group having a pKa of 13 or less is preferable. The acid dissociation constant of the acid group is preferably 13 or less, more preferably 3-13, even more preferably 5-10.
When the resin (A) has an acid group with a pKa of 13 or less, the content of the acid group in the resin (A) is not particularly limited, but is often 0.2 to 6.0 mmol/g. Among them, 0.8 to 6.0 mmol/g is preferable, 1.2 to 5.0 mmol/g is more preferable, and 1.6 to 4.0 mmol/g is even more preferable. If the content of the acid group is within the above range, the development proceeds satisfactorily, the formed pattern shape is excellent, and the resolution is also excellent.
The acid group is preferably, for example, a carboxyl group, a fluoroalcohol group (preferably a hexafluoroisopropanol group), a sulfonic acid group, a sulfonamide group, or an isopropanol group.
In the hexafluoroisopropanol group, one or more (preferably 1 to 2) fluorine atoms may be substituted with a group other than a fluorine atom (such as an alkoxycarbonyl group).
Also preferred as the acid group is -C(CF ₃ )(OH)-CF ₂ - thus formed. Also, one or more of the fluorine atoms may be substituted with a group other than a fluorine atom to form a ring containing -C(CF ₃ )(OH)-CF ₂ -.
The repeating unit having an acid group is different from the repeating unit having a structure in which the polar group is protected by a group that leaves under the action of an acid, and the repeating unit having a lactone group, a sultone group, or a carbonate group, which will be described later. It is preferably a repeating unit.
A repeating unit having an acid group may have a fluorine atom or an iodine atom.

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

(Repeating unit having neither an acid-decomposable group nor an acid group and having a fluorine atom, a bromine atom, or an iodine atom)
Resin (A), in addition to the repeating unit represented by the general formula (N1) and the repeating unit represented by the general formula (S1), further has neither an acid-decomposable group nor an acid group, It may have a repeating unit having a fluorine atom, a bromine atom, or an iodine atom (hereinafter also referred to as unit X). The <repeating unit having neither an acid-decomposable group nor an acid group and having a fluorine atom, a bromine atom, or an iodine atom> referred to here is a <repeating unit having a lactone group, a sultone group, or a carbonate group> described later. , and <repeating unit having photoacid-generating group>.

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

_L5 represents a single bond or an ester group. _R9 represents a hydrogen atom or an alkyl group optionally having a fluorine atom or an iodine atom. R ₁₀ may have a hydrogen atom, an alkyl group optionally having a fluorine atom or an iodine atom, a cycloalkyl group optionally having a fluorine atom or an iodine atom, a fluorine atom or an iodine atom represents an aryl group or a group combining these;

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

(Repeating unit having a lactone group, a sultone group, or a carbonate 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), is further selected from the group consisting of a lactone group, a sultone group, and a carbonate group. may have a repeating unit (hereinafter also referred to as “unit Y”) having at least one type of
It is also preferable that the unit Y does not have a hydroxyl group and an acid group such as a hexafluoropropanol group.

The lactone group or sultone group may have a lactone structure or sultone structure. 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, a 5- to 7-membered ring lactone structure in which a bicyclo structure or spiro structure is formed and another ring structure is condensed with another ring structure, or a 5- to 7-membered ring sultone in a form to form a bicyclo structure or spiro structure. More preferably, the structure is condensed with another ring structure.
The resin (A) has a lactone structure represented by any one of the following formulas (LC1-1) to (LC1-21), or any one of the following formulas (SL1-1) to (SL1-3). It may have a repeating unit having a lactone group or a sultone group formed by removing one or more hydrogen atoms from a ring member atom of a sultone structure, and the lactone group or sultone group may be directly bonded to the main chain. . For example, ring member atoms of a lactone group or a sultone group may constitute the main chain of resin (A).

The lactone structure or sultone structure may have a substituent (Rb ₂ ). Preferred 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, alkoxycarbonyl groups having 1 to 8 carbon atoms, and carboxyl groups. , halogen atoms, cyano groups, and acid-labile groups. n2 represents an integer of 0-4. When n2 is 2 or more, multiple Rb ₂ may be different, and multiple Rb ₂ may combine to form a ring.

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

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

When an optical isomer exists in the repeating unit having a lactone group or a sultone group, any optical isomer may be used. Moreover, one optical isomer may be used alone, or a plurality of optical isomers may be mixed and used. When one kind of optical isomer is mainly used, 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 preferable.

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 of 0 or more. R _A ² represents a substituent. When n is 2 or more, a plurality of R _A ² may be the same or different. A represents a single bond or a divalent linking group. The divalent linking group includes an alkylene group, a divalent linking group having a monocyclic or polycyclic alicyclic hydrocarbon structure, an ether group, an ester group, a carbonyl group, a carboxyl group, or a combination of these. A valent linking group is preferred. Z represents an atomic group forming a monocyclic or polycyclic ring together with the group represented by -O-CO-O- in the formula.

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

(Repeating unit having a photoacid-generating group)
In addition to the repeating unit represented by the general formula (N1) and the repeating unit represented by the general formula (S1), the resin (A) further contains a group that generates an acid upon exposure to actinic rays or radiation (hereinafter , also referred to as a “photoacid-generating group”).
Repeating units having a photoacid-generating group include repeating units represented by formula (4).

^R41 represents a hydrogen atom or a methyl group. ^L41 represents a single bond or a divalent linking group. ^L42 represents a divalent linking group. ^R40 represents a structural site that is decomposed by exposure to actinic rays or radiation to generate an acid in the side chain.
Examples of repeating units having a photoacid-generating group are shown below, but are not limited thereto.

In addition, the repeating unit represented by formula (4) includes, for example, repeating units described in paragraphs [0094] to [0105] of JP-A-2014-041327, and International Publication No. 2018/193954. Examples include repeating units described in paragraph [0094].

(Repeating unit represented by formula (V-1) or formula (V-2) below)
In addition to the repeating unit represented by the general formula (N1) and the repeating unit represented by the general formula (S1), the resin (A) further includes the following formula (V-1) or the following formula (V- 2) may have a repeating unit.
Repeating units represented by the following formulas (V-1) and (V-2) below are preferably different repeating units from the repeating units described above.

During the ceremony,
R ₆ and R ₇ each independently represent a hydrogen atom, an alkyl group, an alkoxy group, an acyloxy group, a cyano group, a nitro group, an amino group, a halogen atom, an ester group (-OCOR or -COOR: R has 1 to 6 alkyl group or fluorinated alkyl group), or a carboxyl group. The alkyl group is preferably a linear, branched or cyclic alkyl group having 1 to 10 carbon atoms.
_n3 represents an integer of 0-6.
_n4 represents an integer of 0-4.
_X4 is a methylene group, an oxygen atom, or a sulfur atom.
The repeating units represented by formula (V-1) or (V-2) are exemplified below.
Examples of the repeating unit represented by formula (V-1) or (V-2) include repeating units described in paragraph [0100] of WO 2018/193954.

(Repeating unit for reducing the mobility of the main chain)
The resin (A) preferably has a high glass transition temperature (Tg) from the viewpoint of suppressing excessive diffusion of generated acid or pattern collapse during development. Tg is preferably greater than 90°C, more preferably greater than 100°C, even more preferably greater than 110°C, and particularly preferably greater than 125°C. The Tg is preferably 400° C. or less, more preferably 350° C. or less, from the viewpoint of excellent dissolution rate in the developer.
In the present specification, the glass transition temperature (Tg) of a polymer such as resin (A) (hereinafter "Tg of repeating unit") is calculated by the following method. First, the Tg of a homopolymer consisting only of each repeating unit contained in the polymer is calculated by the Bicerano method. Next, the mass ratio (%) of each repeating unit to all repeating units in the polymer is calculated. Next, the Fox formula (described in Materials Letters 62 (2008) 3152, etc.) is used to calculate the Tg at each mass ratio, and these are totaled to obtain the Tg (°C) of the polymer.
The Bicerano method is described in Prediction of polymer properties, Marcel Dekker Inc, New York (1993). Calculation of Tg by the Bicerano method can be performed using a polymer physical property estimation software MDL Polymer (MDL Information Systems, Inc.).

In order to increase the Tg of the resin (A) (preferably to make the Tg higher than 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 the resin (A) include the following methods (a) to (e).
(a) Introduction of bulky substituents into the main chain (b) Introduction of multiple substituents into the main chain (c) Introduction of substituents that induce interaction between the resin (A) in the vicinity of the main chain ( d) Main Chain Formation in Cyclic Structure (e) Linking of Cyclic Structure to Main Chain The resin (A) preferably has a repeating unit exhibiting a homopolymer Tg of 130° C. or higher.
The type of repeating unit exhibiting a homopolymer Tg of 130° C. or higher is not particularly limited as long as it is a repeating unit having a homopolymer Tg of 130° C. or higher as calculated by the Bicerano method. Depending on the type of functional group in the repeating units represented by the formulas (A) to (E) described below, the homopolymers correspond to repeating units exhibiting a homopolymer Tg of 130° C. or higher.

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

Formula (A), _RA represents a group containing a polycyclic structure. R _x represents a hydrogen atom, a methyl group, or an ethyl group. A group containing a polycyclic structure is a group containing multiple ring structures, and the multiple ring structures may or may not be condensed.
Specific examples of the repeating unit represented by formula (A) include those described in paragraphs [0107] to [0119] of WO2018/193954.

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

In formula (B), R _b1 to R _b4 each independently represent a hydrogen atom or an organic group, and at least two or more of R _b1 to R _b4 represent an organic group.
When at least one of the organic groups is a group in which a ring structure is directly linked to the main chain in the repeating unit, the type of other organic group is not particularly limited.
Further, when none of the organic groups is a group in which the ring structure is directly linked to the main chain in the repeating unit, at least two of the organic groups have three or more constituent atoms excluding hydrogen atoms. is a substituent.
Specific examples of the repeating unit represented by formula (B) include those described in paragraphs [0113] to [0115] of WO2018/193954.

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

In formula (C), R _c1 to R _c4 each independently represent a hydrogen atom or an organic group, and at least one of R _c1 to R _c4 is hydrogen bonding hydrogen within 3 atoms from the main chain carbon It is a group containing atoms. Above all, it is preferable to have a hydrogen-bonding hydrogen atom within 2 atoms (closer to the main chain side) in order to induce interaction between the main chains of the resin (A).
Specific examples of the repeating unit represented by formula (C) include those described in paragraphs [0119] to [0121] of WO2018/193954.

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

In formula (D), "Cyclic" represents a group forming a main chain with a cyclic structure. The number of constituent atoms of the ring is not particularly limited.
Specific examples of the repeating unit represented by formula (D) include those described in paragraphs [0126] to [0127] of WO2018/193954.

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

In formula (E), each Re independently represents a hydrogen atom or an organic group. Examples of organic groups include alkyl groups, cycloalkyl groups, aryl groups, aralkyl groups, and alkenyl groups, which may have substituents.
A "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 those described in paragraphs [0131] to [0133] of WO2018/193954.

(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 repeating units having at least one group selected from lactone groups, sultone groups, carbonate groups, hydroxyl groups, cyano groups, and alkali-soluble groups.
Examples of the repeating unit having a lactone group, a sultone group, or a carbonate group that the resin (A) has include the repeating units described in the above <Repeating unit having a lactone group, sultone group, or carbonate group>. The preferable content is also as described in <Repeating unit having lactone group, sultone group, or carbonate group>.

Resin (A) may have a repeating unit having a hydroxyl group or a cyano group. This improves the adhesion to the substrate and the compatibility with the developer.
A 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.
A repeating unit having a hydroxyl group or a cyano group preferably does not have an acid-decomposable group. Examples of repeating units having a hydroxyl group or a cyano group include those described in paragraphs [0081] to [0084] of JP-A-2014-098921.

Resin (A) may have a repeating unit having an alkali-soluble group.
The alkali-soluble group includes a carboxyl group, a sulfonamide group, a sulfonylimide group, a bissulfonylimide group, and an aliphatic alcohol group substituted with an electron-withdrawing group at the α-position (e.g., hexafluoroisopropanol group). , is preferably a carboxyl group. When the resin (A) contains a repeating unit having an alkali-soluble group, the resolution for contact holes is increased. Repeating units having an alkali-soluble group include those described in paragraphs [0085] and [0086] of JP-A-2014-098921.

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

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

In formula (III), _R5 represents a hydrocarbon group having at least one cyclic structure and having neither a hydroxyl group nor a cyano group.
Ra represents a hydrogen atom, an alkyl group or a --CH ₂ --O--Ra ₂ group. In the formula, _Ra2 represents a hydrogen atom, an alkyl group or an acyl group.
Examples of the repeating unit represented by formula (III) having neither a hydroxyl group nor a cyano group include those described in paragraphs [0087] to [0094] of JP-A-2014-098921.

(Other repeating units)
Furthermore, the resin (A) may have repeating units other than the repeating units described above.
For example, the resin (A) has repeating units selected from the group consisting of repeating units having an oxathian ring group, repeating units having an oxazolone ring group, repeating units having a dioxane ring group, and repeating units having a hydantoin ring group. You may have
Specific examples of repeating units other than the repeating units described above are shown below.

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

Resin (A) can be synthesized according to a conventional method (for example, radical polymerization).
The weight-average molecular weight (Mw) of the resin (A) is preferably 30,000 or less, more preferably 10,000 or less, and still more preferably 8,000 or less from the viewpoint of reducing defects, as a polystyrene-equivalent value by GPC method. Moreover, the weight average molecular weight (Mw) of the resin (A) is preferably 1,000 or more, more preferably 3,000 or more.
The degree of dispersion (molecular weight distribution, Pd, Mw/Mn) of the resin (A) is preferably 3.0 or less, more preferably 2.0 or less, and still more preferably 1.7 or less from the viewpoint of defect reduction. Moreover, the dispersion degree of the resin (A) may be 1.0 or more, or may be 1.2 or more.

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

In the composition of the present invention, the content of the resin (A) is preferably 40.0 to 99.9% by mass, preferably 60.0 to 90.0% by mass, based on the total solid content of the composition of the present invention. is more preferred.

[Compound (B) that generates an acid upon exposure to actinic rays or radiation]
The composition of the present invention contains a compound (B) that generates an acid upon exposure to actinic rays or radiation.
Compound (B) may be in the form of a low-molecular-weight compound, or may be in the form of being incorporated into a part of a polymer. Moreover, the form of a low-molecular-weight compound and the form of being incorporated into a part of a polymer may be used in combination.
When compound (B) is in the form of a low-molecular-weight compound, the molecular weight of compound (B) is preferably 3,000 or less, more preferably 2,000 or less, and even more preferably 1,000 or less. Although the lower limit is not particularly limited, 100 or more is preferable.
When the compound (B) is in the form of being incorporated into a part of the polymer, it may be incorporated into a part of the resin (A) or into a resin different from the resin (A).
Compound (B) is preferably in the form of a low-molecular-weight compound.

The ClogP value of the acid (generated acid) generated from the compound (B) by irradiation with actinic rays or radiation is preferably 7.5 or less, more preferably 4.5 or less, and can further reduce defects. For this reason, it is more preferably 3.5 or less. Moreover, the ClogP value of the acid generated from the compound (B) may be 2.5 or more, or 3.0 or more.
The ClogP value is a value obtained by calculating the common logarithm logP of the partition coefficient P between 1-octanol and water. Although known methods and software can be used for calculating ClogP values, unless otherwise specified, the present invention uses the ClogP program incorporated in ChemBioDraw Ultra 12.0 from Cambridge soft.
When the generated acid of compound (B) has an acid-decomposable group, the ClogP value of the structure after the acid-decomposable group of the generated acid is decomposed by the acid is preferably within the above range.

Compound (B) preferably has an acid-decomposable group for the reason that defects can be further reduced.
An acid-decomposable group is a group that is decomposed by the action of an acid to form a polar group. The acid-decomposable group preferably has a structure in which the polar group is protected with a group that is released by the action of an acid (leaving group).
The polar group is preferably an alkali-soluble group such as a carboxyl group, a phenolic hydroxyl group, a fluorinated alcohol group, a sulfonic acid group, a phosphoric acid group, a sulfonamide group, a sulfonylimide group, (alkylsulfonyl)(alkylcarbonyl)methylene group, (alkylsulfonyl)(alkylcarbonyl)imide group, bis(alkylcarbonyl)methylene group, bis(alkylcarbonyl)imide group, bis(alkylsulfonyl)methylene group, bis(alkylsulfonyl)imide group, tris(alkylcarbonyl) Methylene groups, acidic groups such as tris(alkylsulfonyl)methylene groups, and alcoholic hydroxyl groups are included.
Among them, the polar group is preferably a carboxyl group, a phenolic hydroxyl group, a fluorinated alcohol group (preferably a hexafluoroisopropanol group), or a sulfonic acid group.

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

In formulas (Y1) and (Y2), Rx ₁ to Rx ₃ each independently represent an alkyl group (linear or branched), a cycloalkyl group (monocyclic or polycyclic), an alkenyl group (linear or branched chain) or an aryl group (monocyclic or polycyclic). When all of Rx ₁ to Rx ₃ are alkyl groups (linear or branched), at least two of Rx ₁ to Rx ₃ are preferably methyl groups.
Among them, Rx ₁ to Rx ₃ preferably each independently represent a linear or branched alkyl group, and Rx ₁ to Rx ₃ each independently represent a linear alkyl group. is more preferred.
Two of Rx ₁ to Rx ₃ may combine to form a monocyclic or polycyclic ring.
The alkyl groups of Rx ₁ to Rx ₃ are alkyl groups having 1 to 5 carbon atoms such as methyl group, ethyl group, n-propyl group, isopropyl group, n-butyl group, isobutyl group and t-butyl group. preferable.
The cycloalkyl groups represented by Rx ₁ to Rx ₃ include monocyclic cycloalkyl groups such as cyclopentyl and cyclohexyl groups, norbornyl, tetracyclodecanyl, tetracyclododecanyl, and adamantyl groups. is preferred.
The aryl group represented by Rx ₁ to Rx ₃ is preferably an aryl group having 6 to 10 carbon atoms, such as phenyl group, naphthyl group and anthryl group.
A vinyl group is preferable as the alkenyl group for Rx ₁ to Rx ₃ .
The ring formed by combining two of Rx ₁ to Rx ₃ is preferably a cycloalkyl group. The cycloalkyl group formed by combining two of Rx ₁ to Rx ₃ includes a monocyclic cycloalkyl group such as a cyclopentyl group or a cyclohexyl group, a norbornyl group, a tetracyclodecanyl group, and a tetracyclododeca. A polycyclic cycloalkyl group such as a nyl group or an adamantyl group is preferable, and a monocyclic cycloalkyl group having 5 to 6 carbon atoms is more preferable.
In the cycloalkyl group formed by combining two of Rx ₁ to Rx ₃ , one of the methylene groups constituting the ring is a group containing a heteroatom such as an oxygen atom, a heteroatom such as a carbonyl group, or a vinylidene group. may be replaced with In these cycloalkyl groups, one or more ethylene groups constituting the cycloalkane ring may be replaced with a vinylene group.
In the group represented by formula (Y1) or formula (Y2), for example, Rx ₁ is a methyl group or an ethyl group, and Rx ₂ and Rx ₃ combine to form the above-described cycloalkyl group. is preferred.

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 combine with each other to form a ring. Monovalent organic groups include alkyl groups, cycloalkyl groups, aryl groups, aralkyl groups, and alkenyl groups. It is also preferred that R ₃₆ is a hydrogen atom.
The alkyl group, cycloalkyl group, aryl group, and aralkyl group may contain a heteroatom such as an oxygen atom and/or a group containing a heteroatom such as a carbonyl group. For example, in the alkyl group, cycloalkyl group, aryl group, and aralkyl group, one or more of the methylene groups may be replaced with a heteroatom such as an oxygen atom and/or a group containing a heteroatom such as a carbonyl group. good.
R ₃₈ may combine with another substituent of the main chain of the repeating unit to form a ring. The group formed by bonding R ₃₈ and another substituent of the main chain of the repeating unit to each other is preferably an alkylene group such as a methylene group.

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

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 (e.g., a group combining an alkyl group and an aryl group). .
M represents a single bond or a divalent linking group.
Q is an alkyl group optionally containing a heteroatom, a cycloalkyl group optionally containing a heteroatom, an aryl group optionally containing a heteroatom, an amino group, an ammonium group, a mercapto group, a cyano group, an aldehyde group, or a group combining these (for example, a group combining an alkyl group and a cycloalkyl group).
In alkyl groups and cycloalkyl groups, for example, one of the methylene groups may be replaced by a heteroatom such as an oxygen atom or a heteroatom-containing group such as a carbonyl group.
One of L ₁ and L ₂ is preferably a hydrogen atom, and the other is preferably 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 _L1 may combine to form a ring (preferably a 5- 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 may combine with each other to form a non-aromatic ring. Ar is preferably an aryl group.

Examples of the compound (B) include a compound (onium salt) represented by “M ⁺ X ⁻ ”, preferably a compound that generates an organic acid 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, aralkylcarboxylic acid, etc.), carbonylsulfonylimide, acids, bis(alkylsulfonyl)imidic acids, and tris(alkylsulfonyl)methide acids.

In the compound represented by "M ⁺ X ^- ", M ⁺ represents a cation, preferably an organic cation.
The cation represented by M ⁺ is not particularly limited. The cation may have a valence of 1 or 2 or more. As the cation, a cation represented by the formula (ZaI) (hereinafter also referred to as “cation (ZaI)”) or a cation represented by the formula (ZaII) (hereinafter also referred to as “cation (ZaII)”) is used. preferable.
M ⁺ particularly preferably represents a sulfonium cation.

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

Suitable embodiments of the organic cation in formula (ZaI) include cation (ZaI-1), cation (ZaI-2), cation (ZaI-3b), and cation (ZaI-4b), which will be described later.

First, the cation (ZaI-1) will be described.
Cation (ZaI-1) is an arylsulfonium cation in which at least one of R ²⁰¹ to R ²⁰³ in formula (ZaI) above is an aryl group.
In the arylsulfonium cation, all of R ²⁰¹ to R ²⁰³ may be aryl groups, or part of R ²⁰¹ to R ²⁰³ may be aryl groups and the rest may be alkyl groups or cycloalkyl groups.
One of R ²⁰¹ to R ²⁰³ is an aryl group, and the remaining two of R ²⁰¹ to R ²⁰³ may combine to form a ring structure, in which an oxygen atom, a sulfur atom and an ester group , an amide group, or a carbonyl group. The group formed by bonding two of R ²⁰¹ to R ²⁰³ includes, for example, one or more methylene groups substituted with an oxygen atom, a sulfur atom, an ester group, an amide group and/or a carbonyl group. alkylene groups (eg, butylene group, pentylene group, and —CH ₂ —CH ₂ —O—CH ₂ —CH ₂ —).
Arylsulfonium cations include triarylsulfonium cations, diarylalkylsulfonium cations, aryldialkylsulfonium cations, diarylcycloalkylsulfonium cations, and aryldicycloalkylsulfonium cations.

The aryl group contained in the arylsulfonium cation is preferably a phenyl group or a naphthyl group, more preferably a phenyl group. The aryl group may be an aryl group having a heterocyclic structure having an oxygen atom, a nitrogen atom, a sulfur atom, or the like. Heterocyclic structures include pyrrole, furan, thiophene, indole, benzofuran, and benzothiophene residues. When the arylsulfonium cation has two or more aryl groups, the two or more aryl groups may be the same or different.
The alkyl group or cycloalkyl group optionally possessed by the arylsulfonium cation is a linear alkyl group having 1 to 15 carbon atoms, a branched alkyl group having 3 to 15 carbon atoms, or 3 to 15 carbon atoms. is preferred, and a methyl group, ethyl group, propyl group, n-butyl group, sec-butyl group, t-butyl group, cyclopropyl group, cyclobutyl group or cyclohexyl group is more preferred.

Examples of substituents that the aryl group, alkyl group and cycloalkyl group of R ²⁰¹ to R ²⁰³ may have include an alkyl group (eg, 1 to 15 carbon atoms), a cycloalkyl group (eg, 3 to 3 carbon atoms). 15), aryl groups (eg, 6 to 14 carbon atoms), alkoxy groups (eg, 1 to 15 carbon atoms), cycloalkylalkoxy groups (eg, 1 to 15 carbon atoms), halogen atoms (eg, fluorine and iodine) , hydroxyl group, carboxyl group, ester group, sulfinyl group, sulfonyl group, alkylthio group or phenylthio group.
If possible, the substituent may further have a substituent, and the alkyl group preferably has a halogen atom as a substituent to form a halogenated alkyl group such as a trifluoromethyl group.
It is also preferable to form an acid-decomposable group by any combination of the above substituents.

Next, the cation (ZaI-2) will be explained.
Cation (ZaI-2) is a cation in which R ²⁰¹ to R ²⁰³ in formula (ZaI) each independently represents an organic group having no aromatic ring. Aromatic rings also include aromatic rings containing heteroatoms.
The number of carbon atoms in the organic group having no aromatic ring as R ²⁰¹ to R ²⁰³ is preferably 1-30, more preferably 1-20.
R ²⁰¹ to R ²⁰³ are each independently preferably an alkyl group, a cycloalkyl group, an allyl group, or a vinyl group, and a linear or branched 2-oxoalkyl group, 2-oxocycloalkyl group, or An alkoxycarbonylmethyl group is more preferred, and a linear or branched 2-oxoalkyl group is even more preferred.

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

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

In 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, an alkylcarbonyloxy group, a cycloalkyl represents a carbonyloxy group, a halogen atom, a hydroxyl group, a nitro group, an alkylthio group, or an arylthio group;
R _6c and R _7c each independently represent a hydrogen atom, an alkyl group (eg, t-butyl group), a cycloalkyl group, a halogen atom, a cyano group, or an aryl group.
R _x and R _y each independently represent an alkyl group, a cycloalkyl group, a 2-oxoalkyl group, a 2-oxocycloalkyl group, an alkoxycarbonylalkyl group, an allyl group, or a vinyl group.
It is also preferred that the substituents of R _1c to R _7c , R _x and R _y independently form an acid-decomposable group by any combination of substituents.

Any two or more of R _1c to R _5c , R _5c and R _6c , R _6c and R _7c , R _5c and R _x , and R _x and R _y may combine with each other to form a ring. The rings may each independently contain an oxygen atom, a sulfur atom, a ketone group, an ester bond, or an amide bond.
Examples of the ring include aromatic or non-aromatic hydrocarbon rings, aromatic or non-aromatic hetero rings, and polycyclic condensed rings in which two or more of these rings are combined. The ring includes a 3- to 10-membered ring, preferably a 4- to 8-membered ring, more preferably a 5- or 6-membered ring.

Examples of groups formed by bonding 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 a butylene group and a pentylene group. A methylene group in this alkylene group may be substituted with a heteroatom such as an oxygen atom.
The group formed by combining R _5c and R _6c and R _5c and R _x is preferably a single bond or an alkylene group. Alkylene groups include methylene and ethylene groups.

R _1c to R _5c , R _6c , R _7c , R _x , R _y , and 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 combining each other with R _x and R _y may have a substituent.

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

In formula (ZaI-4b), l represents an integer of 0-2 and r represents an integer of 0-8.
R ₁₃ is a hydrogen atom, a halogen atom (e.g., fluorine atom, iodine atom, etc.), a hydroxyl group, an alkyl group, a halogenated alkyl group, an alkoxy group, a carboxyl group, an alkoxycarbonyl group, or a group containing a cycloalkyl group (cycloalkyl may be the group itself, or may be a group partially containing a cycloalkyl group). These groups may have a substituent.
R ₁₄ is a hydroxyl group, a halogen atom (e.g., a fluorine atom, an iodine atom, etc.), an alkyl group, a halogenated alkyl group, an alkoxy group, an alkoxycarbonyl group, an alkylcarbonyl group, an alkylsulfonyl group, a cycloalkylsulfonyl group, or a cycloalkyl represents a group containing a group (either a cycloalkyl group itself or a group partially containing a cycloalkyl group). These groups may have a substituent. When two or more R ₁₄ are present, each independently represents the above group such as a hydroxyl group.
Each R ₁₅ independently represents an alkyl group, a cycloalkyl group, or a naphthyl group. Two R ₁₅ may be joined together to form a ring. When two R ₁₅ are combined to form a ring, the ring skeleton may contain a heteroatom such as an oxygen atom or a nitrogen atom.
In one aspect, two R ₁₅ are alkylene groups, preferably joined together to form a ring structure. The ring formed by combining the alkyl group, the cycloalkyl group, the naphthyl group, and the two R ₁₅ groups may have a substituent.

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

Next, formula (ZaII) will be described.
In formula (ZaII), R ²⁰⁴ and R ²⁰⁵ each independently represent an aryl group, an alkyl group or a cycloalkyl group.
The aryl group for R ²⁰⁴ and R ²⁰⁵ is preferably a phenyl group or a naphthyl group, more preferably a phenyl group. The aryl group for 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. Skeletons of heterocyclic aryl groups include, for example, pyrrole, furan, thiophene, indole, benzofuran, and benzothiophene.
The alkyl group and cycloalkyl group for R ²⁰⁴ and R ²⁰⁵ include a linear alkyl group having 1 to 10 carbon atoms or a branched alkyl group having 3 to 10 carbon atoms (e.g., methyl group, ethyl group, propyl group, butyl group, or pentyl group), or a cycloalkyl group having 3 to 10 carbon atoms (eg, cyclopentyl group, cyclohexyl group, or norbornyl group).

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 (eg, 1 to 15 carbon atoms) and a cycloalkyl group (eg, 3 to 15), aryl groups (eg, 6 to 15 carbon atoms), alkoxy groups (eg, 1 to 15 carbon atoms), halogen atoms, hydroxyl groups, and phenylthio groups. It is also preferred that the substituents of R ²⁰⁴ and R ²⁰⁵ each independently form an acid-decomposable group by any combination of substituents.

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

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

Examples of non-nucleophilic anions include sulfonate anions (aliphatic sulfonate anions, aromatic sulfonate anions, camphorsulfonate anions, etc.), carboxylate anions (aliphatic carboxylate anions, aromatic carboxylate anions, and aralkyl carboxylic acid anions), sulfonylimide anions, bis(alkylsulfonyl)imide anions, and tris(alkylsulfonyl)methide anions.

The aliphatic moiety in the aliphatic sulfonate anion and the aliphatic carboxylate anion may be a linear or branched alkyl group or a cycloalkyl group, and may be a straight chain having 1 to 30 carbon atoms. Alternatively, a branched alkyl group or a cycloalkyl group having 3 to 30 carbon atoms is preferred.
The alkyl group may be, for example, a fluoroalkyl group (which may have a substituent other than a fluorine atom, or may be a perfluoroalkyl group).

The aryl group in the aromatic sulfonate anion and the aromatic carboxylate anion is preferably an aryl group having 6 to 14 carbon atoms, such as a phenyl group, a tolyl group, and a naphthyl group.

The alkyl group, cycloalkyl group, and aryl group listed above may have a substituent. The substituents are not particularly limited, but examples include nitro groups, halogen atoms such as fluorine atoms and chlorine atoms, carboxyl groups, hydroxyl groups, amino groups, cyano groups, alkoxy groups (preferably having 1 to 15 carbon atoms), alkyl groups ( preferably 1 to 10 carbon atoms), a cycloalkyl group (preferably 3 to 15 carbon atoms), an aryl group (preferably 6 to 14 carbon atoms), an alkoxycarbonyl group (preferably 2 to 7 carbon atoms), an acyl group ( preferably 2 to 12 carbon atoms), alkoxycarbonyloxy group (preferably 2 to 7 carbon atoms), alkylthio group (preferably 1 to 15 carbon atoms), alkylsulfonyl group (preferably 1 to 15 carbon atoms), alkylimino A sulfonyl group (preferably having 1 to 15 carbon atoms) and an aryloxysulfonyl group (preferably having 6 to 20 carbon atoms) can be mentioned.

As the aralkyl group in the aralkylcarboxylate anion, an aralkyl group having 7 to 14 carbon atoms is preferred.
Aralkyl groups having 7 to 14 carbon atoms include, for example, benzyl, phenethyl, naphthylmethyl, naphthylethyl and naphthylbutyl groups.

　Sulfonylimide anions include, for example, saccharin anions.

As the alkyl group in the bis(alkylsulfonyl)imide anion and the tris(alkylsulfonyl)methide anion, an alkyl group having 1 to 5 carbon atoms is preferable. Examples of substituents of these alkyl groups include halogen atoms, halogen-substituted alkyl groups, alkoxy groups, alkylthio groups, alkyloxysulfonyl groups, aryloxysulfonyl groups, and cycloalkylaryloxysulfonyl groups. A fluorine atom or an alkyl group substituted with a fluorine atom is preferred.
In addition, the alkyl groups in the bis(alkylsulfonyl)imide anion may combine with each other to form a ring structure. This increases the acid strength.

Other non-nucleophilic anions include, for example, phosphorous fluorides (eg, PF ₆ ⁻ ), boron fluorides (eg, BF ₄ ⁻ ), and antimony fluorides (eg, SbF ₆ ⁻ ).

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

In formula (AN1), R ¹ and R ² each independently represent a hydrogen atom or a substituent.
Although the substituent is not particularly limited, a group that is not an electron-withdrawing group is preferred. Examples of groups that are not electron-withdrawing groups include hydrocarbon groups, hydroxyl groups, oxyhydrocarbon groups, oxycarbonyl hydrocarbon groups, amino groups, hydrocarbon-substituted amino groups, and hydrocarbon-substituted amide groups.
Groups that are not electron-withdrawing groups are preferably -R', -OH, -OR', -OCOR', -NH ₂ , -NR' ₂ , -NHR' or -NHCOR' each independently. . R' is a monovalent hydrocarbon group.

Examples of the monovalent hydrocarbon group represented by R' include alkyl groups such as methyl, ethyl, propyl, and butyl; alkenyl groups such as ethenyl, propenyl, and butenyl; ethynyl monovalent linear or branched hydrocarbon groups such as alkynyl groups such as groups, propynyl groups, and butynyl groups; cyclopropyl groups, cyclobutyl groups, cyclopentyl groups, cyclohexyl groups, norbornyl groups, and adamantyl groups Cycloalkyl group; monovalent alicyclic hydrocarbon group such as cycloalkenyl group such as cyclopropenyl group, cyclobutenyl group, cyclopentenyl group, and norbornenyl group; phenyl group, tolyl group, xylyl group, mesityl group, naphthyl group, methyl aryl groups such as naphthyl group, anthryl group and methylanthryl group; monovalent aromatic hydrocarbon groups such as aralkyl groups such as benzyl group, phenethyl group, phenylpropyl group, naphthylmethyl group and anthrylmethyl group; mentioned.
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 divalent linking group.
When there are multiple L's, each L may be the same or different.
Examples of divalent linking groups include -O-CO-O-, -COO-, -CONH-, -CO-, -O-, -S-, -SO-, -SO ₂ -, alkylene groups ( preferably 1 to 6 carbon atoms), a cycloalkylene group (preferably 3 to 15 carbon atoms), an alkenylene group (preferably 2 to 6 carbon atoms), and a divalent linking group combining a plurality of these. . Among them, the divalent linking group includes -O-CO-O-, -COO-, -CONH-, -CO-, -O-, -SO ₂ -, and -O-CO-O-alkylene group- , -COO-alkylene group-, or -CONH-alkylene group- is preferred, and -O-CO-O-, -O-CO-O-alkylene group-, -COO-, -CONH-, -SO ₂ - , or -COO-alkylene group- is more preferred.

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

In formula (AN1-1), * ^a represents the bonding position with ^R3 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 of 0-10, preferably an integer of 0-3.
R ^2a and R ^2b each independently represent a hydrogen atom or a substituent.
When multiple R ^2a and R ^2b are present, the multiple R ^2a and R ^2b may be the same or different.
However, when Y is 1 or more, R ^2b in CR ^2b ₂ directly bonded to —C(R ¹ )(R ² )— in formula (AN1) is other than a fluorine atom.
Q is * ^A -O-CO-O-* ^B , * ^A -CO-* ^B , * ^A -CO-O-* ^B , * ^A -O-CO-* ^B , * ^A -O-* ^B , * ^A -S-* ^B or * ^A - _SO2- * ^B .
However, when X + Y in formula (AN1-1) is 1 or more, and both R ^2a and R ^2b in formula (AN1-1) are hydrogen atoms, Q is * ^A —O—CO -O-* ^B , * ^A -CO-* ^B , * ^A -O-CO-* ^B , * ^A -O-* ^B , * ^A -S-* ^B , or * ^A - _SO2- * ^B represents
* ^A represents the bonding position on the R ³ side in formula (AN1), and * ^B represents the bonding position on the —SO ₃ ^— side in formula (AN1).

In formula (AN1), ^R3 represents an organic group.
The organic group is not particularly limited as long as it has 1 or more carbon atoms. branched chain alkyl group) or a cyclic group. The organic group may or may not have a substituent. The organic group may or may not have a heteroatom (oxygen atom, sulfur atom, and/or nitrogen atom, etc.).

Among them, R ³ is preferably an organic group having a cyclic structure. The cyclic structure may be monocyclic or polycyclic, and may have a substituent. The ring in the organic group containing a cyclic structure is preferably directly bonded to L in formula (AN1).
The organic group having a cyclic structure may or may not have a heteroatom (oxygen atom, sulfur atom, and/or nitrogen atom, etc.), for example. Heteroatoms may replace one or more of the carbon atoms that form the ring structure.
The organic group having a cyclic structure is preferably, for example, a hydrocarbon group having a cyclic structure, a lactone ring group, or a sultone ring group. Among them, the organic group having a cyclic structure is preferably a hydrocarbon group having a cyclic structure.
The above hydrocarbon group having a cyclic structure is preferably a monocyclic or polycyclic cycloalkyl group. These groups may have a substituent.
The cycloalkyl group may be monocyclic (such as cyclohexyl group) or polycyclic (such as adamantyl group), and preferably has 5 to 12 carbon atoms.
Examples of the lactone group and sultone group include structures represented by the above formulas (LC1-1) to (LC1-21) and structures represented by formulas (SL1-1) to (SL1-3). , preferably a group obtained by removing one hydrogen atom from a ring member atom constituting a lactone structure or a sultone structure.

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

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

In formula (AN2), o represents an integer of 1-3. 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 this alkyl group is preferably 1-10, more preferably 1-4. A perfluoroalkyl group is preferred as the alkyl group substituted with at least one fluorine atom.
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 even more preferably both Xf are fluorine atoms.

^R4 and ^R5 each independently represent a hydrogen atom, a fluorine atom, an alkyl group, or an alkyl group substituted with at least one fluorine atom. When multiple R ⁴ and R ⁵ are present, each of R ⁴ and R ⁵ may be the same or different.
The alkyl groups represented by R ⁴ and R ⁵ preferably have 1 to 4 carbon atoms. The above alkyl group may have a substituent. Hydrogen atoms are preferred as R ⁴ and R ⁵ .

　L represents a divalent 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 preferable.
Cyclic organic groups include, for example, alicyclic groups, aryl groups, and heterocyclic groups.
The alicyclic group may be monocyclic or polycyclic. Monocyclic alicyclic groups include, for example, monocyclic cycloalkyl groups such as a cyclopentyl group, a cyclohexyl group, and a cyclooctyl group. The polycyclic alicyclic group includes, for example, a norbornyl group, a tricyclodecanyl group, a tetracyclodecanyl group, a tetracyclododecanyl group, and a polycyclic cycloalkyl group such as an adamantyl group. Among them, alicyclic groups having a bulky structure with 7 or more carbon atoms, such as norbornyl, tricyclodecanyl, tetracyclodecanyl, tetracyclododecanyl, and adamantyl groups, are preferred.

Aryl groups may be monocyclic or polycyclic. Examples of the aryl group include phenyl group, naphthyl group, phenanthryl group, and anthryl group.
A heterocyclic group may be monocyclic or polycyclic. Especially, when it is a polycyclic heterocyclic group, diffusion of acid can be further suppressed. A heterocyclic group may or may not have an aromatic character. Heterocyclic rings having aromaticity include, for example, furan ring, thiophene ring, benzofuran ring, benzothiophene ring, dibenzofuran ring, dibenzothiophene ring, and pyridine ring. Non-aromatic heterocycles include, for example, a tetrahydropyran ring, a lactone ring, a sultone ring, and a decahydroisoquinoline ring. The heterocyclic ring in the heterocyclic group is preferably a furan ring, a thiophene ring, a pyridine ring, or a decahydroisoquinoline ring.

The cyclic organic group may have a substituent. Examples of the substituents include alkyl groups (either linear or branched, preferably having 1 to 12 carbon atoms), cycloalkyl groups (monocyclic, polycyclic, and spirocyclic). any group, preferably having 3 to 20 carbon atoms), aryl group (preferably having 6 to 14 carbon atoms), hydroxyl group, alkoxy group, ester group, amide group, urethane group, ureido group, thioether group, sulfonamide and sulfonate ester groups. In addition, carbonyl carbon may be sufficient as carbon (carbon which contributes to ring formation) which comprises a cyclic|annular organic group.

Examples of anions represented by formula (AN2) include SO ₃ ⁻ —CF ₂ —CH ₂ —OCO-(L) _q′ —W, SO ₃ ⁻ —CF ₂ —CHF—CH ₂ —OCO-(L) _{q '} -W, SO ₃ ^- -CF ₂ -COO-(L) _q' -W, SO ₃ ^- -CF ₂ -CF ₂ _{-CH 2} -CH ₂ -(L) _q -W, or SO ₃ ^- - CF ₂ —CH(CF ₃ )—OCO—(L) _q′ —W is preferred. Here, L, q and W are the same as in formula (AN2). q' represents an integer from 0 to 10;

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

In formula (AN3), Ar represents an aryl group (such as a phenyl group) and may further have a substituent other than the sulfonate anion and -(D-B) group. Substituents which may be further included include, for example, a fluorine atom and a hydroxyl group.
n represents an integer of 0 or more. n is preferably 1 to 4, more preferably 2 to 3, and still more preferably 3.

D represents a single bond or a divalent linking group. Divalent linking groups include ether groups, thioether groups, carbonyl groups, sulfoxide groups, sulfone groups, sulfonate ester groups, ester groups, and groups consisting of combinations of two or more thereof.

B represents a hydrocarbon group.
B is preferably an aliphatic hydrocarbon group, more preferably an isopropyl group, a cyclohexyl group, or an optionally substituted aryl group (such as a tricyclohexylphenyl group).

Disulfonamide anions are also preferred as non-nucleophilic anions.
A disulfonamide anion is, for example, an anion represented by N ⁻ (SO ₂ —R ^q ) ₂ .
Here, R ^q represents an optionally substituted alkyl group, preferably a fluoroalkyl group, more preferably a perfluoroalkyl group. Two R ^q may combine with each other to form a ring. The group formed by bonding two R ^q together is preferably an optionally substituted alkylene group, more preferably a fluoroalkylene group, and even more preferably a perfluoroalkylene group. The alkylene group preferably has 2 to 4 carbon atoms.

The compound (B) is preferably 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 hydroxy group, an alkoxy group, or a cycloalkyloxy group. R ^1P to R ^5P do not contain fluorine atoms.
Mp ⁺ represents a cation.

The alkyl groups of R ^1P to R ^5P may be linear or branched. Although the number of carbon atoms in the alkyl group is not particularly limited, it is preferably 1-5, more preferably 1-3.
The number of carbon atoms in the cycloalkyl groups of R ^1P to R ^5P is not particularly limited, but is preferably 3-20, more preferably 5-15. The cycloalkyl groups of R ^1P to R ^5P may be monocyclic cycloalkyl groups such as cyclopentyl and cyclohexyl groups, and polycyclic groups such as norbornyl, tetracyclodecanyl, tetracyclododecanyl and adamantyl groups. may be a cycloalkyl group of
The number of carbon atoms in the aryl group of R ^1P to R ^5P is not particularly limited, but is preferably 6-20, more preferably 6-15. The aryl groups of R ^1P to R ^5P are preferably phenyl groups.
The alkoxy groups of R ^1P to R ^5P may be linear or branched. Although the number of carbon atoms in the alkoxy group is not particularly limited, it is preferably 1-5, more preferably 1-3.
The number of carbon atoms in the cycloalkyloxy groups of R ^1P to R ^5P is not particularly limited, but is preferably 3-20, more preferably 5-15. The cycloalkyloxy groups of R ^1P to R ^5P may be monocyclic cycloalkyloxy groups or polycyclic cycloalkyloxy groups.

When R ^1P to R ^5P represent an alkyl group, a cycloalkyl group, an aryl group, an alkoxy group, or a cycloalkyloxy group, they may further have a substituent. However, R ^1P to R ^5P do not contain a fluorine atom. That is, the alkyl group, cycloalkyl group, aryl group, alkoxy group, and cycloalkyloxy group do not have a fluorine atom as a substituent.
When R ^1P to R ^5P do not contain a fluorine atom, the hydrophobicity of the compound (B) can be lowered and defects can be further reduced, which is preferable.

Mp ⁺ in general formula (P1) represents a cation, and specific examples and preferred ranges are the same as for M ⁺ 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 moieties X shown below and one or more structural moieties Y shown below, wherein the first acidic It is a compound that generates an acid containing a site and a second acidic site described below derived from the structural site Y described below.
Structural site X: Structural site consisting of an anionic site A ₁ ⁻ and a cation site M ₁ ⁺ and forming a first acidic site represented by HA ₁ upon exposure to actinic rays or radiation Structural site Y: anionic site A structural site consisting of A ₂ ^- and a cationic site M ₂ ⁺ and forming a second acidic site represented by HA ₂ upon exposure to actinic rays or radiation. The compound (I) satisfies the following condition I. .

Condition I: A compound PI obtained by replacing the cation site M ₁ ⁺ in the structural site X and the cation site M ₂ ⁺ in the structural site Y in the compound (I) with H ⁺ in the structural site X and an acid dissociation constant a1 derived from the acidic site represented by HA ₁ obtained by replacing the cation site M 1 ⁺ with H ⁺ , and replacing the cation site M ₂ ⁺ in the structural site _Y with H ⁺ It has an acid dissociation constant a2 derived from the acidic site represented by _HA2 , and the acid dissociation constant a2 is greater than the acid dissociation constant a1.

Condition I will be described in more detail below.
When the compound (I) is, for example, an acid-generating compound having one first acidic site derived from the structural site X and one second acidic site derived from the structural site Y , compound PI corresponds to "a compound having HA ₁ and HA ₂ ".
More specifically, the acid dissociation constant a1 and the acid dissociation constant a2 of compound PI are defined as "a compound having A ₁ ^- and HA ₂ " when the acid dissociation constant of compound PI is determined. is the acid dissociation constant a1, and the pKa when the "compound having A ₁ ^- and HA ₂ " becomes the "compound having A ₁ ^- and A ₂ ^- " is the acid dissociation constant a2 be.

When compound (I) is, for example, an acid-generating compound having two first acidic sites derived from the structural site X and one second acidic site derived from the structural site Y , compound PI corresponds to "a compound having two HA ₁ and one HA ₂ ".
When the acid dissociation constant of compound PI is obtained, the acid dissociation constant when compound PI becomes "a compound having one A ₁ ^- , one HA ₁ and one HA ₂ " and "one A ₁ ^- and one HA ₁ and one HA ₂ ” becomes a “compound having two A ₁ ^- and one HA ₂ ” corresponds to the acid dissociation constant a1 described above. . 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 ^- " corresponds to the acid dissociation constant a2. That is, in the case of the compound PI, when it has a plurality of acid dissociation constants derived from the acidic site represented by HA ₁ obtained by replacing the cation site M ₁ ⁺ in the structural site X with H ⁺ , a plurality of acid dissociation constants The value of the acid dissociation constant a2 is larger than the largest value of a1. The acid dissociation constant when the compound PI becomes "a compound having one A ₁ ^- , one HA ₁ and one HA ₂ " is aa, and "one A ₁ ^- and one HA ₁ and 1 The relationship ^between aa and ab satisfies aa<ab, where ab is the acid dissociation constant when a compound having two _HA2 's becomes _a compound having two A1- and one _HA2 . .

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

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

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

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

The anion site A ₁ ^- and the anion site A ₂ ^- are structural sites containing negatively charged atoms or atomic groups, for example, formulas (AA-1) to (AA-3) and formula (BB -1) to (BB-6).
The anion site A ₁ ^- is preferably one capable of forming an acidic site with a small acid dissociation constant, and more preferably one of the formulas (AA-1) to (AA-3). AA-1) and (AA-3) are more preferred.
Further, the anion site A ₂ ^- is preferably one capable of forming an acidic site with a larger acid dissociation constant than the anion site A ₁ ^- , and is any of the formulas (BB-1) to (BB-6). is more preferred, and either formula (BB-1) or (BB-4) is even more preferred.
In formulas (AA-1) to (AA-3) and formulas (BB-1) to (BB-6) below, * represents a bonding position.
In formula (AA-2), ^RA represents a monovalent organic group. Although the monovalent organic group represented by ^RA is not particularly limited, examples thereof include a cyano group, a trifluoromethyl group and a methanesulfonyl group.

The cation site M ₁ ⁺ and the cation site M ₂ ⁺ are structural sites containing positively charged atoms or atomic groups, such as monovalent organic cations. Organic cations include, for example, the organic cations described above as the cations represented by M ⁺ .

The specific structure of compound (I) is not particularly limited, but includes, for example, compounds represented by formulas (Ia-1) to (Ia-5) described below.

-Compound represented by Formula (Ia-1)-
First, the compound represented by Formula (Ia-1) will be described below.

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 upon exposure to actinic rays or radiation.

In formula (Ia-1), M ₁₁ ⁺ and M ₁₂ ⁺ each independently represent an organic cation.
A ₁₁ ^- and A ₁₂ ^- each independently represent a monovalent anionic functional group.
L ₁ represents a divalent linking group.
M ₁₁ ⁺ and M ₁₂ ⁺ may be the same or different.
A ₁₁ ^- and A ₁₂ ^- may be the same or different, but are preferably different from each other.
However, in the compound PIa (HA ₁₁ -L ₁ -A ₁₂ H) obtained by replacing the cations represented by M ₁₁ ⁺ and M ₁₂ ⁺ with H ⁺ in the above formula (Ia- ₁ ), The acid dissociation constant a2 derived from the acidic site represented by HA11 is greater than the acid dissociation constant a1 derived from the acidic site represented by _HA11 . The preferred values of the acid dissociation constant a1 and the acid dissociation constant a2 are as described above. The same acid is generated from compound PIa and the compound represented by formula (Ia-1) upon exposure to actinic rays or radiation.
At least one of M ₁₁ ⁺ , M ₁₂ ⁺ , A ₁₁ ⁻ , A ₁₂ ⁻ , and L ₁ may have an acid-decomposable group as a substituent.

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

The monovalent anionic functional group represented by A ₁₁ ^- intends a monovalent group containing the above-mentioned anionic site A ₁ ^- . Moreover, the monovalent anionic functional group represented by A ₁₂ ^- intends a monovalent group containing the above-mentioned anion site A ₂ ^- .
The monovalent anionic functional groups represented by A ₁₁ ^- and A ₁₂ ^- include any of the above formulas (AA-1) to (AA-3) and formulas (BB-1) to (BB-6). It is preferably a monovalent anionic functional group containing an anion site, selected from the group consisting of formulas (AX-1) to (AX-3) and formulas (BX-1) to (BX-7) is more preferably a monovalent anionic functional group. The monovalent anionic functional group represented by A ₁₁ ^- is, among others, a monovalent anionic functional group represented by any one of formulas (AX-1) to (AX-3). preferable. As the monovalent anionic functional group represented by A ₁₂ ^- , monovalent anionic functional groups represented by any one of formulas (BX-1) to (BX-7) are preferred, and A monovalent anionic functional group represented by any one of (BX-1) to (BX-6) is more preferred.

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

The monovalent organic group represented by ^RA2 is preferably a linear, branched or cyclic alkyl group or aryl group.
The number of carbon atoms in the alkyl group is preferably 1-15, more preferably 1-10, even more preferably 1-6.
The above alkyl group may have a substituent. The substituent is preferably a fluorine atom or a cyano group, more preferably a fluorine atom. When the alkyl group has a fluorine atom as a substituent, it may be a perfluoroalkyl group.

The aryl group is preferably a phenyl group or a naphthyl group, more preferably a phenyl group.
The aryl group may have a substituent. The substituent is preferably a fluorine atom, an iodine atom, a perfluoroalkyl group (eg, preferably having 1 to 10 carbon atoms, more preferably having 1 to 6 carbon atoms), or a cyano group, a fluorine atom, an iodine atom, or , perfluoroalkyl groups are more preferred.

In formulas (BX-1) to (BX-4) and formula (BX-6), R 2 ^B represents a monovalent organic group. * represents a binding position.
The monovalent organic group represented by ^RB is preferably a linear, branched or cyclic alkyl group or aryl group.
The number of carbon atoms in the alkyl group is preferably 1-15, more preferably 1-10, even more preferably 1-6.
The above alkyl group may have a substituent. Although the substituent is not particularly limited, the substituent is preferably a fluorine atom or a cyano group, more preferably a fluorine atom. When the alkyl group has a fluorine atom as a substituent, it may be a perfluoroalkyl group.
In addition, when the carbon atom serving as the bonding position in the alkyl group has a substituent, it is also preferably a substituent other than a fluorine atom or a cyano group. Here, the carbon atom to be the bonding position in the alkyl group is, for example, in the case of formulas (BX-1) and (BX-4), the carbon directly bonded to -CO- indicated in the formula in the alkyl group In the case of formulas (BX-2) and (BX-3), the carbon atom directly bonded to —SO ₂ — indicated in the formula in the alkyl group corresponds to the formula (BX-6) In the case of , the carbon atom in the alkyl group that is directly bonded to the N ^{2 -} specified in the formula is applicable.
A carbon atom of the alkyl group may be substituted with a carbonyl carbon.

The aryl group is preferably a phenyl group or a naphthyl group, more preferably a phenyl group.
The aryl group may have a substituent. Examples of substituents include a fluorine atom, an iodine atom, a perfluoroalkyl group (eg, preferably having 1 to 10 carbon atoms, more preferably 1 to 6 carbon atoms), a cyano group, an alkyl group (eg, 1 to 10 carbon atoms). is preferred, and more preferably 1 to 6 carbon atoms.), an alkoxy group (eg, preferably 1 to 10 carbon atoms, more preferably 1 to 6 carbon atoms.), or an alkoxycarbonyl group (eg, 2 to 10 carbon atoms are preferred, and those having 2 to 6 carbon atoms are more preferred.), and more preferred is a fluorine atom, an iodine atom, a perfluoroalkyl group, an alkyl group, an alkoxy group, or an alkoxycarbonyl group.

In formula (Ia-1), the divalent linking group represented by L ₁ is not particularly limited, and includes -CO-, -NR-, -O-, -S-, -SO-, -SO ₂ - , an alkylene group (preferably having 1 to 6 carbon atoms, which may be linear or branched), a cycloalkylene group (preferably having 3 to 15 carbon atoms), an alkenylene group (preferably having 2 to 6 carbon atoms), divalent of an 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 a 5- to 7-membered ring, a 5- to 6-membered ring is more preferable), 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, and a 5- to 7-membered ring is More preferably, a 5- to 6-membered ring is more preferable.), a divalent aromatic hydrocarbon ring group (preferably a 6- to 10-membered ring, more preferably a 6-membered ring.), and a bivalent combination of a plurality of these A connecting group of The above R includes a hydrogen atom or a monovalent organic group. Although the monovalent organic group is not particularly limited, for example, an alkyl group (preferably having 1 to 6 carbon atoms) is preferable.
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 have a substituent. may Substituents include, for example, halogen atoms (preferably fluorine atoms).

Among them, the divalent linking group represented by _L1 is preferably a divalent linking group represented by formula (L1).

In formula (L1), L ₁₁₁ represents a single bond or a divalent linking group.
The divalent linking group represented by L ₁₁₁ is not particularly limited, and may be, for example, —CO—, —NH—, —O—, —SO—, —SO ₂ —, or have a substituent. Alkylene group (preferably having 1 to 6 carbon atoms, which may be linear or branched), optionally substituted cycloalkylene group (preferably having 3 to 15 carbon atoms), substituted An aryl group (preferably having 6 to 10 carbon atoms) optionally having a group, and a divalent linking group combining a plurality of these groups may be mentioned. The substituent is not particularly limited, and examples thereof include halogen atoms.
p represents an integer of 0-3, preferably an integer of 1-3.
v represents an integer of 0 or 1;
Each Xf ₁ independently represents a fluorine atom or an alkyl group substituted with at least one fluorine atom. The number of carbon atoms in this alkyl group is preferably 1-10, more preferably 1-4. A perfluoroalkyl group is preferred as the alkyl group substituted with at least one fluorine atom.
Each _Xf2 independently represents a hydrogen atom, an alkyl group optionally having a fluorine atom as a substituent, or a fluorine atom. The number of carbon atoms in this alkyl group is preferably 1-10, more preferably 1-4. _Xf2 preferably represents a fluorine atom or an alkyl group substituted with at least one fluorine atom, more preferably a fluorine atom or a perfluoroalkyl group.
Among them, Xf ₁ and Xf ₂ are each independently preferably a fluorine atom or a perfluoroalkyl group having 1 to 4 carbon atoms, more preferably a fluorine atom or CF ₃ . In particular, both Xf ₁ and Xf ₂ are more preferably fluorine atoms.
* represents a binding position.
When L ₁ in formula (Ia-1) represents a divalent linking group represented by formula (L1), the bond (*) on the L ₁₁₁ side in formula (L1) is represented by formula (Ia-1 ) is preferred to bind to A ₁₂ ⁻ in

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

In formula (Ia-2), A _21a ^- and A _21b ^- each independently represent a monovalent anionic functional group. Here, the monovalent anionic functional groups represented by A _21a ^- and A _21b ^- are meant to be monovalent groups containing the above-described anionic site A ₁ ^- . The monovalent anionic functional groups represented by A _21a ^- and A _21b ^- are not particularly limited. Anionic functional groups are included.
A ₂₂ ^- represents a divalent anionic functional group. Here, the divalent anionic functional group represented by A ₂₂ ^- intends a divalent linking group containing the above-mentioned anion site A ₂ ^- . Examples of the divalent anionic functional group represented by A ₂₂ ^- include divalent anionic functional groups represented by formulas (BX-8) to (BX-11) shown below.

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 M ₁ ⁺ described above, and the preferred embodiments are also the same.
_L21 and _L22 each independently represent a divalent organic group.

In the compound PIa-2 obtained by replacing the organic cations represented by M _21a ⁺ , M _21b ⁺ , and M ₂₂ ⁺ in the above formula (Ia-2) with H ⁺ , at the acidic site represented by A ₂₂ H The derived 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. The acid dissociation constant a1-1 and the acid dissociation constant a1-2 correspond to the acid dissociation constant a1 described above.
A _21a ^- and A _21b ^- may be the same or different. M _21a ⁺ , M _21b ⁺ , and M ₂₂ ⁺ may be the same or different.
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. The definition of the monovalent anionic functional group represented by A _31a ^- is synonymous with A _21a ^- and A _21b ^- in formula (Ia-2) described above, and the preferred embodiments are also the same.
The monovalent anionic functional group represented by A ₃₂ ^- intends a monovalent group containing the anion site A ₂ ^- described above. The monovalent anionic functional group represented by A ₃₂ ^- is not particularly limited, and is, for example, a monovalent anionic functional group selected from the group consisting of the above formulas (BX-1) to (BX-7). is mentioned.
A _31b ^- represents a divalent anionic functional group. Here, the divalent anionic functional group represented by A _31b ^- intends a divalent linking group containing the anionic site A ₁ ^- described above. Examples of the divalent anionic functional group represented by A _31b ^- include divalent anionic functional groups represented by formula (AX-4) shown below.

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 ⁺ described above, and the preferred embodiments are also the same.
L ₃₁ and L ₃₂ each independently represent a divalent organic group.

In the compound PIa-3 obtained by replacing the organic cations represented by M _31a ⁺ , M _31b ⁺ , and M ₃₂ ⁺ in the above formula (Ia-3) with H ⁺ , at the acidic site represented by A ₃₂ H The derived 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. The acid dissociation constant a1-3 and the acid dissociation constant a1-4 correspond to the acid dissociation constant a1 described above.
A _31a ^- and A ₃₂ ^- may be the same or different. In addition, M _31a ⁺ , M _31b ⁺ , and M ₃₂ ⁺ may be the same or different.
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. The definitions of the monovalent anionic functional groups represented by A _41a ^- and A _41b ^- are the same as those of A _21a ^- and A _21b ^- in formula (Ia-2) described above. The definition of the monovalent anionic functional group represented by A ₄₂ ^- is the same as A ₃₂ ^- in formula (Ia-3) described above, and the preferred embodiments are also the same.
M _41a ⁺ , M _41b ⁺ , and M ₄₂ ⁺ each independently represent an organic cation.
_L41 represents a trivalent organic group.

In the compound PIa-4 obtained by replacing the organic cations represented by M _41a ⁺ , M _41b ⁺ , and M ₄₂ ⁺ in the above formula (Ia-4) with H ⁺ , at the acidic site represented by A ₄₂ H The derived 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. The acid dissociation constant a1-5 and the acid dissociation constant a1-6 correspond to the acid dissociation constant a1 described above.
A _41a ⁻ , A _41b ⁻ , and A ₄₂ ⁻ may be the same or different. In addition, M _41a ⁺ , M _41b ⁺ , and M ₄₂ ⁺ may be the same or different.
At least one of M _41a ⁺ , M _41b ⁺ , M ₄₂ ⁺ , A _41a ⁻ , A _41b ⁻ , A ₄₂ ⁻ , and L ₄₁ may have an acid-decomposable group as a substituent.

The divalent organic groups represented by L ₂₁ and L ₂₂ in formula (Ia-2) and L ₃₁ and L ₃₂ in formula (Ia-3) are not particularly limited, for example, —CO— , —NR—, —O—, —S—, —SO—, —SO ₂ —, an alkylene group (preferably having 1 to 6 carbon atoms, which may be linear or branched), a cycloalkylene group (preferably 3 to 15 carbon atoms), alkenylene groups (preferably 2 to 6 carbon atoms), divalent aliphatic heterocyclic groups (at least one N atom, O atom, S atom, or Se atom in the ring structure 5 A to 10-membered ring is preferred, a 5- to 7-membered ring is more preferred, and a 5- to 6-membered ring is even more preferred.), a divalent aromatic heterocyclic group (at least one N atom, O atom, S atom, or Se A 5- to 10-membered ring having an atom in the ring structure is preferred, a 5- to 7-membered ring is more preferred, and a 5- to 6-membered ring is even more preferred.), a divalent aromatic hydrocarbon ring group (6- to 10-membered ring is preferred, and a 6-membered ring is more preferred.), and a divalent organic group combining a plurality of these. R in -NR- is a hydrogen atom or a monovalent organic group. Although the monovalent organic group is not particularly limited, for example, an alkyl group (preferably having 1 to 6 carbon atoms) is preferable.
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 have a substituent. may Substituents include, for example, halogen atoms (preferably fluorine atoms).

Examples of divalent organic groups represented by L ₂₁ and L ₂₂ in formula (Ia-2) and L ₃₁ and L ₃₂ in formula (Ia-3) are represented by the following formula (L2): It is also preferred that it is a divalent organic group that

In formula (L2), q represents an integer of 1-3. * represents a binding position.
Each Xf independently represents a fluorine atom or an alkyl group substituted with at least one fluorine atom. The number of carbon atoms in this alkyl group is preferably 1-10, more preferably 1-4. A perfluoroalkyl group is preferred as the alkyl group substituted with at least one fluorine atom.
Xf is preferably a fluorine atom or a C 1-4 perfluoroalkyl group, more preferably a fluorine atom or CF ₃ . In particular, it is more preferable that both Xf are fluorine atoms.

_LA represents a single bond or a divalent linking group.
The divalent linking group represented by L _A is not particularly limited, and examples thereof include -CO-, -O-, -SO-, -SO ₂ -, alkylene groups (preferably having 1 to 6 carbon atoms, straight-chain may be in the form of a branched chain), a cycloalkylene group (preferably having 3 to 15 carbon atoms), a divalent aromatic hydrocarbon ring group (preferably a 6- to 10-membered ring, more preferably a 6-membered ring), and Divalent linking groups in which a plurality of these are combined are included.
The alkylene group, the cycloalkylene group, and the divalent aromatic hydrocarbon ring group may have a substituent. Substituents include, for example, halogen atoms (preferably fluorine atoms).

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- _SO2 - _CF2- *, *-Ph-O- _SO2 - _CF2 - _CF2- *, *-Ph-O- _SO2 - _CF2 - _CF2 - _CF2- *, and , *—Ph—OCO—CF ₂ —*. Ph is an optionally substituted phenylene group, preferably a 1,4-phenylene group. Although the substituent is not particularly limited, an alkyl group (eg, preferably having 1 to 10 carbon atoms, more preferably 1 to 6 carbon atoms), an alkoxy group (eg, preferably having 1 to 10 carbon atoms, 1 to 1 carbon atoms, 6 is more preferable), or an alkoxycarbonyl group (eg, preferably having 2 to 10 carbon atoms, more preferably 2 to 6 carbon atoms).
When L ₂₁ and L ₂₂ in formula (Ia-2) represent a divalent organic group represented by formula (L2), the bond (*) on the L _A side in formula (L2) is represented by formula ( It preferably binds to A _21a ^- and A _21b ^- in Ia-2).
When L ₃₁ and L ₃₂ in formula (Ia-3) represent a divalent organic group represented by formula (L2), the bond (*) on the L _A side in formula (L2) is represented by formula ( It preferably binds to A _31a ^- and A ₃₂ ^- in Ia-3).

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

In formula (Ia-5), A _51a ⁻ , A _51b ⁻ , and A _51c ⁻ each independently represent a monovalent anionic functional group. Here, the monovalent anionic functional groups represented by A _51a ⁻ , A _51b ⁻ , and A _51c ⁻ are intended to be monovalent groups containing the above-described anionic site A ₁ ⁻ . The monovalent anionic functional groups represented by A _51a ⁻ , A _51b ⁻ , and A _51c ⁻ are not particularly limited, but are, for example, the group consisting of the above formulas (AX-1) to (AX-3) A selected monovalent anionic functional group can be mentioned.
A _52a ^- and A _52b ^- represent divalent anionic functional groups. Here, the divalent anionic functional groups represented by A _52a ^- and A _52b ^- are intended to be divalent linking groups containing the above-mentioned anion site A ₂ ^- . The divalent anionic functional groups represented by A _52a ^- and A _52b ^- are, for example, divalent anionic functional groups selected from the group consisting of the above formulas (BX-8) to (BX-11). is mentioned.

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 M ₁ ⁺ described above, and preferred embodiments are also the same.
_L51 and _L53 each independently represent a divalent organic group. The divalent organic groups represented by L ₅₁ and L ₅₃ have the same meanings as L ₂₁ and L ₂₂ in formula (Ia-2) above, and the preferred embodiments are also the same.
_L52 represents a trivalent organic group. The trivalent organic group represented by L ₅₂ has the same definition as L ₄₁ in formula (Ia-4) above, and the preferred embodiments are also the same.

In the compound PIa-5, wherein the organic cations represented by M _51a ⁺ , M _51b ⁺ , M _51c ⁺ , M _52a ⁺ , and M _52b ⁺ in the above formula (Ia-5) are replaced with H ⁺ , A _52a The acid dissociation constant a2-1 derived from the acidic site represented by H and the acid dissociation constant a2-2 derived from the acidic site represented by A _52b H are the acid dissociation constant a1-1 derived from A _51a H, It is larger than the acid dissociation constant a1-2 derived from the acidic site represented by A _51b H and the acid dissociation constant a1-3 derived from the acidic site represented by A _51c H. The acid dissociation constants a1-1 to a1-3 correspond to the acid dissociation constant a1 described above, and the acid dissociation constants a2-1 and a2-2 correspond to the acid dissociation constant a2 described above.
A _51a ⁻ , A _51b ⁻ , and A _51c ⁻ may be the same or different. In addition, A _52a ^- and A _52b ^- may be the same or different. M _51a ⁺ , M _51b ⁺ , M _51c ⁺ , M _52a ⁺ , and M _52b ⁺ may be the same or different.
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 is an acid-decomposable group as a substituent may have

(Compound (II))
Compound (II) is a compound having two or more of the above structural moieties X and one or more of the following structural moieties Z, wherein the first acidic It is a compound that generates an acid containing two or more sites and the structural site Z described above.
Structural site Z: nonionic site capable of neutralizing acid

The definition of structural site X and the definitions of A ₁ ^- and M ₁ ⁺ in compound (II) are the same as the definitions of structural site X and the definitions of A ₁ ^- and M ₁ ⁺ in compound (I) above. is synonymous with and preferred embodiments are also the same.

HA ₁ obtained by replacing the cation site M ₁ ⁺ in the structural site X with H ⁺ in the compound PII, which is obtained by replacing the cation site M ₁ ⁺ in the structural site X with H ⁺ in the compound (II). The preferred range of the acid dissociation constant a1 derived from the acidic site represented by is the same as the acid dissociation constant a1 in the above compound PI.
In addition, for example, when the compound (II) is a compound that generates an acid having two of the first acidic sites derived from the structural site X and the structural site Z, the compound PII is "two HA ₁ It corresponds to "a compound having When the acid dissociation constant of this compound PII is determined, the acid dissociation constant when the compound PII is "a compound having one A ₁ ^- and one HA ₁ " and "one A ₁ ^- and one HA The acid dissociation constant when the "compound having ₁ " becomes "the compound having two A ₁ ^- " corresponds to the acid dissociation constant a1.

The acid dissociation constant a1 is obtained by the method for measuring the acid dissociation constant described above.
The above compound PII corresponds to an acid generated when compound (II) is irradiated with actinic rays or radiation.
The two or more structural sites X may be the same or different. Two or more of A ₁ ⁻ and two or more of M ₁ ⁺ may be the same or different.

The nonionic site capable of neutralizing the acid in the structural site Z is not particularly limited. For example, a site containing a group capable of electrostatically interacting with protons or a functional group having electrons is preferred.
A group capable of electrostatically interacting with protons or a functional group having electrons is a functional group having a macrocyclic structure such as a cyclic polyether, or a lone pair of electrons that does not contribute to π conjugation. A functional group having a nitrogen atom is included. A nitrogen atom having a lone pair of electrons that does not contribute to π-conjugation is, for example, a nitrogen atom having a partial structure represented by the following formula.

Partial structures of functional groups having electrons or groups capable of electrostatically interacting with protons include, for example, 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 them, primary to tertiary amine structures are preferred.

The compound (II) is not particularly limited, but includes, for example, compounds represented by the following formulas (IIa-1) and (IIa-2).

In formula (IIa-1) above, A _61a ^- and A _61b ^- have the same meanings as A ₁₁ ^- in formula (Ia-1) above, and preferred embodiments are also the same. M _61a ⁺ and M _61b ⁺ have the same meanings as M ₁₁ ⁺ in formula (Ia-1) described above, and the preferred embodiments are also the same.
In formula (IIa-1) above, L ₆₁ and L ₆₂ have the same definitions as L ₁ in formula (Ia-1) above, and the preferred embodiments 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 may be an alkyl group (preferably having 1 to 10 carbon atoms, which may be linear or branched), a cycloalkyl group (preferably having 3 to 15), or an alkenyl group (preferably having 2 to 6 carbon atoms). —CH ₂ — contained in the alkyl group, cycloalkyl group and alkenyl group in the monovalent organic group represented by R _2X is —CO—, —NH—, —O—, —S—, and —SO— , and —SO ₂ — may be substituted with one or a combination of two or more.
The alkylene group, the cycloalkylene group, and the alkenylene group may have a substituent. Examples of substituents include, but are not particularly limited to, halogen atoms (preferably fluorine atoms).

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

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

The acidic site represented by A 71a H in the compound PIIa-2 obtained by replacing the organic cations represented by M _71a ⁺ , M _71b ⁺ , and M _71c ⁺ in the above formula ₍ IIa-2) with H ⁺ The acid dissociation constant a1-9 derived from, 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 are It corresponds to the acid dissociation constant a1 described above.
The compound PIIa-2, which is obtained by replacing the cation sites M _71a ⁺ , M _71b ⁺ , and M _71c ⁺ in the structural site X of the compound (IIa-1) with H ⁺ , has HA _71a -L ₇₁ -N(L ₇₃ -A _71c H) -L ₇₂ -A _71b H. In addition, compound PIIa-2 is the same as the acid generated from the compound represented by formula (IIa-2) upon exposure to actinic rays or radiation.
at least one of M _71a ⁺ , M _71b ⁺ , M _71c ⁺ , A _71a ⁻ , A _71b ⁻ , A _71c ⁻ , L ₇₁ , L ₇₂ and L ₇₃ has an acid-decomposable group as a substituent; may

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

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

The content of compound (B) in the composition of the present invention is not particularly limited, but is preferably 0.5% by mass or more, more preferably 1.0% by mass or more, based on the total solid content of the composition of the present invention. preferable. 25. The content of compound (B) in the composition of the present invention is preferably 50.0% by mass or less, more preferably 30.0% by mass or less, relative to the total solid content of the composition of the present invention. 0% by mass or less is more preferable.
Compound (B) may be used alone or in combination of two or more.

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

Examples of the organic group represented by R ^1Z in the general formula (Q1) include an alkyl group (linear or branched), a cycloalkyl group (monocyclic or polycyclic), and an alkenyl group (linear or branched). , or an aryl group (monocyclic or polycyclic) is preferred, an aryl group is more preferred, and a phenyl group is even more preferred.
The alkyl group for R ^1Z is preferably an alkyl group having 1 to 5 carbon atoms such as methyl group, ethyl group, n-propyl group, isopropyl group, n-butyl group, isobutyl group and t-butyl group.
Examples of the cycloalkyl group for R ^1Z include cycloalkyl groups having 3 to 20 carbon atoms, such as monocyclic cycloalkyl groups such as cyclopentyl and cyclohexyl, norbornyl, tetracyclodecanyl, tetra A polycyclic cycloalkyl group such as a cyclododecanyl group and an adamantyl group is preferred.
The aryl group of R ^1Z is preferably an aryl group having 6 to 20 carbon atoms, such as a phenyl group, a naphthyl group and an anthryl group, with a phenyl group being particularly preferred.
As the alkenyl group for R ^1Z , an alkenyl group having 2 to 5 carbon atoms such as a vinyl group is preferable.
The alkyl group, the cycloalkyl group, the alkenyl group, and the aryl group may further have a substituent. Examples of the substituent include the substituent T described above, and particularly preferred are an alkyl group, a cycloalkyl group, an aryl group, an alkoxy group, a cycloalkyloxy group, a hydroxy group, and a halogen atom.

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

The compound (C) is preferably a compound represented by the following general formula (Q2). The compound represented by the following general formula (Q2) can achieve both resistance to volatilization and solubility as a carboxylic acid after cationic decomposition.

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 hydroxy group, an alkoxy group, a cycloalkyloxy group, a fluorine atom or an iodine atom.
Mq ⁺ represents a cation.

The alkyl groups of R ^2Z to R ^6Z include alkyl groups having 1 to 5 carbon atoms such as methyl group, ethyl group, n-propyl group, isopropyl group, n-butyl group, isobutyl group and t-butyl group. preferable.
The cycloalkyl groups of R ^2Z to R ^6Z include cycloalkyl groups having 3 to 20 carbon atoms, such as monocyclic cycloalkyl groups such as cyclopentyl and cyclohexyl groups, norbornyl and tetracyclodecanyl. , tetracyclododecanyl groups and polycyclic cycloalkyl groups such as adamantyl groups are preferred.
The aryl group represented by R ^2Z to R ^6Z is preferably an aryl group having 6 to 20 carbon atoms, such as a phenyl group, a naphthyl group and an anthryl group, with a phenyl group being particularly preferred.
Alkenyl groups of R ^2Z to R ^6Z are preferably alkenyl groups having 2 to 5 carbon atoms such as vinyl groups.
The alkoxy groups of R ^2Z to R ^6Z are preferably alkoxy groups having 1 to 5 carbon atoms.
Cycloalkyloxy groups of R ^2Z to R ^6Z are preferably monocyclic or polycyclic cycloalkyloxy groups having 3 to 20 carbon atoms.

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

Compound (C) is preferably a compound that generates an acid that is relatively weaker in acidity than the acid generated from compound (B) upon exposure to actinic rays or radiation.
The compound (C) can act as a quencher that traps the acid generated from the compound (B) during exposure and suppresses the reaction of the resin (A) in the unexposed area due to excess generated acid.

Specific examples of compound (C) are shown below, but are not limited to these.

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

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

In 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 a plurality of ^RKT1 , ^RKT2 and ^RKT3 , the plurality of ^RKT1 , the plurality of ^RKT2 and the plurality of ^RKT3 may be the same or different. w1, w2 and w3 each independently represents an integer of 0 to 5; However, 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 linear or branched. Although the number of carbon atoms in the alkyl group is not particularly limited, it is preferably 1-5, more preferably 1-3.
The number of carbon atoms in the cycloalkyl groups of R ^KT1 , R ^KT2 and R ^KT3 is not particularly limited, but is preferably 3-20, more preferably 5-15. Cycloalkyl groups of R ^KT1 , R ^KT2 and R ^KT3 may be monocyclic cycloalkyl groups such as cyclopentyl group and cyclohexyl group, norbornyl group, tetracyclodecanyl group, tetracyclododecanyl group and adamantyl group. It may be a polycyclic cycloalkyl group such as
The halogen atoms of R ^KT1 , R ^KT2 and R ^KT3 include a fluorine atom, a chlorine atom, a bromine atom and an iodine atom, preferably a fluorine atom or an iodine atom.
The alkyl groups contained in the alkoxy groups of R ^KT1 , R ^KT2 and R ^KT3 may be linear or branched. Although the number of carbon atoms in the alkyl group contained in the alkoxy group is not particularly limited, it is preferably 1-5, more preferably 1-3.
The alkyl groups contained in the alkoxycarbonyl groups of R ^KT1 , R ^KT2 and R ^KT3 may be linear or branched. Although the number of carbon atoms in the alkyl group contained in the alkoxycarbonyl group is not particularly limited, it is preferably 1-5, more preferably 1-3.

Each of w1, w2 and w3 independently represents an integer of 0 to 5, preferably an integer of 0 to 4, more preferably an integer of 1 to 3. However, 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)”) different from resin (A).
The hydrophobic resin (D) is preferably designed so as to be unevenly distributed on the surface of the resist film. It does not have to contribute to uniform mixing.
The effects of adding the hydrophobic resin (D) include control of the static and dynamic contact angles of the resist film surface with respect to water, and suppression of outgassing.

Hydrophobic resin (D) preferably has one or more of fluorine atoms, silicon atoms, and _CH3 partial structures contained in the side chain portion of the resin, from the viewpoint of uneven distribution on the film surface layer. , more preferably two or more. The hydrophobic resin preferably has a hydrocarbon group with 5 or more carbon atoms. These groups may be present in the main chain of the resin or may be substituted on the side chain.
The hydrophobic resin (D) includes compounds described in paragraphs [0275] to [0279] of WO2020/004306.

When the composition of the present invention contains a hydrophobic resin (D), the content of the hydrophobic resin (D) is 0.01 to 20.0% by mass with respect to the total solid content of the composition of the present invention. Preferably, 0.1 to 15.0% by mass is more preferable.

[Surfactant]
The composition of the invention may contain a surfactant. When a surfactant is contained, it is possible to form a pattern with excellent adhesion and fewer development defects.
The surfactant is preferably a fluorine-based and/or silicon-based surfactant.
Fluorinated and/or silicon-based surfactants include surfactants disclosed in paragraphs [0218] and [0219] of WO2018/193954.

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

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

[solvent]
The composition of the invention preferably contains a solvent.
Solvent consists of (M1) propylene glycol monoalkyl ether carboxylate and (M2) propylene glycol monoalkyl ether, lactate, acetate, alkoxypropionate, linear ketone, cyclic ketone, lactone, and alkylene carbonate. It is preferable to include at least one selected from the group. The solvent may further contain components other than components (M1) and (M2).

A combination of the above-described solvent and the above-described resin is preferable from the viewpoint of improving the coatability of the composition of the present invention and reducing the number of pattern development defects. Since the solvent described above has a good balance of solubility, boiling point, and viscosity of the resin described above, it is possible to suppress unevenness in the thickness of the resist film and generation of deposits during spin coating.
Details of component (M1) and component (M2) are described in paragraphs [0218] to [0226] of WO2020/004306, the contents of which are incorporated herein.

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 determined so that the solid content concentration is 0.5 to 30% by mass, more preferably 1 to 20% by mass. By doing so, the coatability of the composition of the present invention can be further improved.

[Other additives]
The composition of the present invention contains a dissolution-inhibiting compound, a dye, a plasticizer, a photosensitizer, a light-absorbing agent, and/or a compound that promotes solubility in a developer (for example, a phenolic compound having a molecular weight of 1000 or less, or An alicyclic or aliphatic compound containing a carboxyl group) may further be included.

The "dissolution-inhibiting compound" is a compound with a molecular weight of 3000 or less, which is decomposed by the action of an acid to reduce its solubility in an organic developer.

The composition of the present invention is suitably used as a photosensitive composition for EUV exposure.
EUV light has a wavelength of 13.5 nm, which is shorter than ArF (wavelength 193 nm) light and the like, so the number of incident photons is smaller when exposed with the same sensitivity. Therefore, the influence of "photon shot noise", in which the number of photons stochastically varies, is large, leading to deterioration of line edge roughness (LER) and bridge defects. To reduce the photon shot noise, there is a method of increasing the number of incident photons by increasing the amount of exposure, but this is a trade-off with the demand for higher sensitivity.

When the A value obtained by the following formula (1) is high, the EUV light and electron beam absorption efficiency of the resist film formed from the resist composition increases, which is effective in reducing photon shot noise. The A value represents the absorption efficiency of the EUV light and the electron beam relative to the mass ratio of the resist film.
Formula (1): A = ([H] x 0.04 + [C] x 1.0 + [N] x 2.1 + [O] x 3.6 + [F] x 5.6 + [S] x 1.5 + [I] × 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, the optical image profile in the resist film will deteriorate, and as a result, it will be difficult to obtain a good pattern shape. Therefore, 0.240 or less is preferable, and 0.220 or less is more preferable.

In the formula (1), [H] represents the molar ratio of hydrogen atoms derived from the total solid content to the total atoms of the total solid content in the actinic ray-sensitive or radiation-sensitive resin composition, and [C] represents the molar ratio of carbon atoms derived from the total solid content to the total atoms of the total solid content in the actinic ray-sensitive or radiation-sensitive resin composition, [N] is the actinic ray-sensitive or radiation-sensitive resin Represents the molar ratio of nitrogen atoms derived from the total solid content with respect to the total atoms of the total solid content in the composition, [O] is the total atoms of the total solid content in the actinic ray-sensitive or radiation-sensitive resin composition , represents the molar ratio of oxygen atoms derived from the total solid content, and [F] represents the molar ratio of fluorine atoms derived from the total solid content to the total atoms of the total solid content in the actinic ray-sensitive or radiation-sensitive resin composition. represents, [S] represents the molar ratio of sulfur atoms derived from the total solid content to the total atoms of the total solid content in the actinic ray-sensitive or radiation-sensitive resin composition, [I] is the actinic ray-sensitive represents the molar ratio of iodine atoms derived from the total solid content to the total atoms of the total solid content in the curable or radiation-sensitive resin composition.
For example, when the resist composition contains an acid-decomposable resin, a photoacid generator, an acid diffusion controller, and a solvent, the acid-decomposable resin, the photoacid generator, and the acid diffusion controller correspond to the solid content. do. That is, the total 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 the total atoms of the total solid content. , hydrogen atoms derived from the acid-decomposable resin, hydrogen atoms derived from the photoacid generator, and the acid, with respect to the sum of all atoms derived from the photoacid generator and all atoms derived from the acid diffusion control agent It represents the total molar ratio of hydrogen atoms derived from the diffusion control agent.

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

<Actinic ray-sensitive or radiation-sensitive film, pattern forming method>
The present invention also relates to actinic or radiation sensitive films formed from the compositions of the present invention. The actinic ray-sensitive or radiation-sensitive film of the present invention is preferably a resist film.
Although the procedure of the pattern forming method using the composition of the present invention is not particularly limited, it preferably includes the following steps.
Step 1: Using the composition of the present invention, a step of forming a resist film on a substrate Step 2: A step of exposing the resist film Step 3: A step of developing the exposed resist film using a developer Below, the above The procedure of each step will be described in detail.

(Step 1: resist film forming step)
Step 1 is a step of forming a resist film on a substrate using the composition of the present invention.

Examples of the method of forming a resist film on a substrate using the composition of the present invention include 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 before application, if necessary. The pore size of the filter is preferably 0.1 µm or less, more preferably 0.05 µm or less, and even more preferably 0.03 µm or less. Filters are preferably made of polytetrafluoroethylene, polyethylene, or nylon.

The compositions of the present invention can be applied onto substrates such as those used in the manufacture of integrated circuit devices (eg, silicon, silicon dioxide coatings) by any suitable coating method such as a spinner or coater. The coating method is preferably spin coating using a spinner. The number of rotations for spin coating using a spinner is preferably 1000 to 3000 rpm (rotations per minute).
After applying the composition of the present invention, the substrate may be dried to form a resist film. If necessary, various base films (inorganic film, organic film, antireflection film) may be formed under the resist film.

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

Although the film thickness of the resist film is not particularly limited, it is preferably 10 to 120 nm from the viewpoint of forming fine patterns with higher precision. In particular, when EUV exposure is used, the film thickness of the resist film is more preferably 10 to 65 nm, and even more preferably 15 to 50 nm. In the case of ArF liquid immersion exposure, the film thickness of the resist film is more preferably 10 to 120 nm, still more preferably 15 to 90 nm.

A topcoat composition may be used to form a topcoat on the upper layer of the resist film.
It is preferable that the topcoat composition does not mix with the resist film and can be uniformly coated on the upper layer of the resist film. The topcoat is not particularly limited, and a conventionally known topcoat can be formed by a conventionally known method. can be formed.
For example, it is preferable to form a topcoat containing a basic compound as described in JP-A-2013-61648 on the resist film. Specific examples of basic compounds that the topcoat may contain include basic compounds that the composition of the present invention may contain.
The topcoat also preferably contains a compound containing at least one group or bond selected from the group consisting of an ether bond, a thioether bond, a hydroxyl group, a thiol group, a carbonyl bond, and an ester bond.

(Step 2: Exposure step)
Step 2 is a step of exposing the resist film.
Examples of the exposure method include a method of irradiating the formed resist film with actinic rays or radiation through a predetermined mask.
Actinic rays or radiation include infrared light, visible light, ultraviolet light, far ultraviolet light, extreme ultraviolet light, X-rays, and electron beams, preferably 250 nm or less, more preferably 220 nm or less, 1 to 200 nm Particularly preferred are wavelengths of deep UV light, specifically KrF excimer lasers (248 nm), ArF excimer lasers (193 nm), _F2 excimer lasers (157 nm), EUV (13.5 nm), X-rays, and electron beams.

After exposure, baking (heating) is preferably performed before development. Baking accelerates the reaction in the exposed area, resulting in better sensitivity and pattern shape.
The heating temperature is preferably 80 to 150°C, more preferably 80 to 140°C, even more preferably 80 to 130°C.
The heating time is preferably 10 to 1000 seconds, more preferably 10 to 180 seconds, even more preferably 30 to 120 seconds.
Heating can be carried out by a means provided in a normal exposing machine and/or developing machine, and may be carried out using a hot plate or the like.
This step is also called a post-exposure bake.

(Step 3: Development step)
Step 3 is a step of developing the exposed resist film using a developer to form a pattern.
The developer may be an alkaline developer or a developer containing an organic solvent (hereinafter also referred to as an organic developer).

Examples of the developing method include a method of immersing the substrate in a tank filled with a developer for a certain period of time (dip method), and a method of developing by standing the developer on the surface of the substrate for a certain period of time by raising the developer by surface tension (puddle method). method), a method of spraying the developer onto the substrate surface (spray method), and a method of continuously discharging the developer while scanning the developer discharge nozzle at a constant speed onto the substrate rotating at a constant speed (dynamic dispensing method). ).
Further, after the step of developing, a step of stopping development may be performed while replacing the solvent with another solvent.
The development time is not particularly limited as long as the resin in the unexposed area is sufficiently dissolved, and is preferably 10 to 300 seconds, more preferably 20 to 120 seconds.
The temperature of the developer is preferably 0 to 50°C, more preferably 15 to 35°C.

It is preferable to use an alkaline aqueous solution containing alkali as the alkaline developer. Although the type of alkaline aqueous solution is not particularly limited, for example, quaternary ammonium salts represented by tetramethylammonium hydroxide, inorganic alkalis, primary amines, secondary amines, tertiary amines, alcohol amines, or cyclic amines. and an alkaline aqueous solution containing Among them, the alkaline developer is preferably an aqueous solution of a quaternary ammonium salt represented by tetramethylammonium hydroxide (TMAH). Suitable amounts of alcohols, surfactants and the like may be added to the alkaline developer. The alkali concentration of the alkali developer is usually preferably 0.1 to 20% by mass. The pH of the alkaline developer is preferably 10.0 to 15.0.

The organic developer is 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. Preferably.

A plurality of the above solvents may be mixed, or may be mixed with a solvent other than the above or water. The water content of the developer as a whole is preferably less than 50% by mass, more preferably less than 20% by mass, even more preferably less than 10% by mass, and particularly preferably substantially free of water.
The content of the organic solvent in the organic developer is preferably 50% by mass or more and 100% by mass or less, more preferably 80% by mass or more and 100% by mass or less, and 90% by mass or more and 100% by mass with respect to the total amount of the developer. The following are more preferable, and 95% by mass or more and 100% by mass or less are particularly preferable.

(Other processes)
The pattern forming method preferably includes a step of washing with a rinse after step 3.

Pure water is an example of the rinse solution used in the rinse step after the step of developing with an alkaline developer. An appropriate amount of surfactant may be added to pure water.
An appropriate amount of surfactant may be added to the rinse solution.

The rinse solution used in the rinse step after the development step using the 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 solution should contain at least one organic solvent selected from the group consisting of hydrocarbon solvents, ketone solvents, ester solvents, alcohol solvents, amide solvents, and ether solvents. is preferred.

The method of the rinsing step is not particularly limited. For example, a method of continuously discharging the rinsing liquid onto the substrate rotating at a constant speed (rotation coating method), or a method of immersing the substrate in a tank filled with the rinsing liquid for a certain period of time. a method (dip method) and a method of spraying a rinse liquid onto the substrate surface (spray method).
Also, the pattern forming method may include a heating step (Post Bake) after the rinsing step. In this step, the developing solution and the rinse solution remaining between the patterns and inside the patterns due to baking are removed. In addition, this process smoothes the resist pattern, and has the effect of improving the roughness of the surface of the pattern. The heating step after the rinsing step is usually carried out at 40 to 250° C. (preferably 90 to 200° C.) for 10 seconds to 3 minutes (preferably 30 seconds to 120 seconds).

Also, the substrate may be etched using the formed pattern as a mask. That is, the pattern formed in step 3 may be used as a mask to process the substrate (or the underlying film and substrate) to form a pattern on the substrate.
The method for processing the substrate (or the underlying film and the substrate) is not particularly limited, but the substrate (or the underlying film and the substrate) is dry-etched using the pattern formed in step 3 as a mask. A method of forming a pattern is preferred. Dry etching is preferably oxygen plasma etching.

The composition of the present invention and various materials used in the pattern forming method (e.g., solvent, developer, rinse, composition for forming an antireflection film, composition for forming a top coat, etc.) contain impurities such as metals. preferably not included. The content of impurities contained in these materials is preferably 1 mass ppm (parts per million) or less, more preferably 10 mass ppb (parts per billion) or less, still more preferably 100 mass ppt or less, particularly 10 mass ppt or less. Preferably, 1 mass ppt or less is most preferred. The lower limit is not particularly limited, and 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 filtration using filters are described in paragraph [0321] of WO2020/004306.

Methods for reducing impurities such as metals contained in various materials include, for example, a method of selecting raw materials with a low metal content as raw materials constituting various materials, and a method of filtering raw materials constituting various materials with a filter. and a method of performing distillation under conditions in which contamination is suppressed as much as possible by, for example, lining the inside of the apparatus with Teflon (registered trademark).

In addition to filter filtration, impurities may be removed with an adsorbent, or filter filtration and adsorbent may be used in combination. As the adsorbent, known adsorbents can be used. For example, inorganic adsorbents such as silica gel and zeolite, and organic adsorbents such as activated carbon can be used. In order to reduce impurities such as metals contained in the various materials described above, it is necessary to prevent metal impurities from entering during the manufacturing process. Whether the metal impurities are sufficiently removed from the manufacturing equipment can be confirmed by measuring the content of the metal component contained in the cleaning liquid used for cleaning the manufacturing equipment. The content of the metal component contained in the cleaning liquid after use is preferably 100 mass ppt (parts per trillion) or less, more preferably 10 mass ppt or less, and even more preferably 1 mass ppt or less. The lower limit is not particularly limited, and is preferably 0 mass ppt or more.

Organic processing liquids such as rinsing liquids should contain conductive compounds to prevent damage to chemical piping and various parts (filters, O-rings, tubes, etc.) due to electrostatic charging and subsequent electrostatic discharge. may be added. The conductive compound is not particularly limited, and examples thereof include methanol. The amount added is not particularly limited, but is preferably 10% by mass or less, more preferably 5% by mass or less, from the viewpoint of maintaining preferable developing properties or rinsing properties. The lower limit is not particularly limited, and is preferably 0.01% by mass or more.
As the chemical liquid pipe, for example, SUS (stainless steel), antistatic treated polyethylene, polypropylene, or various pipes coated with fluororesin (polytetrafluoroethylene, perfluoroalkoxy resin, etc.) can be used. Antistatic treated polyethylene, polypropylene, or fluororesin (polytetrafluoroethylene, perfluoroalkoxy resin, etc.) can also be used for filters and O-rings.

<Method for manufacturing electronic device>
The present specification also relates to an electronic device manufacturing method, including the pattern forming method described above, and an electronic device manufactured by this manufacturing method.
A preferred embodiment of the electronic device of the present specification includes a mode in which it is installed in electric/electronic equipment (household appliances, OA (Office Automation), media-related equipment, optical equipment, communication equipment, etc.).

The present invention will be described in more detail below based on examples. The materials, amounts used, ratios, processing details, and processing procedures shown in the following examples can be changed as appropriate without departing from the gist of the present invention. Therefore, the scope of the present invention should not be construed as limited by the examples shown below.

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

<Resin (A)>
AP-1 to AP-18 were used as the resin (A).
In Comparative Examples 1 and 3, AX-2 and AX-1 were used as resins other than the 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 through AP-18, AX-1 and AX-2 are shown below. The following repeating unit content ratio (content relative to all repeating units in the resin) is a molar ratio (mol %).
The weight average molecular weights (Mw) and dispersity (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). The content of repeating units was measured by ¹³ C-NMR (nuclear magnetic resonance).

<Compound (B)>
B-1 to B-5 were used as compounds (B).

Tables 1 and 2 below list the ClogP values of the acid (generated acid) generated from compound (B) upon exposure to actinic rays or radiation. For B-1 and B-5, the ClogP values for the structures after the acid-decomposable groups of the generated acid are decomposed by acid are shown. When two types of compound (B) were used, the ClogP value was described by separating with "/". For example, in the resist composition R-20 of Example 20, B-1 and B-2 are used, and "3.1/7.2" This is because the ClogP value of the generated acid of B-1 (the structure after the acid-decomposable group is decomposed by acid) is 3.1, and the ClogP value of the generated acid of B-2 is 7.2.

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

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

<Surfactant>
D-1 was used as a surfactant. 20 in the following structural formula represents the number of repeating units.

<Preparation of resist composition>
The components shown in Tables 1 and 2 are used at the contents (% by mass) shown in Tables 1 and 2, dissolved in the solvents shown in Tables 1 and 2, and the solid content concentrations (% by mass) shown in Tables 1 and 2. was prepared and filtered through a polyethylene filter having a pore size of 0.02 μm to obtain resist compositions R-1 to R-32 and RX-1 to RX-3. As for the solvents, Tables 1 and 2 show the types of compounds used and their mass ratios. The content of components other than the solvent is the mass ratio to the total solid content of the resist composition. When two or more kinds of each component were used, each kind and content were separated by "/". For example, "C-1/C-2" in resist composition R-21 indicates that two types of C-1 and C-2 were used as compounds (C), and "7.00/7.00 ” indicates that the content of C-1 is 7.00% by mass and the content of C-2 is 7.00% by mass.

<Coating of resist composition>
The prepared resist composition is coated on a 6-inch Si (silicon) wafer that has been previously treated with hexamethyldisilazane (HMDS) using a Tokyo Electron spin coater Mark 8, and dried on a hot plate at 130° C. for 300 seconds. Then, a resist film having a film thickness shown in Table 3 was formed.
Similar results can be obtained by replacing the Si wafer with a chromium substrate.

<Examples 1 to 14, 16 to 32, Comparative Examples 1 to 3 EB exposure, alkali development (positive)>
The wafer coated with the resist film obtained above was subjected to pattern irradiation using an electron beam lithography system (manufactured by Advantest Co., Ltd.; F7000S, acceleration voltage 50 keV). 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% by mass tetramethylammonium hydroxide aqueous solution (TMAHaq) for 60 seconds, rinsed with water for 45 seconds, and dried. . After that, the wafer was rotated at a rotation speed of 4000 rpm for 30 seconds, and then dried by baking at 90° C. for 60 seconds. A pattern was thus formed.

<Example 15 EB exposure, organic solvent development (negative)>
The wafer coated with the resist film obtained above was subjected to pattern irradiation using an electron beam lithography system (manufactured by Advantest Co., Ltd.; F7000S, acceleration voltage 50 keV). 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, the film 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. After that, the wafer was rotated at a rotation speed of 4000 rpm for 30 seconds, and then dried by baking at 90° C. for 60 seconds. A pattern was thus formed.

[evaluation]
The formed pattern was subjected to defect evaluation using a defect evaluation apparatus (KLA2360; manufactured by KLA-Tencor). A review image was acquired by a review SEM (SEMVision G3E FIB; manufactured by AMAT), and the number of defects was counted.
The results are shown in Table 3 below.

From the results in Table 3, the resist compositions used in Examples 1 to 32 can suppress the occurrence of defects in ultrafine pattern formation as compared to the resist compositions used in Comparative Examples 1 to 3. Do you get it.

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

Claims

An actinic ray-sensitive or radiation-sensitive resin composition comprising a resin (A), a compound (B) that generates an acid upon exposure to actinic rays or radiation, and a compound (C) different from the compound (B), ,
The resin (A) includes a repeating unit represented by the following general formula (N1) and a repeating unit represented by the following general formula (S1),
The content of repeating units represented by the following general formula (N1) in the resin (A) is 55 mol% or more with respect to all repeating units in the resin (A),
The compound (C) is a compound represented by the following general formula (Q1),
Actinic ray-sensitive or radiation-sensitive resin composition.

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.
R4N represents a hydrogen atom or a substituent other than a hydroxy group. R 4N may be combined with at least one of R 1N to R 3N . When multiple R4Ns are present, the multiple R4Ns may be the same or different, and multiple R4Ns may be bonded.
k1 represents 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.

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 bound to at least one of R 1S to R 3S . When multiple R 4S are present, the multiple R 4S may be the same or different, and multiple R 4S may be combined.
R5S represents a group that leaves under the action of an acid. When multiple R 5S are present, the multiple 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, and m3 represents 7-m2.

In general formula (Q1), R 1Z represents an organic group. Mq + represents a cation.
2. The actinic ray-sensitive 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.
R6S represents an organic group.
R 7S represents a substituent other than —COOR 5S . When multiple R7S are present, the multiple R7S may be the same or different. R5S represents a group that leaves under the action of an acid.
R8S represents a substituent. When multiple R 8S are present, the multiple R 8S may be the same or different, and multiple R 8S may be combined.
m4 represents an integer of 1-3.
m5 represents an integer of 0-4.
m6 represents an integer from 0 to (2×m4+6).
The actinic ray-sensitive 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 hydroxy group, an alkoxy group, or a cycloalkyloxy group. R 1P to R 5P do not contain fluorine atoms.
Mp + represents a cation.
The actinic ray-sensitive or radiation-sensitive resin composition according to claim 1, wherein the ClogP value of the acid generated from the compound (B) upon exposure to actinic rays or radiation is 3.5 or less.
The actinic ray-sensitive 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 each independently represent a hydrogen atom, an alkyl group, a cycloalkyl group, an aryl group, a hydroxy group, an alkoxy group, a cycloalkyloxy group, a fluorine atom or an iodine atom.
Mq + represents a cation.
4. The actinic ray-sensitive 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 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 a plurality of RKT1 , RKT2 and RKT3 , the plurality of RKT1 , the plurality of RKT2 and the plurality of RKT3 may be the same or different. w1, w2 and w3 each independently represents an integer of 0 to 5; However, at least one of w1, w2 and w3 represents an integer of 1 or more.
2. The method according to claim 1, wherein the content of the repeating unit represented by the general formula (N1) in the resin (A) is 65 mol % or more based on the total repeating units in the resin (A). Actinic ray-sensitive or radiation-sensitive resin composition.
2. The method according to claim 1, wherein the content of the repeating unit represented by the general formula (S1) in the resin (A) is 25 mol % or more based on the total repeating units in the resin (A). Actinic ray-sensitive or radiation-sensitive resin composition.
The activator according to claim 1, wherein the repeating units contained in the resin (A) are only repeating units represented by the general formula (N1) and repeating units represented by the general formula (S1). Light sensitive or radiation sensitive resin composition.
The actinic ray-sensitive or radiation-sensitive resin composition according to claim 1, wherein the resin (A) has a weight average molecular weight of 8000 or less.
The actinic ray-sensitive or radiation-sensitive resin composition according to claim 1, wherein the resin (A) has a degree of dispersion of 1.7 or less.
The actinic ray-sensitive or radiation-sensitive resin composition according to claim 1, wherein the compound (B) has an acid-decomposable group.
A resist film formed using the actinic ray-sensitive or radiation-sensitive resin composition according to any one of claims 1 to 12.
forming a resist film on a substrate using the actinic ray-sensitive or radiation-sensitive resin composition according to any one of claims 1 to 12; exposing the resist film; and developing the resist film using a developer.
A method for manufacturing an electronic device, comprising the pattern forming method according to claim 14.