WO2024004802A1

WO2024004802A1 - Active-ray-sensitive or radiation-sensitive resin composition, active-ray-sensitive or radiation-sensitive film, pattern formation method, and electronic device manufacturing method

Info

Publication number: WO2024004802A1
Application number: PCT/JP2023/023028
Authority: WO
Inventors: 英治福▲崎▼
Original assignee: 富士フイルム株式会社
Priority date: 2022-07-01
Filing date: 2023-06-21
Publication date: 2024-01-04
Also published as: TW202405559A

Abstract

The present invention provides: an active-ray-sensitive or radiation-sensitive resin composition comprising (A) a resin which contains a repeating unit (a) represented by a specific general formula (a) and having a group capable of being decomposed and capable of being changed with respect to the polarity thereof by the action of an acid and (B) a compound which is capable of generating an acid by the irradiation with an active ray or a radioactive ray; and an active-ray-sensitive or radiation-sensitive film, a pattern formation method, and an electronic device manufacturing method, in each of which the active-ray-sensitive or radiation-sensitive resin composition is used.

Description

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

The present invention relates to an actinic ray-sensitive or radiation-sensitive resin composition, an actinic ray-sensitive or radiation-sensitive film, a pattern forming method, and an electronic device manufacturing method. More specifically, the present invention relates to an ultra-microlithography process applicable to the manufacturing process of ultra-LSI (Large Scale Integration) and high-capacity microchips, the manufacturing process of nanoimprint molds, the manufacturing process of high-density information recording media, etc. The present invention relates to actinic ray-sensitive or radiation-sensitive resin compositions, actinic ray-sensitive or radiation-sensitive films, pattern forming methods, and electronic device manufacturing methods that can be suitably used in other photofabrication processes.

Conventionally, in the manufacturing process of semiconductor devices such as IC (Integrated Circuit) and LSI (Large Scale Integration), microfabrication is performed by lithography using a resist composition. 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 has been a trend towards shorter exposure wavelengths, from g-line to i-line and then to KrF excimer laser light, and now exposure machines that use ArF excimer laser light with a wavelength of 193 nm as a light source have been developed. ing. Furthermore, as a technique to further improve resolution, the so-called immersion method, in which a liquid with a high refractive index (hereinafter also referred to as "immersion liquid") is filled between the projection lens and the sample, has been developed.

Currently, in addition to excimer laser light, lithography using electron beams (EB), X-rays, extreme ultraviolet (EUV), etc. is also being developed. Along with this, resist compositions that are effectively sensitive to various types of actinic rays or radiation have been developed.

Various resins are known as resins used in actinic ray-sensitive or radiation-sensitive resin compositions. For example, Patent Document 1 describes an actinic ray-sensitive or radiation-sensitive resin composition containing a repeating unit having a specific structure in which the carboxyl group of benzoic acid is protected with an alkyl group or a group containing a cycloalkyl group. Things are specifically described.

International Publication No. 2017/138267

In recent years, miniaturization of patterns has been progressing, and there is a demand for further improvements in various performances of actinic ray-sensitive or radiation-sensitive resin compositions for forming such patterns.
However, the actinic ray-sensitive or radiation-sensitive resin compositions described in Patent Documents 1 and 2 have poor resolution, line width roughness (LWR) performance, and pattern shape of the resulting pattern. There remained room for further improvement. LWR performance refers to the ability to reduce the LWR of a pattern.

The present invention has excellent resolution and LWR performance in forming extremely fine patterns (for example, line-and-space patterns with a line width of 50 nm or less, hole patterns with a hole diameter of 50 nm or less, etc.), and can obtain a good pattern shape. An object of the present invention is to provide an actinic ray-sensitive or radiation-sensitive resin composition. Another object of the present invention is to provide an actinic ray-sensitive or radiation-sensitive film, a pattern forming method, and an electronic device manufacturing method using the above-mentioned actinic ray-sensitive or radiation-sensitive resin composition.

The present inventors have discovered that the above problem can be solved by the following configuration.

[1]
An actinic ray-sensitive or radiation-sensitive resin composition containing the following (A) and (B).
(A) A resin containing a repeating unit (a) represented by the following general formula (a) that decomposes under the action of an acid and has a group whose polarity changes. (B) Generates an acid when irradiated with actinic rays or radiation. Compound

In general formula (a), R ₁₀₁ to R ₁₀₃ each independently represent a hydrogen atom, an organic group, or a halogen atom. However, R ₁₀₂ may be combined with L ₁₀₁ to form a ring, and in that case R ₁₀₂ represents a single bond, an alkylene group, or an alkenylene group.
L ₁₀₁ represents a divalent aromatic ring group. When bonded with R ₁₀₂ to form a ring, it represents a trivalent aromatic ring group.
R ₁₀₄ and R ₁₀₅ each independently represent a hydrogen atom, an alkyl group, an aryl group, a heteroaryl group, an alkenyl group, or an alkynyl group.
R ₁₀₆ represents an aromatic heterocyclic group in which lone pairs of heteroatoms constitute a conjugated system. R ₁₀₄ to R ₁₀₆ may be bonded to each other to form a ring.

[2]
The activity sensitivity according to [1], wherein in the general formula (a), R ₁₀₆ is a monocyclic or polycyclic aromatic heterocyclic group having a 5-membered ring skeleton containing S, O, N, Se, or Te. Photosensitive or radiation sensitive resin composition.

[3]
The polymer according to [1] or [2], wherein the repeating unit represented by the above general formula (a) is a repeating unit represented by any of the following general formulas (a-2) to (a-7). Actinic ray-sensitive or radiation-sensitive resin composition.

In general formulas (a-2) to (a-7), R ₁₁₁ to R ₁₁₃ each independently represent a hydrogen atom, an organic group, or a halogen atom.
L ₁₁₁ represents a divalent aromatic ring group.
R ₁₁₄ and R ₁₁₅ each independently represent a hydrogen atom, an alkyl group, an aryl group, a heteroaryl group, an alkenyl group, or an alkynyl group.
R ₁₁₄ and R ₁₁₅ may be combined with each other to form a ring.
R ₁₁₇ to R ₁₂₁ each independently represent a hydrogen atom or a substituent. R ₁₁₇ to R ₁₂₁ may be bonded to each other to form a ring.
A represents S, O, N(R), Se, or Te. R represents a hydrogen atom or a substituent.

[4]
The actinic ray-sensitive or sensitive material according to [3], wherein the repeating unit represented by the above general formula (a) is a repeating unit represented by the above general formula (a-2) or general formula (a-3). Radioactive resin composition.
[5]
The actinic ray-sensitive or radiation-sensitive resin composition according to [3], wherein the repeating unit represented by the above general formula (a) is a repeating unit represented by the above general formula (a-2).

[6]
The actinic ray-sensitive or radiation-sensitive resin composition according to any one of [1] to [5], wherein L ₁₀₁ in the general formula (a) is a phenylene group.
[7]
The actinic ray-sensitive or radiation-sensitive resin according to any one of [1] to [6], wherein the total number of carbon atoms contained in R ₁₀₄ and R ₁₀₅ in the general formula (a) is 1 or more. Composition.

[8]
The actinic ray-sensitive or radiation-sensitive resin composition according to any one of [1] to [7], wherein the resin (A) further contains a repeating unit (c) represented by the following general formula (c). thing.

In general formula (c), R ₆₁ to R ₆₃ each independently represent a hydrogen atom, an organic group, or a halogen atom. However, R ₆₂ may combine with Ar to form a ring, and in that case R ₆₂ represents a single bond or an alkylene group.
L represents a single bond or a divalent linking group.
Ar represents a (k+1)-valent aromatic ring, and when bonded with R ₆₂ to form a ring, represents a (k+2)-valent aromatic ring group.
k represents an integer from 1 to 5.

[9]
Actinic ray sensitivity or radiation sensitivity according to any one of [1] to [8], wherein the content of the repeating unit (a) is 10% by mass or more based on the total mass of the resin (A). Resin composition.

[10]
The actinic ray-sensitive or radiation-sensitive resin composition according to any one of [1] to [9], wherein the compound (B) is a compound represented by the following general formula (1).

In general formula (1), R ₁ and R ₅ each independently represent an aryl group or a heteroaryl group.
R ₂ to R ₄ each independently represent a hydrogen atom or a substituent.
M ⁿ⁺ represents a cation.
n represents an integer of 1 or more.

[11]
The actinic ray-sensitive or radiation-sensitive resin composition according to [10], in which R ₃ represents an aryl group in the general formula (1).
[12]
In the above general formula (1), at least one of R ₁ to R ₅ is a group containing a polar group, a group containing a group whose polarity increases when decomposed by the action of an acid, or a group which decomposes by the action of an alkaline developer. , the actinic ray-sensitive or radiation-sensitive resin composition according to [10] or [11], which is a group containing a group that increases solubility in an alkaline developer.

[13]
The activator according to any one of [10] to [12], wherein R ₁ , R ₃ , and R ₅ in the general formula (1) are each a group represented by the following general formula (Ar). Photosensitive or radiation sensitive resin composition.

In the general formula (Ar), R ₆ to R ₁₀ each independently represent a hydrogen atom or a substituent. At least one of R ₆ to R ₁₀ is a group containing a polar group, a group containing a group whose polarity increases when decomposed by the action of an acid, or a group which decomposes by the action of an alkaline developer and has solubility in the alkaline developer. It is a group containing a group in which . * represents a bond to the benzene ring in general formula (1).

[14]
The activator according to any one of [10] to [13], wherein R ₁ , R ₃ , and R ₅ in the general formula (1) are each a group represented by the following general formula (Ar1). Photosensitive or radiation sensitive resin composition.

In the general formula (Ar1), R ₁₁ to R ₁₅ each independently represent a hydrogen atom or a substituent, and at least one of R ₁₁ to R ₁₅ represents the following substituent Y. * represents a bond to the benzene ring in general formula (1).
Substituent Y: hydroxy group, carboxyl group, group having a carbonyl bond, acyloxy group, alkoxycarbonyloxy group, aryloxycarbonyloxy group, aryloxycarbonyl group, alkoxycarbonyl group, carbamoyl group, or imido group

[15]
An actinic ray-sensitive or radiation-sensitive film formed from the actinic ray-sensitive or radiation-sensitive resin composition according to any one of [1] to [14].

[16]
An actinic ray-sensitive or radiation-sensitive film forming an actinic ray-sensitive or radiation-sensitive film on a substrate using the actinic ray-sensitive or radiation-sensitive resin composition according to any one of [1] to [14]. sexual film formation step;
an exposure step of exposing the actinic ray-sensitive or radiation-sensitive film;
A pattern forming method comprising a developing step of developing the exposed actinic ray-sensitive or radiation-sensitive film using a developer.
[17]
A method for manufacturing an electronic device, including the pattern forming method according to [16].

According to the present invention, it is possible to obtain a good pattern shape with excellent resolution and LWR performance in the formation of extremely fine patterns (for example, line and space patterns with a line width of 50 nm or less, hole patterns with a hole diameter of 50 nm or less, etc.). Actinic ray-sensitive or radiation-sensitive resin compositions can be provided.
Further, the present invention can provide an actinic ray-sensitive or radiation-sensitive film, a pattern forming method, and an electronic device manufacturing method using the above-mentioned actinic ray-sensitive or radiation-sensitive resin composition.

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

In this specification, "active rays" or "radiation" include, for example, the bright line spectrum of a mercury lamp, far ultraviolet rays typified by excimer lasers, extreme ultraviolet (EUV), 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 this specification, "exposure" refers not only to exposure to the bright line spectrum of a mercury lamp, far ultraviolet rays typified by excimer lasers, extreme ultraviolet rays, X-rays, and EUV, but also to electron beams and ion beams, unless otherwise specified. It also includes drawing using particle beams such as beams.
In the present specification, "~" is used to include the numerical values described before and after it as a lower limit value and an upper limit value.

In this specification, (meth)acrylate represents at least one of acrylate and methacrylate. Moreover, (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 degree of dispersion (also referred to as molecular weight distribution) (Mw/Mn) of the resin are determined using a GPC (Gel Permeation Chromatography) apparatus (HLC manufactured by Tosoh Corporation). -8120GPC) GPC measurement (solvent: tetrahydrofuran, flow rate (sample injection amount): 10 μL, column: Tosoh Corporation TSK gel Multipore HXL-M, column temperature: 40 ° C., flow rate: 1.0 mL/min, detector: It is defined as a polystyrene equivalent value measured by a differential refractive index detector (Refractive Index Detector).

Regarding the notation of a group (atomic group) in this specification, unless it goes against the spirit of the present invention, the notation that does not indicate substituted or unsubstituted includes a group containing a substituent as well as a group having no substituent. do. For example, the term "alkyl group" includes not only an alkyl group without a substituent (unsubstituted alkyl group) but also an alkyl group having a substituent (substituted alkyl group). Furthermore, the term "organic group" as used herein refers to a group containing at least one carbon atom.
As the substituent, unless otherwise specified, monovalent substituents are preferred. Examples of the substituent include monovalent nonmetallic atomic groups excluding hydrogen atoms, and can be selected from the following substituents T, for example.

(Substituent T)
Examples of the substituent T include halogen atoms such as fluorine, chlorine, bromine and iodine; alkoxy groups such as methoxy, ethoxy and tert-butoxy; cycloalkyloxy; phenoxy and p-tolyloxy groups; Aryloxy groups; alkoxycarbonyl groups such as methoxycarbonyl and butoxycarbonyl groups; cycloalkyloxycarbonyl groups; aryloxycarbonyl groups such as phenoxycarbonyl groups; acyloxy groups such as acetoxy, propionyloxy and benzoyloxy groups; acetyl Acyl groups such as benzoyl, isobutyryl, acryloyl, methacryloyl and methoxalyl groups; sulfanyl groups; alkylsulfanyl groups such as methylsulfanyl and tert-butylsulfanyl groups; phenylsulfanyl groups and p-tolylsulfanyl groups; Arylsulfanyl group; alkyl group; alkenyl group; cycloalkyl group; aryl group; aromatic heterocyclic group; hydroxy group; carboxyl group; formyl group; sulfo group; cyano group; alkylaminocarbonyl group; arylaminocarbonyl group; sulfone Examples include amide group; silyl group; amino group; carbamoyl group; and the like. In addition, when these substituents can further have one or more substituents, the further substituent is a group having one or more substituents selected from the above-mentioned substituents (for example, a monoalkylamino group). , dialkylamino group, arylamino group, trifluoromethyl group, etc.) are also included as examples of the substituent T.

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

In this specification, acid dissociation constant (pKa) refers to pKa in an aqueous solution, and specifically, it is a value based on Hammett's substituent constant and a database of known literature values using the following software package 1. is the value obtained by calculation. All pKa values described herein are values calculated using this software package.
Software package 1: Advanced Chemistry Development (ACD/Labs) Software V8.14 for Solaris (1994-2007 ACD/Labs).

Furthermore, pKa can also be determined by molecular orbital calculation method. A specific method for this includes a method of calculating H 2 ⁺ dissociation free energy in an aqueous solution based on a thermodynamic cycle. The H ⁺ dissociation free energy can be calculated, for example, by DFT (density functional theory), but various other methods have been reported in the literature, and the method is not limited to this. . Note that there is a plurality of software that can perform DFT, and one example is Gaussian 16.

In this 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 calculation is not possible, a value obtained by Gaussian 16 based on DFT (density functional theory) is used.
In this specification, pKa refers to "pKa in aqueous solution" as described above, but if pKa in aqueous solution cannot be calculated, "pKa in dimethyl sulfoxide (DMSO) solution" is adopted. shall be.

In this specification, "solid content" means a component that forms an actinic ray-sensitive or radiation-sensitive film, and does not include a solvent. Furthermore, if the component forms an actinic ray-sensitive or radiation-sensitive film, it is considered to be a solid content even if the component 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 "composition of the present invention") is an actinic ray-sensitive or radiation-sensitive resin composition containing the following (A) and (B). It is.
(A) A resin containing a repeating unit (a) represented by the following general formula (a) that decomposes under the action of an acid and has a group whose polarity changes. (B) Generates an acid when irradiated with actinic rays or radiation. Compound

Although it is not necessarily clear why the composition of the present invention has excellent resolution and LWR performance and is able to obtain a good pattern shape in ultrafine pattern formation, the present inventors speculate as follows. are doing.
The resin (A) contained in the composition of the present invention contains a repeating unit (a) having a group that decomposes and changes polarity under the action of an acid. The repeating unit (a) has a structure in which a carboxyl group bonded to an aromatic ring group is protected with a protecting group containing an aromatic heterocyclic group in which lone pairs of heteroatoms constitute a conjugated system.
The repeating unit (a) has an acid-decomposable structure in which the carboxyl group bonded to the aromatic ring group is protected, and the carboxyl group after removal of the protecting group is conjugated and stabilized by the aromatic ring, so it cannot be removed. Protective reactivity increases. Furthermore, since the above-mentioned protecting group in the repeating unit (a) becomes electron-rich due to the unshared electron pair forming a conjugated system, compound (B) is eliminated by the action of the acid generated. The group is more easily stabilized, and the deprotection reactivity is further improved. As a result, it is estimated that resolution will improve, and LWR performance and pattern shape will also improve.
In addition, since repeating unit (a) contains an aromatic heterocyclic group as a leaving group, there is a large difference in hydrophilicity and hydrophobicity due to deprotection, and a large difference in solubility contrast also contributes to improved resolution. It is thought that there are.

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 alkaline development or an organic solvent development resist composition. Among these, a positive resist composition and a resist composition for alkaline development are preferred.
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, and more preferably a chemically amplified positive 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 will be explained in detail.

<Resin (A)>
(A) A resin (also referred to as "resin (A)") having a repeating unit (a) represented by general formula (a), which has a group whose polarity changes when decomposed by the action of an acid, will be described.
The resin (A) preferably has a repeating unit having a group that is decomposed by the action of an acid to increase its polarity (hereinafter also referred to as an "acid-decomposable group"). (hereinafter also referred to as "acid-decomposable resin") is preferable.
The repeating unit (a) contained in the resin (A) is a repeating unit represented by the general formula (a) that has a group that decomposes and changes polarity by the action of an acid. It is a repeating unit that has a group that decomposes to produce carboxylic acid and increases polarity. That is, resin (A) is an acid-decomposable resin.

It is preferable that the resin (A) is a resin whose solubility in a developer changes under the action of an acid.
The resin whose solubility in the developer changes due to the action of an acid may be a resin whose solubility in the developer increases due to the action of the acid, or a resin whose solubility in the developer decreases due to the action of the acid.

Since the resin (A) has a group that can be decomposed by the action of an acid to produce a carboxylic acid, typically in the pattern forming method of the present invention, when an alkaline developer is used as the developer, In this case, a positive pattern is preferably formed, and when an organic developer is used as the developer, a negative pattern is preferably formed.

(Repeat unit (a))
The repeating unit (a) is a repeating unit represented by the following general formula (a), which has a group that is decomposed by the action of an acid and whose polarity changes.
The repeating unit (a) is also referred to as "a repeating unit having an acid-decomposable group."

In general formula (a), R ₁₀₁ to R ₁₀₃ each independently represent a hydrogen atom, an organic group, or a halogen atom.

Examples of the organic group represented by R ₁₀₁ to R ₁₀₃ include an alkyl group, an alkenyl group, a cycloalkyl group, and an aromatic ring group.
The alkyl group may be linear or branched. The number of carbon atoms in the alkyl group is not particularly limited, but is preferably 1 to 10, more preferably 1 to 3.
The alkenyl group may be linear or branched. The number of carbon atoms in the alkenyl group is not particularly limited, but is preferably from 2 to 10, more preferably from 2 to 3.
The cycloalkyl group may be monocyclic or polycyclic. The number of carbon atoms in this cycloalkyl group is preferably 3 to 8.

Examples of the aromatic ring group include an aryl group and a heteroaryl group.
Examples of the aryl group include aryl groups having 6 to 15 carbon atoms, and specific examples include phenyl, naphthyl, anthryl, and the like.
Examples of the heteroaryl group include heteroaryl groups having 2 to 15 carbon atoms, including those having a 5- to 10-membered ring, and specifically, a furyl group, a thienyl group, Preferred examples include a thiazolyl group, a pyrrolyl group, an oxazolyl group, a pyridyl group, a benzofuranyl group, a benzothienyl group, a quinolinyl group, and a carbazolyl group.

Examples of the halogen atom represented by R ₁₀₁ to R ₁₀₃ include a fluorine atom, a chlorine atom, a bromine atom, and an iodine atom.

R ₁₀₂ may combine with L ₁₀₁ to form a ring, in which case R ₁₀₂ represents a single bond, an alkylene group, or an alkenylene group.
Examples of the alkylene group include groups obtained by removing one arbitrary hydrogen atom from the alkyl groups represented by R ₁₀₁ to R ₁₀₃ .
Examples of the alkenylene group include groups obtained by removing one arbitrary hydrogen atom from the alkenyl group represented by R ₁₀₁ to R ₁₀₃ .

In general formula (a), R ₁₀₁ to R ₁₀₃ are preferably each independently a hydrogen atom or an alkyl group, R ₁₀₁ and R ₁₀₂ are a hydrogen atom, and R ₁₀₃ is a hydrogen atom or a methyl group. More preferably, R ₁₀₁ to R ₁₀₃ are hydrogen atoms.

In general formula (a), L ₁₀₁ represents a divalent aromatic ring group.
The divalent aromatic ring group represented by L ₁₀₁ includes an arylene group or a heteroarylene group.

Examples of the arylene group as L ₁₀₁ include arylene groups having 6 to 15 carbon atoms, and specifically, preferred examples include phenylene group, naphthylene group, and anthrylene group.
Examples of the heteroarylene group as L ₁₀₁ include heteroarylene groups having 2 to 15 carbon atoms, including 5- to 10-membered rings, and specifically, furyl groups. , thienyl group, thiazolyl group, pyrrolyl group, oxazolyl group, pyridyl group, benzofuranyl group, benzothienyl group, quinolinyl group, carbazolyl group, etc., with one arbitrary hydrogen atom removed.

The divalent aromatic ring group represented by L ₁₀₁ may further have a substituent, such as a halogen atom.

L ₁₀₁ may be combined with R ₁₀₂ to form a ring, and in this case, L ₁₀₁ represents a trivalent aromatic ring group.
Examples of the trivalent aromatic ring group include a group obtained by removing one arbitrary hydrogen atom from the above-mentioned divalent aromatic ring group.

L ₁₀₁ is preferably an arylene group, more preferably a phenylene group.

In general formula (a), R ₁₀₄ and R ₁₀₅ each independently represent a hydrogen atom, an alkyl group, a cycloalkyl group, an aryl group, a heteroaryl group, an alkenyl group, or an alkynyl group.

Examples of the alkyl group represented by R ₁₀₄ and R ₁₀₅ include alkyl groups having 1 to 8 carbon atoms, which may be linear or branched, such as methyl group, ethyl group, n-propyl group, etc. Preferred are alkyl groups having 1 to 4 carbon atoms, such as isopropyl group, n-butyl group, isobutyl group, and t-butyl group.

The cycloalkyl group represented by R ₁₀₄ and R ₁₀₅ includes a monocyclic or polycyclic cycloalkyl group having 3 to 10 carbon atoms, preferably a monocyclic cycloalkyl group having 4 to 6 carbon atoms, a cyclopentyl group, Or a cyclohexyl group is preferred.

The aryl group represented by R ₁₀₄ and R ₁₀₅ includes aryl groups having 6 to 15 carbon atoms such as phenyl group and naphthyl group.

The heteroaryl group represented by R ₁₀₄ and R ₁₀₅ has 2 to 15 carbon atoms, such as furyl group, thienyl group, thiazolyl group, pyrrolyl group, oxazolyl group, pyridyl group, benzofuranyl group, benzothienyl group, quinolinyl group, carbazolyl group, etc. heteroaryl groups.

Examples of the alkenyl group represented by R ₁₀₄ and R ₁₀₅ include alkenyl groups having 2 to 6 carbon atoms, including vinyl group, 1-methylvinyl group, 1-propenyl group, allyl group, and 2-methyl-1-propenyl group. Alkenyl groups having 2 to 4 carbon atoms such as penyl group are preferred.

The alkynyl group represented by R ₁₀₄ and R ₁₀₅ includes an alkynyl group having 2 to 6 carbon atoms.

R ₁₀₄ to R ₁₀₆ may be bonded to each other to form a ring, and R ₁₀₄ and R ₁₀₅ are preferably bonded to each other to form a ring.
When R ₁₀₄ and R ₁₀₅ combine with each other to form a ring, it is preferable that they form a cycloalkyl group or a cycloalkenyl group.

Examples of the cycloalkyl group formed by combining R ₁₀₄ and R ₁₀₅ include monocyclic or polycyclic cycloalkyl groups having 3 to 10 carbon atoms, and monocyclic cycloalkyl groups such as cyclopentyl and cyclohexyl groups. Examples include alkyl groups and polycyclic cycloalkyl groups such as norbornyl groups, tetracyclodecanyl groups, tetracyclododecanyl groups, and adamantyl groups. Among these, a monocyclic cycloalkyl group having 5 to 6 carbon atoms is preferred.

Examples of the cycloalkenyl group formed by combining R ₁₀₄ and R ₁₀₅ include monocyclic or polycyclic cycloalkenyl groups having 3 to 10 carbon atoms, and among them, monocyclic cycloalkenyl groups having 5 to 6 carbon atoms. Groups are preferred.

The substituents represented by R ₁₀₄ and R ₁₀₅ may be further substituted with an organic group. It is preferable that the organic group contains 0 to 1 heteroatom.
When each of the above substituents represented by R ₁₀₄ and R ₁₀₅ is substituted with an organic group, examples of the organic group include an alkyl group (having 1 to 4 carbon atoms), an alkoxy group (having 1 to 4 carbon atoms), etc. can be mentioned. One of the methylene groups in the above substituents represented by R ₁₀₄ and R ₁₀₅ may be replaced with a group having a hetero atom such as a carbonyl group.

In the cycloalkyl group and cycloalkenyl group formed by combining R ₁₀₄ and R ₁₀₅ , for example, one of the methylene groups constituting the ring is a hetero atom such as an oxygen atom or a sulfur atom, or a hetero atom such as a carbonyl group. It may be substituted with a group having an atom.

More preferably, the total number of heteroatoms contained in R ₁₀₄ and R ₁₀₅ is 0 to 1.

The number of carbon atoms contained in each group of R ₁₀₄ and R ₁₀₅ is preferably 1 to 7.

Further, the total number of carbon atoms contained in R ₁₀₄ and R ₁₀₅ is not particularly limited, but is preferably 1 or more. It is preferable to set the total number of carbon atoms to 1 or more because the deprotection reactivity of the protecting group can be increased. Further, the total number of carbon atoms is preferably 9 or less, more preferably 7 or less. By setting the total number of carbon atoms to 9 or less, the desorbed product released from the resin (A) by the acid generated by the compound (B) described below is unlikely to remain in the actinic ray-sensitive or radiation-sensitive film. Resolution is further improved.
The total number of carbon atoms contained in R ₁₀₄ and R ₁₀₅ is preferably 5 to 9, more preferably 5 to 7.

It is preferable that R ₁₀₄ and R ₁₀₅ each independently represent a hydrogen atom, an alkyl group, or an alkenyl group. R ₁₀₄ and R ₁₀₅ may be combined with each other to form a ring.
In R ₁₀₄ and R ₁₀₅ , R ₁₀₄ is preferably a hydrogen atom, R ₁₀₅ is preferably an alkyl group, and more preferably R ₁₀₄ is a hydrogen atom, and R ₁₀₅ is a methyl group.
Another preferred embodiment is one in which R ₁₀₄ and R ₁₀₅ combine to form a cyclopentyl group or a cyclohexyl group.

In the general formula (a), R ₁₀₆ represents an aromatic heterocyclic group in which lone pairs of heteroatoms constitute a conjugated system.
Examples of the heteroatom in which the lone pair of electrons constitutes a conjugated system in the aromatic heterocyclic group represented by _R106 include S, O, N, Se, or Te; Preferably, S or O is more preferable.

The aromatic heterocyclic group represented by R ₁₀₆ in which the lone pair of electrons of the heteroatom constitutes a conjugated system may be monocyclic or polycyclic. Among these, monocyclic or polycyclic aromatic heterocyclic groups having a 5-membered ring skeleton containing S, O, N, Se, or Te are preferred; More preferred is an aromatic heterocyclic group.

Specific examples of the aromatic heterocyclic group represented by R ₁₀₆ include S of a thiophene ring, a furan ring, a pyrrole ring, a thiazole ring, an oxazole ring, an imidazole ring, a triazole ring, a thiadiazole ring, and a thiophene ring. A monocyclic aromatic heterocyclic group such as a ring in which Se or Te is substituted for S in a benzothiophene ring, benzofuran ring, benzopyrrole ring, benzimidazole ring, dibenzofuran ring, dibenzothiophene ring, or benzothiophene ring Examples include, but are not limited to, polycyclic aromatic heterocyclic groups containing the heterocyclic skeleton listed above as the monocyclic ring, such as a ring in which S is replaced with Se or Te in the dibenzothiophene ring, and a ring in which S in the dibenzothiophene ring is replaced with Se or Te. It's not something you can do.

The aromatic heterocyclic group represented by R ₁₀₆ may further have a substituent, such as a halogen atom, an alkyl group, an alkoxy group, an alkenyl group, a thiol group, and the like. The number of further substituents may be one, or two or more. When it has two or more substituents, they may be bonded to each other to form a ring.
R ₁₀₆ does not include aromatic heterocyclic groups in which the lone pair of heteroatoms does not constitute a conjugated system (eg, pyridine, quinoline, isoquinoline, pyrazine, pyrimidine, quinazoline, acridine, etc.).

The repeating unit represented by general formula (a) is preferably a repeating unit represented by general formula (a-1) below.

In general formula (a-1), R ₁₁₁ to R ₁₁₃ each independently represent a hydrogen atom, an organic group, or a halogen atom.
R ₁₁₄ and R ₁₁₅ each independently represent a hydrogen atom, an alkyl group, an aryl group, a heteroaryl group, an alkenyl group, or an alkynyl group. R ₁₁₄ and R ₁₁₅ may be combined with each other to form a ring.
R ₁₁₆ represents an aromatic heterocyclic group in which lone pairs of heteroatoms constitute a conjugated system.

R ₁₁₁ to R ₁₁₃ in general formula (a-1) have the same meanings as R ₁₀₁ to R ₁₀₃ in general formula (a) above, and preferred examples are also the same. However, an embodiment in which R ₁₀₂ in general formula (a) is combined with L ₁₀₁ to form a ring is excluded.
R ₁₁₄ to R ₁₁₆ in general formula (a-1) have the same meanings as R ₁₀₄ to R ₁₀₆ in general formula (a) above, and preferred examples are also the same. However, an embodiment in which R ₁₀₆ in general formula (a) is combined with at least one of R ₁₀₄ and R ₁₀₅ to form a ring is excluded.

The repeating unit represented by general formula (a) is preferably a repeating unit represented by any of the following general formulas (a-2) to (a-7).

In general formulas (a-2) to (a-7), R ₁₁₁ to R ₁₁₃ and L ₁₁₁ have the same meanings as R ₁₀₁ to R ₁₀₃ and L ₁₀₁ in general formula (a), and are preferred examples. The same is true. However, an embodiment in which R ₁₀₂ in general formula (a) is combined with L ₁₀₁ to form a ring is excluded.
In general formulas (a-2) to (a-7), R ₁₁₄ and R ₁₁₅ have the same meanings as R ₁₀₄ and R ₁₀₅ in the above general formula (a), and preferred examples are also the same. However, an embodiment in which R ₁₀₆ in general formula (a) is combined with at least one of R ₁₀₄ and R ₁₀₅ to form a ring is excluded.

In general formulas (a-2) to (a-7), R ₁₁₇ to R ₁₂₁ each independently represent a hydrogen atom or a substituent.
Examples of the substituent represented by R ₁₁₇ to R ₁₂₁ include a halogen atom, an alkyl group, an aryl group, an alkoxy group, an alkenyl group, and a thiol group.
Examples of the halogen atom include a fluorine atom, a chlorine atom, a bromine atom, and an iodine atom, with a fluorine atom or an iodine atom being preferred.
The alkyl group may be linear or branched, and includes an alkyl group having 1 to 10 carbon atoms, preferably an alkyl group having 1 to 3 carbon atoms.
Examples of the aryl group include aryl groups having 6 to 15 carbon atoms, with phenyl groups being preferred.
The alkyl group contained in the alkoxy group is preferably the same as the alkyl group represented by R ₁₁₇ to R ₁₂₁ above.
The alkenyl group may be linear or branched, and includes an alkenyl group having 2 to 10 carbon atoms, preferably an alkenyl group having 2 to 4 carbon atoms.

When R ₁₁₇ to R ₁₂₁ combine with each other to form a ring, examples of the ring include a cycloalkyl group, a cycloalkenyl group, an aryl group, and a heteroaryl group.
Examples of the cycloalkyl group include monocyclic or polycyclic cycloalkyl groups having 3 to 10 carbon atoms, and monocyclic cycloalkyl groups having 5 to 6 carbon atoms are preferred.
Examples of the cycloalkenyl group include monocyclic or polycyclic cycloalkenyl groups having 3 to 10 carbon atoms, and monocyclic cycloalkenyl groups having 5 to 6 carbon atoms are preferred.
As the aryl group, a phenyl group is preferred.
As the heteroaryl group, a thiophene ring group is preferred.

When R ₁₁₇ to R ₁₂₁ combine with each other to form a ring, the form of the ring is not particularly limited, but examples include the following forms.
In general formula (a-2), an embodiment in which two of R ₁₁₇ to R ₁₁₉ are bonded to each other to form a ring.
In general formula (a-3), an embodiment in which two of R ₁₁₈ to R ₁₁₉ are bonded to each other to form a ring.
In general formula (a-4), an embodiment in which two of R ₁₁₇ to R ₁₁₈ are bonded to each other to form a ring, and an embodiment in which two of R ₁₁₉ to R ₁₂₁ are bonded to each other to form a ring.
In general formula (a-5), an embodiment in which two of R ₁₁₇ to R ₁₁₈ are bonded to each other to form a ring, and an embodiment in which two of R ₁₁₉ to R ₁₂₀ are bonded to each other to form a ring.
In general formula (a-6), an embodiment in which two of R ₁₁₇ to R ₁₁₈ are bonded to each other to form a ring, and an embodiment in which two of R ₁₂₀ to R ₁₂₁ are bonded to each other to form a ring.
In general formula (a-7), an embodiment in which two of R ₁₁₇ to R ₁₁₈ are bonded to each other to form a ring, and an embodiment in which two of R ₁₁₉ to R ₁₂₁ are bonded to each other to form a ring.

R ₁₁₇ to R ₁₂₁ preferably represent a hydrogen atom, a fluorine atom, or an alkyl group having 1 to 3 carbon atoms. Further, it is also preferable that they are bonded to each other to form an aryl group or a heteroaryl group.

In general formulas (a-2) to (a-7), A represents S, O, N(R), Se, or Te. R represents a hydrogen atom or a substituent.
The substituent represented by R is not particularly limited, and examples thereof include an alkyl group (having 1 to 3 carbon atoms), an aryl group, and a heteroaryl group.
Examples of the aryl group include aryl groups having 6 to 15 carbon atoms, with phenyl groups being preferred.
Examples of the heteroaryl group include heteroaryl groups having 2 to 15 carbon atoms such as furyl group, thienyl group, thiazolyl group, pyrrolyl group, oxazolyl group, pyridyl group, benzofuranyl group, benzothienyl group, quinolinyl group, and carbazolyl group. It will be done.
R is preferably a hydrogen atom or a methyl group.
A preferably represents S, O, or N(R), and more preferably S or O.

The repeating unit represented by general formula (a) is more preferably a repeating unit represented by general formula (a-2) or general formula (a-3) above, and in general formula (a-2), More preferably, it is a repeating unit represented by:

Specific examples of the repeating unit (a) are shown below, but the present invention is not limited thereto. Me represents a methyl group.

The resin (A) may contain one type of repeating unit (a), or may contain two or more types in combination.

The content of the repeating unit (a) contained in the resin (A) (if there are multiple repeating units (a), the total) is 15 mol% or more with respect to all repeating units of the resin (A). It is preferably at least 20 mol%, even more preferably at least 30 mol%. When the content is 15 mol% or more, the effects of the present invention are more likely to occur.
In addition, the content of repeating units (a) contained in resin (A) (if there are multiple repeating units (a), the total) is 70 mol% or less with respect to all repeating units of resin (A). The content is preferably 60 mol% or less, more preferably 50 mol% or less, and even more preferably 50 mol% or less.

The content of the repeating unit (a) contained in the resin (A) (if there are multiple repeating units (a), the total) shall be 10% by mass or more based on the total mass of the resin (A). The content is preferably 20% by mass or more, more preferably 30% by mass or more. When the content is 10% by mass or more, the effects of the present invention are more likely to occur.
In addition, the content of the repeating unit (a) contained in the resin (A) (if there are multiple repeating units (a), the total) is 70% by mass or less with respect to the total mass of the resin (A). It is preferably at most 60% by mass, more preferably at most 50% by mass.

The resin (A) may contain a repeating unit having an acid-decomposable group other than the repeating unit (a) as long as the effects of the present invention are not impaired.

As the repeating unit having an acid-decomposable group other than repeating unit (a), known repeating units can be used as appropriate. For example, paragraphs [0055] to [0191] of US Patent Application Publication No. 2016/0274458A1, paragraphs [0035] to [0085] of US Patent Application Publication No. 2015/0004544A1, and US Patent Application Publication No. 2016/0147150A1. Repeating units having acid-decomposable groups in known resins disclosed in paragraphs [0045] to [0090] of the specification can be suitably used.

The content of repeating units having an acid-decomposable group contained in the resin (A) (if there are multiple repeating units having an acid-decomposable group, the total thereof) is based on all the repeating units of the resin (A). It is preferably 10 to 90 mol%, more preferably 20 to 80 mol%, even more preferably 30 to 70 mol%.
The resin (A) may contain repeating units other than the repeating unit (a) as long as the effects of the present invention are not impaired.

(Repeat unit (c))
The resin (A) preferably contains a repeating unit having an acid group, and preferably contains a repeating unit (c) represented by the following general formula (c).

In general formula (c), R ₆₁ to R ₆₃ each independently represent a hydrogen atom, an organic group, or a halogen atom. However, R ₆₂ may combine with Ar to form a ring, and in that case R ₆₂ represents a single bond or an alkylene group.
L represents a single bond or a divalent linking group.
Ar represents a (k+1)-valent aromatic ring group, and when bonded to R ₆₂ to form a ring, represents a (k+2)-valent aromatic ring group.
k represents an integer from 1 to 5.

In general formula (c), R ₆₁ to R ₆₃ each independently represent a hydrogen atom, an organic group, or a halogen atom.
The organic group represented by R ₆₁ to R ₆₃ is, for example, an alkyl group, a cycloalkyl group, a cyano group or an alkoxycarbonyl group.

Examples of the alkyl group represented by R ₆₁ to R ₆₃ include methyl group, ethyl group, propyl group, isopropyl group, n-butyl group, sec-butyl group, hexyl group, 2-ethylhexyl group, octyl group, and dodecyl group. An alkyl group having 20 or less carbon atoms is preferable, an alkyl group having 8 or less carbon atoms is more preferable, and an alkyl group having 3 or less carbon atoms is still more preferable.

The cycloalkyl group represented by R ₆₁ to R ₆₃ may be monocyclic or polycyclic. Among these, monocyclic cycloalkyl groups having 3 to 8 carbon atoms such as cyclopropyl group, cyclopentyl group, and cyclohexyl group are preferred.
The alkyl group contained in the alkoxycarbonyl group represented by R ₆₁ to R ₆₃ is preferably the same as the alkyl group in R ₆₁ to R ₆₃ above.

When R ₆₂ is combined with Ar to form a ring, the alkylene group for R ₆₂ is preferably a group obtained by removing one arbitrary hydrogen atom from the alkyl group in R ₆₁ to R ₆₃ above.

Examples of the halogen atom represented by R ₆₁ to R ₆₃ include a fluorine atom, a chlorine atom, a bromine atom, and an iodine atom, with a fluorine atom being preferred.

Preferred substituents for each of the above groups include, for example, an alkyl group, a cycloalkyl group, an aryl group, an amino group, an amide group, a ureido group, a urethane group, a hydroxyl group, a carboxyl group, a halogen atom, an alkoxy group, a thioether group, and an acyl group. , an acyloxy group, an alkoxycarbonyl group, a cyano group, and a nitro group. The number of carbon atoms in the substituent is preferably 8 or less.

In the general formula (c), Ar represents a (k+1)-valent aromatic ring group. The divalent aromatic ring group when k is 1 may have a substituent, for example, an arylene group having 6 to 18 carbon atoms such as a phenylene group, tolylene group, naphthylene group, and anthracenylene group. or an aromatic compound containing a hetero ring such as a thiophene ring, a furan ring, a pyrrole ring, a benzothiophene ring, a benzofuran ring, a benzopyrrole ring, a triazine ring, an imidazole ring, a benzimidazole ring, a triazole ring, a thiadiazole ring, and a thiazole ring. A ring group is preferred.

Specific examples of (k+1)-valent aromatic ring groups when k is an integer of 2 or more include (k-1) arbitrary hydrogen atoms removed from the above-mentioned specific examples of divalent aromatic ring groups. The following groups are mentioned.
The (k+1)-valent aromatic ring group may further have a substituent.

Examples of substituents that the (k+1)-valent aromatic ring group may have include a halogen atom, an alkyl group, a cycloalkyl group, an aryl group, an alkenyl group, an aralkyl group, an alkoxy group, an alkylcarbonyloxy group, and an alkylsulfonyloxy group. , an alkyloxycarbonyl group, an aryloxycarbonyl group, and the like.

Ar is preferably an aromatic ring group having 6 to 18 carbon atoms, and more preferably a benzene ring group, a naphthalene ring group, and a biphenylene ring group.
The repeating unit represented by general formula (c) preferably has a hydroxystyrene structure. That is, Ar is preferably a benzene ring group, more preferably a phenylene group (a divalent benzene ring group).

In general formula (c), L represents a single bond or a divalent linking group.
The divalent linking group represented by L includes *-X ₄ -L ₄ -**.
In the above formula, X ₄ represents a single bond, -COO-, or -CONR ₆₄ -, and R ₆₄ represents a hydrogen atom or an alkyl group.
L ₄ represents a single bond or an alkylene group.
* is a bond with the carbon atom of the main chain in general formula (c), and ** is a bond with Ar.

The alkyl group of R ₆₄ in -CONR ₆₄ - (R ₆₄ represents a hydrogen atom or an alkyl group) represented by X ₄ includes a methyl group, an ethyl group, a propyl group, an isopropyl group, an n-butyl group, a sec Examples include alkyl groups having 20 or less carbon atoms such as -butyl group, hexyl group, 2-ethylhexyl group, octyl group, and dodecyl group, with alkyl groups having 8 or less carbon atoms being preferred.
X ₄ is preferably a single bond, -COO-, or -CONH-, and more preferably a single bond or -COO-.

The alkylene group for L ₄ is preferably an alkylene group having 1 to 8 carbon atoms such as a methylene group, an ethylene group, a propylene group, a butylene group, a hexylene group, and an octylene group.

L is preferably a single bond, -COO-, or -CONH-, and more preferably a single bond.

In the general formula (c), k represents an integer of 1 to 5.
k is preferably an integer of 1 to 3, more preferably 1 or 2, and even more preferably 1.

The repeating unit represented by general formula (c) is preferably a repeating unit represented by general formula (1) below.

In general formula (1),
A represents a hydrogen atom, an alkyl group, a cycloalkyl group, a halogen atom, or a cyano group.
R represents a halogen atom, an alkyl group, a cycloalkyl group, an aryl group, an alkenyl group, an aralkyl group, an alkoxy group, an alkylcarbonyloxy group, an alkylsulfonyloxy group, an alkyloxycarbonyl group, or an aryloxycarbonyl group, and there are a plurality of them. They may be the same or different depending on the case. When a plurality of R's are present, they may cooperate with each other to form a ring. R is preferably a hydrogen atom.
a represents an integer from 1 to 3.
b represents an integer from 0 to (3-a).

Hereinafter, specific examples of the repeating unit (c) will be shown, but the present invention is not limited thereto. In the formula, a represents an integer of 1 to 3.

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

The content of the repeating unit (c) is preferably 10 to 80 mol%, more preferably 15 to 75 mol%, and even more preferably 20 to 50 mol%, based on all repeating units in the resin (A).

The resin (A) may contain at least one repeating unit selected from the group consisting of the following group A, and/or at least one repeating unit selected from the group consisting of the following group B. good.
Group A: A group consisting of the following repeating units (20) to (25).
(20) A repeating unit having an acid group, as described below. A repeating unit having a lactone group, a sultone group, or a carbonate group (23) A repeating unit having a photoacid generating group described below (24) A repeating unit having a photoacid generating group described later (25) Repeating units for reducing the mobility of the main chain Group B: A group consisting of the following repeating units (30) to (32).
(30) A repeating unit having at least one type of 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 formula (III) that does not have either a hydroxyl group or a cyano group and is not acid-decomposable.

A preferred embodiment of the resin (A) includes an embodiment in which the resin (A) contains at least one of a repeating unit having a phenolic hydroxyl group other than the repeating unit (c) and a repeating unit having a lactone group. This improves the adhesion of the actinic ray-sensitive or radiation-sensitive film formed from the composition of the present invention to the substrate.

The resin (A) preferably has an acid group, and as described below, preferably contains a repeating unit having an acid group. When the resin (A) has an acid group, the interaction between the resin (A) and the acid generated from the photoacid generator is more excellent. As a result, acid diffusion is further suppressed, and the cross-sectional shape of the formed pattern can be made more rectangular.

The resin (A) may have at least one repeating unit selected from the group consisting of the above group A. When the composition of the present invention is used as an actinic ray-sensitive or radiation-sensitive resin composition for EUV exposure, the resin (A) should have at least one repeating unit selected from the group consisting of the above group A. is preferred.
The resin (A) may contain at least one of a fluorine atom and an iodine atom. When the composition of the present invention is used as an actinic ray-sensitive or radiation-sensitive resin composition for EUV exposure, the resin (A) preferably contains at least one of a fluorine atom and an iodine atom. When the resin (A) contains both a fluorine atom and an iodine atom, the resin (A) may have one repeating unit containing both a fluorine atom and an iodine atom; It may contain two types: a repeating unit having a fluorine atom and a repeating unit containing an iodine atom.
The resin (A) may have at least one repeating unit selected from the group consisting of Group B above. When the composition of the present invention is used as an actinic ray-sensitive or radiation-sensitive resin composition for ArF, the resin (A) may have at least one repeating unit selected from the group consisting of the above group B. preferable.
In addition, when the composition of the present invention is used as an actinic ray-sensitive or radiation-sensitive resin composition for ArF, it is preferable that the resin (A) contains neither a fluorine atom nor a silicon atom.

(Repeating unit with acid group)
The resin (A) may have a repeating unit having an acid group other than the repeating unit (c).
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 to 13, and even more preferably 5 to 10.
When the resin (A) has acid groups with a pKa of 13 or less, the content of acid groups in the resin (A) is not particularly limited, but is often 0.2 to 6.0 mmol/g. Among these, 0.8 to 6.0 mmol/g is preferable, 1.2 to 5.0 mmol/g is more preferable, and even more preferably 1.6 to 4.0 mmol/g. When the content of acid groups is within the above range, development proceeds well, the formed pattern shape is excellent, and the resolution is also excellent.
As the acid group, for example, a carboxyl group, a phenolic hydroxyl group, a fluorinated alcohol group (preferably a hexafluoroisopropanol group), a sulfonic acid group, a sulfonamide group, or an isopropanol group is preferable.
In the above-mentioned 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).
As the acid group, -C(CF ₃ )(OH)-CF ₂ - formed in this way is also preferred. Furthermore, 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 preferably a repeating unit different from the above-mentioned repeating unit having an acid-decomposable group and the repeating unit having a lactone group, sultone group, or carbonate group described below.
The repeating unit having an acid group may have a fluorine atom or an iodine atom.

Examples of repeating units having an acid group other than the above repeating unit (c) include the following repeating units.

When the resin (A) contains a repeating unit having an acid group, the content of the repeating unit having an acid group is preferably 5 mol% or more, and 10 mol% or more, based on all the repeating units in the resin (A). is more preferable. The upper limit thereof is preferably 70 mol% or less, more preferably 65 mol% or less, and even more preferably 60 mol% or less, based on all repeating units in the resin (A).

(Repeating unit that has neither an acid-decomposable group nor an acid group, but has a fluorine atom, a bromine atom, or an iodine atom)
Resin (A) does not have any acid-decomposable groups or acid groups, and does not contain fluorine, bromine, or iodine atoms, in addition to the above-mentioned repeating units having acid-decomposable groups and repeating units having acid groups. (hereinafter also referred to as unit X). The <repeat unit having neither an acid-decomposable group nor an acid group but a fluorine atom, a bromine atom, or an iodine atom> referred to herein means the <repeat unit having a lactone group, sultone group, or carbonate group> described below. It is preferable that the repeating unit is different from other types of repeating units belonging to Group A, such as , and <repeat unit having a photoacid generating group>.

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

L ₅ represents a single bond or an ester group. R ₉ represents a hydrogen atom or an alkyl group which may have a fluorine atom or an iodine atom. _R10 may have a hydrogen atom, an alkyl group which may have a fluorine atom or an iodine atom, a cycloalkyl group which may have a fluorine atom or an iodine atom, a fluorine atom or an iodine atom. Represents an aryl group or a group combining these.

The content of unit X is preferably 0 mol% or more, more preferably 5 mol% or more, and even more preferably 10 mol% or more, based on all repeating units in the resin (A). Moreover, the upper limit thereof is preferably 50 mol% or less, more preferably 45 mol% or less, and even more preferably 40 mol% or less, based on all repeating units in the resin (A).

Among the repeating units of the resin (A), the total content of repeating units containing at least one of a fluorine atom, a bromine atom, and an iodine atom is preferably 10 mol% or more based on all repeating units of the resin (A). , more preferably 20 mol% or more, still more preferably 30 mol% or more, particularly preferably 40 mol% or more. The upper limit is not particularly limited, but is, for example, 100 mol% or less based on all repeating units of the resin (A).
Note that the repeating unit containing at least one of a fluorine atom, a bromine atom, and an iodine atom includes, for example, a repeating unit having a fluorine atom, a bromine atom, or an iodine atom and an acid-decomposable group, a fluorine atom, a bromine atom, and a repeating unit having an acid-decomposable group. Examples include repeating units having an atom or an iodine atom and an acid group, and repeating units having a fluorine atom, a bromine atom, or an iodine atom.

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

The lactone group or sultone group may have a lactone structure or a sultone structure. The lactone structure or sultone structure is preferably a 5- to 7-membered ring lactone structure or a 5- to 7-membered ring sultone structure. Among these, 5- to 7-membered ring lactone structures are fused with other ring structures to form a bicyclo or spiro structure, or 5- to 7-membered sultone structures to form a bicyclo or spiro structure. More preferred is a structure in which another ring structure is condensed.
The resin (A) has a lactone structure represented by any of the following formulas (LC1-1) to (LC1-21), or a lactone structure represented by any of the following formulas (SL1-1) to (SL1-3). It is preferable to have a repeating unit having a lactone group or sultone group formed by abstracting 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 the resin (A).

The lactone structure or sultone structure may have a substituent (Rb ₂ ). Preferred substituents (Rb ₂ ) include an alkyl group having 1 to 8 carbon atoms, a cycloalkyl group having 4 to 7 carbon atoms, an alkoxy group having 1 to 8 carbon atoms, an alkoxycarbonyl group having 1 to 8 carbon atoms, and a carboxyl group. , a halogen atom, a cyano group, and an acid-decomposable group. n2 represents an integer from 0 to 4. When n2 is 2 or more, a plurality of Rb _2s may be different, or a plurality of Rb _2s may be bonded to each other to form a ring.

A repeating group having a lactone structure represented by any one of formulas (LC1-1) to (LC1-21) or a sultone structure represented by any one of formulas (SL1-1) to (SL1-3) Examples of the unit include a repeating unit 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.
Examples of the halogen atom of Rb ₀ include a fluorine atom, a chlorine atom, a bromine atom, and an iodine atom. Rb ₀ is preferably a hydrogen atom or a methyl group.
Ab 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 divalent linkage of a combination thereof. represents a group. Among these, Ab is preferably a single bond or a connecting group represented by -Ab ₁ -CO ₂ -. Ab ₁ is a linear or branched alkylene group, or a monocyclic or polycyclic cycloalkylene group, and is 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 of formulas (LC1-1) to (LC1-21), or Represents a group obtained by abstracting one hydrogen atom from a ring member atom of a sultone structure represented by any of 3).

If an optical isomer exists in the repeating unit having a lactone group or a sultone group, any optical isomer may be used. Further, one type of optical isomer may be used alone or a plurality of optical isomers may be used in combination. When one type 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 preferable.
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 's may be the same or different. A represents a single bond or a divalent linking group. The divalent linking group mentioned above is 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.

When the resin (A) contains the unit Y, the content of the unit Y is preferably 1 mol% or more, more preferably 10 mol% or more, based on all repeating units in the resin (A). In addition, the upper limit thereof is preferably 85 mol% or less, more preferably 80 mol% or less, even more preferably 70 mol% or less, particularly 60 mol% or less, based on all repeating units in the resin (A). preferable.

(Repeating unit with photoacid generating group)
The resin (A) is a repeating unit having a group that generates an acid upon irradiation with actinic rays or radiation (preferably an electron beam or extreme ultraviolet rays) (hereinafter also referred to as a "photoacid generating group") as a repeating unit other than the above. It may have.
One preferable embodiment of the resin (A) is an embodiment in which the resin (A) contains a repeating unit having a group that generates an acid when decomposed by irradiation with an electron beam or extreme ultraviolet rays.
Examples of the repeating unit having a photoacid generating group include a repeating unit represented by formula (4).

R ⁴¹ represents a hydrogen atom or a methyl group. L ⁴¹ represents a single bond or a divalent linking group. L ⁴² represents a divalent linking group. R ⁴⁰ represents a structural moiety that decomposes upon irradiation with actinic rays or radiation to generate an acid in the side chain.
Examples of repeating units having a photoacid generating group are shown below.

In addition, examples of the repeating unit represented by formula (4) include the repeating units described in paragraphs [0094] to [0105] of JP2014-041327A and WO2018/193954A. Examples include the repeating units described in paragraph [0094].

When the resin (A) contains a repeating unit having a photoacid generating group, the content of the repeating unit having a photoacid generating group is preferably 1 mol% or more with respect to all repeating units in the resin (A), More preferably 5 mol% or more. Further, the upper limit thereof is preferably 40 mol% or less, more preferably 35 mol% or less, and even more preferably 30 mol% or less, based on all repeating units in the resin (A).

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

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

(Repeat unit to reduce main chain mobility)
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. In addition, from the viewpoint of excellent dissolution rate in a developer, Tg is preferably 400°C or less, more preferably 350°C or less.
In this specification, the glass transition temperature (Tg) of a polymer such as resin (A) (hereinafter referred to as "Tg of a 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 Tg at each mass ratio is calculated using Fox's formula (described in Materials Letters 62 (2008) 3152, etc.), and these are summed to determine 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 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). Examples of methods for reducing the mobility of the main chain of resin (A) include the following methods (a) to (e).
(a) Introduction of a bulky substituent to the main chain (b) Introduction of multiple substituents to the main chain (c) Introduction of a substituent that induces interaction between resins (A) near the main chain ( d) Main chain formation with a cyclic structure (e) Connection of the cyclic structure to the main chain It is preferable that the resin (A) has a repeating unit whose homopolymer Tg is 130° C. or higher.

As an example of specific means for achieving the above (a) to (e), there is a method of introducing repeating units described in paragraphs [0145] to [0160] of International Publication No. 2022/024928 into the resin (A). Can be mentioned.

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

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

The resin (A) may have a repeating unit having an alkali-soluble group.
Examples of the alkali-soluble group include the groups described in paragraph [0163] of International Publication No. 2022/024928. Examples of the repeating unit having an alkali-soluble group include those described in paragraphs [0085] and [0086] of JP-A-2014-098921.

(Repeating unit that has an alicyclic hydrocarbon structure and does not show acid decomposition)
The resin (A) has an alicyclic hydrocarbon structure and may have repeating units that are not acid-decomposable. Examples of the repeating unit having an alicyclic hydrocarbon structure and not showing acid decomposability include the repeating unit group described in paragraph [0164] of International Publication No. 2022/024928.

(Repeating unit represented by formula (III) that does not have either a hydroxyl group or a cyano group)
The resin (A) may have a repeating unit represented by formula (III) that does not have either a hydroxyl group or a cyano group.
The repeating unit represented by formula (III) that does not have either a hydroxyl group or a cyano group has both a hydroxyl group and a cyano group as described in paragraphs [0165] to [0168] of WO 2022/024928. This is the same as the repeating unit represented by formula (III).

(Other repeat units)
Furthermore, the resin (A) may have repeating units other than the above-mentioned repeating units.
For example, the resin (A) has a repeating unit selected from the group consisting of a repeating unit having an oxathian ring group, a repeating unit having an oxazolone ring group, a repeating unit having a dioxane ring group, and a repeating unit having a hydantoin ring group. You may do so.
Specific examples of repeating units other than the above-mentioned repeating units include those described in paragraph [0170] of International Publication No. 2022/024928.

In addition to the above-mentioned repeating structural units, the resin (A) contains various repeating structural units for the purpose of adjusting dry etching resistance, standard developer suitability, substrate adhesion, resist profile, resolution, heat resistance, sensitivity, etc. It may have.

As the resin (A), especially when the composition of the present invention is used as an actinic ray-sensitive or radiation-sensitive resin composition for ArF, all of the repeating units are derived from a compound having an ethylenically unsaturated bond. It is preferable that the repeating unit is composed of repeating units. Specific embodiments include those described in paragraph [0172] of International Publication No. 2022/024928.

Resin (A) can be synthesized according to conventional methods (eg, radical polymerization).
The weight average molecular weight (Mw) of the resin (A) is preferably 30,000 or less, more preferably 1,000 to 30,000, even more preferably 3,000 to 30,000, as a polystyrene equivalent value determined by GPC method. Particularly preferred is 5,000 to 15,000.
The degree of dispersion (molecular weight distribution, Pd, Mw/Mn) of the resin (A) is preferably 1 to 5, more preferably 1 to 3, even more preferably 1.2 to 3.0, and 1.2 to 2.0. is particularly preferred. The smaller the degree of dispersion, the better the resolution and resist shape, the smoother the sidewalls of the resist pattern, and the better the roughness.

The composition of the present invention may contain one type of resin (A) or two or more types.

In the composition of the present invention, the content of the resin (A) is preferably 40.0 to 99.9% by mass, and 60.0 to 90.0% by mass, based on the total solid content of the composition of the present invention. is more preferable.
The resin (A) may be used alone or in combination.

<(B) Compound that generates acid upon irradiation with actinic rays or radiation>
The composition of the present invention contains a compound (also referred to as "compound (B),""photoacidgenerator," or "photoacid generator (B)") that generates an acid upon irradiation with actinic rays or radiation. The photoacid generator may be in the form of a low molecular compound or may be incorporated into a part of the polymer. Further, a form of a low molecular compound and a form incorporated into a part of a polymer may be used together.
When the photoacid generator is in the form of a low molecular weight compound, the molecular weight of the photoacid generator is preferably 3000 or less, more preferably 2000 or less, and even more preferably 1000 or less. The lower limit is not particularly limited, but is preferably 100 or more.
When the photoacid generator is incorporated into a part of the polymer, it may be incorporated into a part of the resin (A), or may be incorporated into a resin different from the resin (A).
The photoacid generator is preferably in the form of a low molecular weight compound.
The photoacid generator is preferably a compound that generates an acid having a pKa of -10 or more and 5 or less when irradiated with actinic rays or radiation.

The compound (B) is preferably a compound represented by the following general formula (1).

Since the compound represented by the general formula (1) has an aromatic ring group such as an aryl group or a heteroaryl group or a sulfo group, the π -π interaction and the hydrogen bond between the L ₁₀₁ of the repeating unit (a) and the ester bond increase the compatibility between the resin (A) and the compound (B) and make the material distribution uniform. The LWR performance and pattern shape can be further improved.

Examples of the aryl group as R ₁ and R ₅ include aryl groups having 6 to 15 carbon atoms, and specifically, preferred examples include phenyl group, naphthyl group, anthryl group, etc. can.
Examples of the heteroaryl group as R ₁ and R ₅ include a heteroaryl group having 2 to 15 carbon atoms, including a 5- to 10-membered ring, and specifically, , furyl group, thienyl group, pyrrolyl group, oxazolyl group, pyridyl group, quinolinyl group, carbazolyl group, and the like.
Substituents for R ₂ to R ₄ are not particularly limited as long as they are monovalent substituents, but include, for example, alkyl groups; alkenyl groups; cycloalkyl groups; aryl groups; halogen atoms; oxygen atoms, sulfur atoms, and nitrogen atoms. Examples include groups containing atoms and heteroatoms such as silicon atoms; and combinations of two or more thereof.

Examples of the alkyl groups as R ₂ to R ₄ include alkyl groups having 1 to 30 carbon atoms. Preferably, the alkyl group is an alkyl group having 1 to 20 carbon atoms, such as a methyl group, ethyl group, propyl group, isopropyl group, n-butyl group, sec-butyl group, hexyl group, 2-ethylhexyl group, octyl group, or dodecyl group. More preferably, it is an alkyl group having 1 to 8 carbon atoms.

Examples of the alkenyl groups as R ₂ to R ₄ include alkenyl groups having 2 to 30 carbon atoms, and alkenyl groups having 2 to 8 carbon atoms are preferred.
The cycloalkyl groups as R ₂ to R ₄ may be monocyclic or polycyclic. The number of carbon atoms in this cycloalkyl group is not particularly limited, but is preferably 3 to 8.

Examples of the aryl group as R ₂ to R ₄ include aryl groups having 6 to 15 carbon atoms, and specifically, preferred examples include phenyl group, naphthyl group, and anthryl group. can.
Examples of the halogen atoms as R ₂ to R ₄ include fluorine atoms, chlorine atoms, bromine atoms, and iodine atoms.

Groups containing heteroatoms include, for example, hydroxyl group, carboxyl group, alkoxy group, thiol group, thioether group, nitro group, nitroso group, cyano group, amino group, acyloxy group, acylamido group, heteroaryl group, ether bond, carbonyl group, etc. Examples include bonds and combinations of two or more thereof.

The number of carbon atoms in the alkoxy group, acyloxy group and acylamido group is preferably 20 or less, more preferably 8 or less. Examples of the alkoxy group include methoxy group, ethoxy group, propoxy group, isopropoxy group, n-butyloxy group, t-butoxy group and octyloxy group. Among these, methoxy, ethoxy, propoxy, isopropoxy and t-butoxy groups are particularly preferred. In addition, as for the thioether group, the same ones as the alkoxy group can be mentioned, except that a sulfur atom is used instead of an oxygen atom. Examples of the acyloxy group include an acetyloxy group. Examples of the acylamide group include an acetylamide group.
Examples of the heteroaryl group include the same heteroaryl groups as R ₁ and R ₅ .

The aryl group and heteroaryl group as R ₁ and R ₅ may further have a substituent. Further substituents include, for example, alkyl groups; alkenyl groups; cycloalkyl groups; aryl groups; halogen atoms; groups containing heteroatoms such as oxygen atoms, sulfur atoms, nitrogen atoms, and silicon atoms; and two or more of these. A combination of these can be mentioned.
Alkyl group; alkenyl group; cycloalkyl group; aryl group; halogen atom; group containing a heteroatom such as oxygen atom, sulfur atom, nitrogen atom, and silicon atom; and combinations of two or more of these are R ₂ - In specific examples of substituents as R ₄ , alkyl groups; alkenyl groups; cycloalkyl groups; aryl groups; halogen atoms; groups containing heteroatoms such as oxygen atoms, sulfur atoms, nitrogen atoms, and silicon atoms; and 2 of these It is the same as a combination of more than one species.
When the aryl group or heteroaryl group as R ₁ and R ₅ has a plurality of substituents, at least two of the plurality of substituents may be bonded to each other to form a ring.

Alkyl groups; alkenyl groups; cycloalkyl groups; aryl groups; groups containing heteroatoms such as oxygen atoms, sulfur atoms, nitrogen atoms, and silicon atoms as substituents for R ₂ to R ₄ further have a substituent; It's okay. Additional substituents include, for example, alkyl groups, alkenyl groups, cycloalkyl groups, aryl groups, amino groups, amido groups, ureido groups, urethane groups, hydroxy groups, carboxy groups, halogen atoms, alkoxy groups, thioether groups, acyl groups, etc. group, an acyloxy group, an alkoxycarbonyl group, a cyano group, a nitro group, and a combination of two or more thereof.

The above R ₁ and R ₅ are a group containing a polar group as described below, a group containing a group whose polarity increases when decomposed by the action of an acid, or a group which decomposes by the action of an alkaline developer and increases its solubility in the alkaline developer. A group containing a group can be constructed.
The above R ₂ to R ₄ are a group containing a polar group as described below, a group containing a group whose polarity increases when decomposed by the action of an acid, or a group which decomposes by the action of an alkaline developer and increases its solubility in the alkaline developer. A group containing a group can be constructed.

In the above general formula (1), R ₃ preferably represents an aryl group.
Examples of the aryl group as R ₃ include the same aryl groups as R ₁ and R ₅ .
The aryl group as R ₃ may further have a substituent. As further substituents, the above-mentioned groups can be mentioned as specific examples of the substituents that R ₁ and R ₅ described above may further have.
When the aryl group as R ₃ has a plurality of substituents, at least two of the plurality of substituents may be bonded to each other to form a ring.

In the above general formula (1), at least one of R ₁ to R ₅ is a group containing a polar group, a group containing a group whose polarity increases when decomposed by the action of an acid, or a group which decomposes by the action of an alkaline developer. , a group containing a group that increases solubility in an alkaline developer is preferable.

Examples of the polar group in the group containing a polar group as at least one of R ₁ to R ₅ include a carboxyl group, a phenolic hydroxyl group, a fluorinated alcohol group, a sulfonamide group, a sulfonylimide group, and an (alkylsulfonyl) group. (alkylcarbonyl)methylene group, (alkylsulfonyl)(alkylcarbonyl)imide group, bis(alkylcarbonyl)methylene group, bis(alkylcarbonyl)imide group, bis(alkylsulfonyl)methylene group, bis(alkylsulfonyl)imide group, Examples include acidic groups such as a tris(alkylcarbonyl)methylene group and a tris(alkylsulfonyl)methylene group, and alcoholic hydroxyl groups.

In addition, alcoholic hydroxyl group refers to a hydroxyl group bonded to a hydrocarbon group other than a hydroxyl group directly bonded to an aromatic ring (phenolic hydroxyl group), and the hydroxyl group is an electron-withdrawing group such as a fluorine atom at the α position of the hydroxyl group. Excludes aliphatic alcohols substituted with functional groups (for example, hexafluoroisopropanol groups, etc.). The alcoholic hydroxyl group is preferably a hydroxyl group having a pKa (acid dissociation constant) of 12 or more and 20 or less.
Among these, as the polar group, a carboxyl group, a phenolic hydroxyl group, or a fluorinated alcohol group (preferably a hexafluoroisopropanol group) is preferable.

Examples of the group containing a polar group include a group having a carbonyl bond.
Examples of the group having a carbonyl bond include an alkylcarbonyl group and an arylcarbonyl group.
Examples of the alkyl group include the same alkyl groups as R ₂ to R ₄ .
Examples of the aryl group include the same aryl groups as R ₁ and R ₅ .
A group having a carbonyl bond is a group in which a carbonyl bond and an ether bond are not bonded adjacently.

The alkylcarbonyl group and arylcarbonyl group as a group having a carbonyl bond may further have a substituent.
Further substituents include, for example, alkyl groups; alkenyl groups; cycloalkyl groups; aryl groups; halogen atoms; groups containing heteroatoms such as oxygen atoms, sulfur atoms, nitrogen atoms, and silicon atoms; and two or more of these. A combination of these can be mentioned.
Alkyl group; alkenyl group; cycloalkyl group; aryl group; halogen atom; group containing heteroatoms such as oxygen atom, sulfur atom, nitrogen atom, and silicon atom; and combinations of two or more of these are R ₂ - In specific examples of substituents as R ₄ , alkyl groups; alkenyl groups; cycloalkyl groups; aryl groups; halogen atoms; groups containing heteroatoms such as oxygen atoms, sulfur atoms, nitrogen atoms, and silicon atoms; and 2 of these It is the same as a combination of more than one species.

Examples of the group containing a polar group include, but are not particularly limited to, organic groups containing a polar group. Examples of organic groups containing polar groups include alkyl groups; alkenyl groups; cycloalkyl groups; aryl groups; halogen atoms; groups containing heteroatoms such as oxygen atoms, sulfur atoms, nitrogen atoms, and silicon atoms; Examples include a combination of more than one species and a group having a polar group.
Alkyl group; alkenyl group; cycloalkyl group; aryl group; halogen atom; group containing a heteroatom such as oxygen atom, sulfur atom, nitrogen atom, and silicon atom; and combinations of two or more of these are R ₂ - In specific examples of substituents as R ₄ , alkyl groups; alkenyl groups; cycloalkyl groups; aryl groups; halogen atoms; groups containing heteroatoms such as oxygen atoms, sulfur atoms, nitrogen atoms, and silicon atoms; and 2 of these It is the same as a combination of more than one species.

Examples of the group containing a polar group include an alkyl group containing a polar group and an aryl group containing a polar group.
Examples of the alkyl group in the alkyl group containing a polar group include the same alkyl groups as R ₂ to R ₄ .
Examples of the aryl group in the aryl group containing a polar group include the same aryl groups as R ₁ and R ₅ .
Further, the group containing a polar group may be the polar group itself.

A group which decomposes and increases polarity by the action of an acid (hereinafter also referred to as "acid-decomposable group") in a group containing a group which decomposes _and increases polarity by the action of an acid as at least one of R ₁ to R 5 ) preferably has a structure in which the polar group is protected by a group (leaving group) that decomposes and leaves under the action of an acid.
Examples of the polar group include those similar to the polar group in the group containing a polar group as at least one of R ₁ to R ₅ .

Examples of groups that decompose and leave due to the action of acids (leaving groups) include those described in paragraphs [0030] to [0035] and [0037] to [0039] of International Publication No. 2022/024928. Can be done.

The group containing an acid-decomposable group is not particularly limited as long as it is a group containing an acid-decomposable group, and examples include organic groups containing an acid-decomposable group. Examples of organic groups containing acid-decomposable groups include alkyl groups; alkenyl groups; cycloalkyl groups; aryl groups; halogen atoms; groups containing heteroatoms such as oxygen atoms, sulfur atoms, nitrogen atoms, and silicon atoms; Examples include a combination of two or more of the following, which has an acid-decomposable group.
Alkyl group; alkenyl group; cycloalkyl group; aryl group; halogen atom; group containing a heteroatom such as oxygen atom, sulfur atom, nitrogen atom, and silicon atom; and combinations of two or more of these are R ₂ - In specific examples of substituents as R ₄ , alkyl groups; alkenyl groups; cycloalkyl groups; aryl groups; halogen atoms; groups containing heteroatoms such as oxygen atoms, sulfur atoms, nitrogen atoms, and silicon atoms; and 2 of these It is the same as a combination of more than one species.

Examples of the group containing an acid-decomposable group include an alkyl group containing an acid-decomposable group and an aryl group containing an acid-decomposable group.
Examples of the alkyl group in the alkyl group containing an acid-decomposable group include the same alkyl groups as R ₂ to R ₄ .
Examples of the aryl group in the aryl group containing an acid-decomposable group include the same aryl groups as R ₁ and R ₅ .
Further, the group containing an acid-decomposable group may be the acid-decomposable group itself.

At least one of R ₁ to R ₅ contains a group that decomposes under the action of an alkaline developer and increases its solubility in the alkaline developer. A group that increases the solubility in is also called a "polar conversion group", and specific examples include a lactone group, a carboxylic acid ester group (-COO-), an acid anhydride group (-C(O)OC(O) -), acid imide group (-NHCONH-), carboxylic acid thioester group (-COS-), carbonate ester group (-OC(O)O-), sulfuric acid ester group (-OSO ₂ O-), sulfonic acid ester group (-SO ₂ O-) and the like.

Examples of the group containing a polarity converting group include an acyloxy group, an alkoxycarbonyloxy group, an aryloxycarbonyloxy group, an aryloxycarbonyl group, an alkoxycarbonyl group, a carbamoyl group, and an imide group.

The number of carbon atoms in the acyl group in the acyloxy group is preferably 1 to 30, more preferably 1 to 8.
The number of carbon atoms in the alkoxy group in the alkoxycarbonyloxy group is preferably 1 to 30, more preferably 1 to 8.

The number of carbon atoms in the aryl group in the aryloxycarbonyloxy group is preferably 6 to 14, more preferably 6 to 10.
The number of carbon atoms in the aryl group in the aryloxycarbonyl group is preferably 6 to 14, more preferably 6 to 10.
The number of carbon atoms in the alkoxy group in the alkoxycarbonyl group is preferably 1 to 30, more preferably 1 to 8.
An imide group is a group obtained by removing one hydrogen atom from imide.

The acyloxy group, alkoxycarbonyloxy group, aryloxycarbonyloxy group, aryloxycarbonyl group, alkoxycarbonyl group, carbamoyl group, and imide group may further have a substituent.
As further substituents, the above-mentioned groups can be mentioned as specific examples of the substituents that R ₁ and R ₅ described above may further have.

In one preferred embodiment of the present invention, the polarity converting group is a group represented by X in the partial structure represented by general formula (KA-1) or (KB-1).

X in the general formula (KA-1) or (KB-1) is a carboxylic acid ester group: -COO-, an acid anhydride group: -C(O)OC(O)-, an acid imide group: -NHCONH-, Carboxylic acid thioester group: -COS-, carbonate ester group: -OC(O)O-, sulfuric acid ester group: -OSO ₂ O-, sulfonic acid ester group: -SO ₂ O-.
Y ¹ and Y ² may be the same or different, and each represents an electron-withdrawing group.
In addition, as one preferable embodiment of the present invention, the compound represented by the above general formula (1) has a partial structure represented by the general formula (KA-1) or (KB-1) as a group containing a polarity converting group. However, as in the case of the partial structure represented by the general formula (KA-1), and the partial structure represented by (KB-1) when Y ¹ and Y ² are monovalent, When the partial structure does not have a bond, the group having the partial structure is a group having a monovalent or higher valence from which at least one arbitrary hydrogen atom in the partial structure is removed.

The partial structure represented by general formula (KA-1) is a structure that forms a ring structure together with the group as X.
X in general formula (KA-1) is preferably a carboxylic ester group (ie, when KA-1 forms a lactone ring structure), an acid anhydride group, or a carbonate ester group. More preferred is a carboxylic acid ester group.
The ring structure represented by the general formula (KA-1) may have a substituent, for example, it may have nka number of substituents Z _ka1 .
When there is a plurality of Z _ka1 , each independently represents an alkyl group, a cycloalkyl group, an ether group, a hydroxyl group, an amide group, an aryl group, a lactone ring group, or an electron-withdrawing group.
Z _ka1 may be connected to each other to form a ring. Examples of the ring formed by connecting Z _ka1 to each other include a cycloalkyl ring and a hetero ring (cyclic ether ring, lactone ring, etc.).
nka represents an integer from 0 to 10. It is preferably an integer of 0 to 8, more preferably an integer of 0 to 5, even more preferably an integer of 1 to 4, and most preferably an integer of 1 to 3.

The electron-withdrawing group as Z _ka1 is the same as the electron-withdrawing group as Y ¹ and Y ² described below, which are represented by a halogen atom.
Note that the electron-withdrawing group may be substituted with another electron-withdrawing group.

Z _ka1 is preferably an alkyl group, a cycloalkyl group, an ether group, a hydroxyl group, or an electron-withdrawing group, and more preferably an alkyl group, a cycloalkyl group, or an electron-withdrawing group. The ether group is preferably one substituted with an alkyl group or a cycloalkyl group, that is, an alkyl ether group. Preferable examples of the electron-withdrawing group are the same as the electron-withdrawing groups as Y ¹ and Y ² described below.
Examples of the halogen atom as Z _ka1 include a fluorine atom, a chlorine atom, a bromine atom, an iodine atom, and the like, with a fluorine atom being preferred.
The alkyl group as Z _ka1 may have a substituent and may be either linear or branched. The straight chain alkyl group preferably has 1 to 30 carbon atoms, more preferably 1 to 20 carbon atoms, such as methyl group, ethyl group, n-propyl group, n-butyl group, sec-butyl group, t-butyl group. group, n-pentyl group, n-hexyl group, n-heptyl group, n-octyl group, n-nonyl group, n-decanyl group and the like. The branched alkyl group preferably has 3 to 30 carbon atoms, more preferably 3 to 20 carbon atoms, and includes, for example, an i-propyl group, an i-butyl group, a t-butyl group, an i-pentyl group, a t-pentyl group, Examples include i-hexyl group, t-hexyl group, i-heptyl group, t-heptyl group, i-octyl group, t-octyl group, i-nonyl group, and t-decanoyl group. Those having 1 to 4 carbon atoms such as methyl group, ethyl group, n-propyl group, i-propyl group, n-butyl group, i-butyl group, and t-butyl group are preferable.
The cycloalkyl group as Z _ka1 may have a substituent, and may be monocyclic, polycyclic, or bridged. For example, a cycloalkyl group may have a bridged structure. As the monocyclic type, a cycloalkyl group having 3 to 8 carbon atoms is preferable, and examples thereof include a cyclopropyl group, a cyclopentyl group, a cyclohexyl group, a cyclobutyl group, a cyclooctyl group, and the like. Examples of the polycyclic type include groups having a bicyclo, tricyclo, and tetracyclo structure having 5 or more carbon atoms, and preferably a cycloalkyl group having 6 to 20 carbon atoms, such as an adamantyl group, a norbornyl group, an isobornyl group, Examples include camphanyl group, dicyclopentyl group, α-pinel group, tricyclodecanyl group, tetracyclododecyl group, androstannyl group, and the like. The following structures are also preferable as the cycloalkyl group. Note that some of the carbon atoms in the cycloalkyl group may be substituted with heteroatoms such as oxygen atoms.

Preferred examples of the alicyclic moiety include adamantyl group, noradamantyl group, decalin group, tricyclodecanyl group, tetracyclododecanyl group, norbornyl group, cedrol group, cyclohexyl group, cycloheptyl group, cyclooctyl group, and cyclodecanyl group. and cyclododecanyl group. More preferred are adamantyl group, decalin group, norbornyl group, cedrol group, cyclohexyl group, cycloheptyl group, cyclooctyl group, cyclodecanyl group, cyclododecanyl group, and tricyclodecanyl group.
Examples of the substituents of these alicyclic structures include alkyl groups, halogen atoms, hydroxyl groups, alkoxy groups, carboxyl groups, and alkoxycarbonyl groups. The alkyl group is preferably a lower alkyl group such as a methyl group, an ethyl group, a propyl group, an isopropyl group, a butyl group, and more preferably a methyl group, an ethyl group, a propyl group, or an isopropyl group. Preferable examples of the alkoxy group include those having 1 to 4 carbon atoms, such as methoxy, ethoxy, propoxy, and butoxy groups. Examples of substituents that the alkyl group and alkoxy group may have include a hydroxyl group, a halogen atom, and an alkoxy group (preferably having 1 to 4 carbon atoms).

Examples of the lactone ring group of Z _ka1 include groups obtained by removing a hydrogen atom from a structure represented by any of (KA-1-1) to (KA-1-17) described below.

Examples of the aryl group of Z _ka1 include a phenyl group and a naphthyl group.

Substituents that the alkyl group, cycloalkyl group, and aryl group of Z _ka1 may further include a hydroxyl group, a halogen atom (fluorine, chlorine, bromine, iodine), a nitro group, a cyano group, the above-mentioned alkyl groups, a methoxy group, Alkoxy groups such as ethoxy group, hydroxyethoxy group, propoxy group, hydroxypropoxy group, n-butoxy group, isobutoxy group, sec-butoxy group, t-butoxy group, alkoxycarbonyl group such as methoxycarbonyl group, ethoxycarbonyl group, benzyl groups, aralkyl groups such as phenethyl groups and cumyl groups, acyl groups such as aralkyloxy groups, formyl groups, acetyl groups, butyryl groups, benzoyl groups, cyanamyl groups, and valeryl groups, acyloxy groups such as butyryloxy groups, the above alkenyl groups, Examples include alkenyloxy groups such as vinyloxy, propenyloxy, allyloxy, and butenyloxy groups; aryloxy groups such as the above-mentioned aryl groups and phenoxy groups; and aryloxycarbonyl groups such as benzoyloxy.

X in general formula (KA-1) is a carboxylic acid ester group, and the partial structure represented by general formula (KA-1) is preferably a lactone ring, preferably a 5- to 7-membered lactone ring.
In addition, as shown in (KA-1-1) to (KA-1-17) below, the 5- to 7-membered lactone ring as a partial structure represented by the general formula (KA-1) has a bicyclo structure and a spiro structure. It is preferable that other ring structures are condensed to form a structure.
Regarding the surrounding ring structures to which the ring structure represented by general formula (KA-1) may be bonded, for example, those in (KA-1-1) to (KA-1-17) below or to this I can list things that are similar.

As the structure containing a lactone ring structure represented by general formula (KA-1), structures represented by any of the following (KA-1-1) to (KA-1-17) are more preferable. Note that the lactone structure may be directly bonded to the main chain. Preferred structures include (KA-1-1), (KA-1-4), (KA-1-5), (KA-1-6), (KA-1-13), (KA-1- 14), (KA-1-17).

The structure containing the above lactone ring structure may or may not have a substituent. Preferred substituents include those similar to the substituents that the ring structure represented by the above general formula (KA-1) may have.

Although some lactone structures have optically active forms, any optically active form may be used. Further, one type of optically active substance may be used alone, or a plurality of optically active substances may be used in combination. When one kind of optically active substance is mainly used, its optical purity (ee) is preferably 90% or more, more preferably 95% or more, and most preferably 98% or more.

Preferably, X in the general formula (KB-1) is a carboxylic acid ester group (-COO-).

Y ¹ and Y ² in general formula (KB-1) each independently represent an electron-withdrawing group.

The electron-withdrawing group preferably has a partial structure represented by the following formula (EW). * in formula (EW) represents a bond directly connected to (KA-1) or a bond directly connected to X in (KB-1).

In the formula (EW),
_new is the repeating number of the linking group represented by -C(R _ew1 )(R _ew2 )-, and represents an integer of 0 or 1. When _new is 0, it represents a single bond and indicates that Y _ew1 is directly bonded.
Y _ew1 is a halogen atom, a cyano group, a nitrile group, a nitro group, a halo(cyclo)alkyl group represented by -C(R _f1 )(R _f2 )-R _f3 described below, a haloaryl group, an oxy group, a carbonyl group , a sulfonyl group, a sulfinyl group, and a combination thereof, and the electron-withdrawing group may have the following structure, for example. Note that the term "halo(cyclo)alkyl group" refers to an alkyl group and a cycloalkyl group in which at least a portion thereof is halogenated. R _ew3 and R _ew4 each independently represent an arbitrary structure. No matter what structure R _ew3 and R _ew4 have, the partial structure represented by formula (EW) has electron-withdrawing properties, and is preferably an alkyl group, a cycloalkyl group, or a fluorinated alkyl group.

When Y _ew1 is a divalent or higher group, the remaining bond forms a bond with any atom or substituent.
Y _ew1 is preferably a halogen atom, or a halo(cyclo)alkyl group or haloaryl group represented by -C(R _f1 )(R _f2 )-R _f3 .
R _ew1 and R _ew2 each independently represent an arbitrary substituent, for example, a hydrogen atom, an alkyl group, a cycloalkyl group, or an aryl group.
At least two of R _ew1 , R _ew2 and Y _ew1 may be linked to each other to form a ring.

Here, R _f1 represents a halogen atom, a perhaloalkyl group, a perhalocycloalkyl group, or a perhaloaryl group, more preferably a fluorine atom, a perfluoroalkyl group, or a perfluorocycloalkyl group, and even more preferably a fluorine atom or a trifluoroaryl group. Represents a fluoromethyl group.
R _f2 and R _f3 each independently represent a hydrogen atom, a halogen atom, or an organic group, and R _f2 and R _f3 may be connected to form a ring. Examples of the organic group include an alkyl group, a cycloalkyl group, and an alkoxy group, which may be substituted with a halogen atom (preferably a fluorine atom). More preferably, R _f2 and R _f3 are (halo) It is an alkyl group. It is more preferable that R _f2 represents a group similar to R _f1 or is linked to R _f3 to form a ring.
R _f1 and R _f3 may be connected to form a ring, and examples of the ring formed include a (halo)cycloalkyl ring and a (halo)aryl ring.
Examples of the (halo)alkyl group in R _f1 to R _f3 include the alkyl group in Z _ka1 described above and a halogenated structure thereof.
As the (per)halocycloalkyl group and (per)haloaryl group in R _f1 to R _f3 or in the ring formed by connecting R _f2 and R _f3 , for example, the cycloalkyl group in Z _ka1 described above is a halogen group. structure, more preferably a fluorocycloalkyl group represented by -C _(n) F _(2n-2) H, and a perfluoroaryl group represented by -C _(n) F _(n-1). Can be mentioned. Here, the number n of carbon atoms is not particularly limited, but is preferably 5 to 13, and more preferably 6.

The ring which may be formed by connecting at least two of R _ew1 , R _ew2 and Y _ew1 to each other is preferably a cycloalkyl group or a heterocyclic group, and the heterocyclic group is preferably a lactone ring group. Examples of the lactone ring include structures represented by the above formulas (KA-1-1) to (KA-1-17).

In addition, in the compound represented by the above general formula (1), a plurality of partial structures represented by the general formula (KA-1), a plurality of partial structures represented by the general formula (KB-1), or It may have both a partial structure of general formula (KA-1) and general formula (KB-1).
Note that a part or all of the partial structure of general formula (KA-1) may also serve as an electron-withdrawing group as Y ¹ or Y ² in general formula (KB-1). For example, when X in general formula (KA-1) is a carboxylic ester group, the carboxylic ester group functions as an electron-withdrawing group as Y ¹ or Y ² in general formula (KB-1). It is also possible.

Examples of the group containing a polarity converting group include, but are not particularly limited to, organic groups containing a polarity converting group. Examples of organic groups containing polarity converting groups include alkyl groups; alkenyl groups; cycloalkyl groups; aryl groups; halogen atoms; groups containing heteroatoms such as oxygen atoms, sulfur atoms, nitrogen atoms, and silicon atoms; Examples include groups that are a combination of two or more types and have a polarity converting group.
Alkyl group; alkenyl group; cycloalkyl group; aryl group; halogen atom; group containing a heteroatom such as oxygen atom, sulfur atom, nitrogen atom, and silicon atom; and combinations of two or more of these are R ₂ - In specific examples of substituents as R ₄ , alkyl groups; alkenyl groups; cycloalkyl groups; aryl groups; halogen atoms; groups containing heteroatoms such as oxygen atoms, sulfur atoms, nitrogen atoms, and silicon atoms; and 2 of these It is the same as a combination of more than one species.

Examples of the group containing a polarity converting group include an alkyl group containing a polarity converting group, an aryl group containing a polarity converting group, and the like.
Examples of the alkyl group in the alkyl group containing a polarity converting group include the same alkyl groups as R ₂ to R ₄ .
Examples of the aryl group in the aryl group containing a polarity converting group include the same aryl groups as R ₁ and R ₅ .

In the above general formula (1), R ₁ , R ₃ and R ₅ are each preferably a group represented by the following general formula (Ar).

Specific examples of the substituents as R ₆ to R ₁₀ are the same as the specific examples of the substituents as R ₂ to R ₄ described above.
At least one of R ₆ to R ₁₀ is a group containing a polar group, a group containing a group whose polarity increases when decomposed by the action of an acid, or a group which decomposes by the action of an alkaline developer and has solubility in the alkaline developer. It is a group containing a group in which .
The group containing a polar group is the same as the group containing a polar group as at least one of R ₁ to R ₅ .
The group containing a group that decomposes and increases in polarity due to the action of an acid is the same as the group that includes a group that decomposes and increases in polarity due to the action of an acid as at least one of R ₁ to _R 5 .
A group containing a group that decomposes under the action of an alkaline developer and increases its solubility in the alkaline developer is at least one of R ₁ to R ₅ that decomposes under the action of the alkaline developer and increases its solubility in the alkaline developer. This is similar to groups containing groups that increase solubility in

Moreover, in the above general formula (1), it is preferable that R ₁ , R ₃ , and R ₅ are groups each represented by the following general formula (Ar1).

In general formula (Ar1),
R ₁₁ to R ₁₅ each independently represent a hydrogen atom or a substituent, and at least one of R ₁₁ to R ₁₅ represents the following substituent Y. * represents a bond to the benzene ring in general formula (1).
Substituent Y: hydroxy group, carboxyl group, group having a carbonyl bond, acyloxy group, alkoxycarbonyloxy group, aryloxycarbonyloxy group, aryloxycarbonyl group, alkoxycarbonyl group, carbamoyl group, or imido group

Specific examples of the substituents as R ₁₁ to R ₁₅ are the same as the specific examples of the substituents as R ₂ to R ₄ described above.
At least one of R ₁₁ to R ₁₅ represents the above substituent Y.

Specific examples of the group having a carbonyl bond as the substituent Y are the same as the specific examples of the group having a carbonyl bond as the group having a polar group described above.
The number of carbon atoms in the acyl group in the acyloxy group as the substituent Y is preferably 1 to 30, more preferably 1 to 8.
The number of carbon atoms in the alkoxy group in the alkoxycarbonyloxy group as the substituent Y is preferably 1 to 30, more preferably 1 to 8.
The number of carbon atoms in the aryl group in the aryloxycarbonyloxy group as the substituent Y is preferably 6 to 14, more preferably 6 to 10.
The number of carbon atoms in the aryl group in the aryloxycarbonyl group as the substituent Y is preferably 6 to 14, more preferably 6 to 10.
The number of carbon atoms in the alkoxy group in the alkoxycarbonyl group as the substituent Y is preferably 1 to 30, more preferably 1 to 8.
The imide group as the substituent Y is a group obtained by removing one hydrogen atom from imide.

As the substituent Y, a group having a carbonyl bond, an acyloxy group, an alkoxycarbonyloxy group, an aryloxycarbonyloxy group, an aryloxycarbonyl group, an alkoxycarbonyl group, and an imide group may further have a substituent.
As further substituents, the above-mentioned groups can be mentioned as specific examples of the substituents that R ₁ and R ₅ described above may further have.

n in the anion part of general formula (1) represents the number of anions. n represents an integer of 1 or more. The upper limit of n is not particularly limited, but is, for example, 4.
Preferably, n is 1.

M ⁿ⁺ in the above general formula (1) represents a cation.
n in the cation part of general formula (1) represents the valence of the cation. n represents an integer of 1 or more. The upper limit of n is not particularly limited, but is, for example, 4.
Preferably, n is 1.
The cation as M ⁿ⁺ is not particularly limited as long as it is a monovalent or higher cation, but an onium cation is preferable, and a cation represented by the following general formula (ZIA) or general formula (ZIIA) is preferable.

In the above general formula (ZIA),
R ₂₀₁ , R ₂₀₂ and R ₂₀₃ each independently represent an organic group.
The organic group as R ₂₀₁ , R ₂₀₂ and R ₂₀₃ generally has 1 to 30 carbon atoms, preferably 1 to 20 carbon atoms.
Furthermore, two of R ₂₀₁ to R ₂₀₃ may be combined to form a ring structure, and the ring may contain an oxygen atom, a sulfur atom, an ester bond, an amide bond, or a carbonyl group. Examples of the group formed by combining two of R ₂₀₁ to R ₂₀₃ include an alkylene group (eg, butylene group, pentylene group) and -CH ₂ -CH ₂ -O-CH ₂ -CH ₂ -.

Preferred embodiments of the cation as the general formula (ZIA) include the cation (ZI-11) and cation (ZI-12) described below.
The divalent or higher cation in the case where n is 2 or more may be a cation having a plurality of structures represented by the general formula (ZIA). Such cations include, for example, at least one of the cations R ₂₀₁ to R 203 represented by the general formula (ZIA) and at least one of R ₂₀₁ to _{R 203} _of the other cation represented by the general formula (ZIA). Examples include divalent cations having a structure in which at least one of them is bonded via a single bond or a linking group.

First, the cation (ZI-11) will be explained.
The cation (ZI-11) is a cation in which at least one of R ₂₀₁ to R ₂₀₃ in the above general formula (ZIA) is an aryl group, that is, an arylsulfonium cation.
In the arylsulfonium cation, all of R ₂₀₁ to R ₂₀₃ may be an aryl group, or some of R ₂₀₁ to R ₂₀₃ may be an aryl group, and the remainder may be an alkyl group or a cycloalkyl group.
Examples of the arylsulfonium cation include triarylsulfonium cation, diarylalkylsulfonium cation, aryldialkylsulfonium cation, diarylcycloalkylsulfonium cation, and aryldicycloalkylsulfonium cation.

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

The aryl group, alkyl group, and cycloalkyl group of R ₂₀₁ to R ₂₀₃ each independently represent an alkyl group (for example, carbon number 1 to 15), a cycloalkyl group (for example, carbon number 3 to 15), an aryl group (for example, carbon number 6 to 14), an alkoxy group (eg, carbon number 1 to 15), a halogen atom, a hydroxyl group, a lactone ring group, or a phenylthio group as a substituent.
Examples of the lactone ring group include groups obtained by removing a hydrogen atom from the structure represented by any of (KA-1-1) to (KA-1-17) described above.

Next, the cation (ZI-12) will be explained.
The cation (ZI-12) is a compound in which R ₂₀₁ to R ₂₀₃ in formula (ZIA) each independently represent an organic group having no aromatic ring. Here, the aromatic ring includes an aromatic ring containing a hetero atom.
The organic group having no aromatic ring as R ₂₀₁ to R ₂₀₃ generally has 1 to 30 carbon atoms, preferably 1 to 20 carbon atoms.
R ₂₀₁ to R ₂₀₃ are each independently preferably an alkyl group, a cycloalkyl group, an allyl group, or a vinyl group, more preferably a linear or branched 2-oxoalkyl group, a 2-oxocyclo An alkyl group or an alkoxycarbonylmethyl group, more preferably a linear or branched 2-oxoalkyl group.

The alkyl group and cycloalkyl group of R ₂₀₁ to R ₂₀₃ are preferably a linear alkyl group having 1 to 10 carbon atoms or a branched alkyl group having 3 to 10 carbon atoms (for example, a methyl group, an ethyl group, (propyl group, butyl group, 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, having 1 to 5 carbon atoms), a hydroxyl group, a cyano group, or a nitro group.

Next, general formula (ZIIA) will be explained.
In general formula (ZIIA), 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, and more preferably a phenyl group. The aryl group of R ₂₀₄ and R ₂₀₅ may be an aryl group having a heterocyclic structure containing an oxygen atom, a nitrogen atom, a sulfur atom, or the like. Examples of the skeleton of the aryl group having a heterocyclic structure include pyrrole, furan, thiophene, indole, benzofuran, and benzothiophene.
The alkyl group and cycloalkyl group of 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 (for example, a methyl group, an ethyl group, a propyl group, butyl group, pentyl group), or a cycloalkyl group having 3 to 10 carbon atoms (eg, cyclopentyl group, cyclohexyl group, and 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 to R ₂₀₇ may have include an alkyl group (for example, having 1 to 15 carbon atoms), a cycloalkyl group (for example, having 3 to 15 carbon atoms), 15), an aryl group (for example, having 6 to 15 carbon atoms), an alkoxy group (for example, having 1 to 15 carbon atoms), a halogen atom, a hydroxyl group, a lactone ring group, and a phenylthio group.
Examples of the lactone ring group include groups obtained by removing a hydrogen atom from the structure represented by any of (KA-1-1) to (KA-1-17) described above.

Preferred examples of M ⁿ⁺ (cation) in general formula (1) are shown below, but the present invention is not limited thereto. Me represents a methyl group, and Bu represents an n-butyl group.

Preferred examples of the anion moiety in general formula (1) are shown below, but the present invention is not limited thereto. Me represents a methyl group.

It is preferable that the pKa of the acid generated by the above compound (B) is -10 or more and 5 or less.

Preferred examples of the compound represented by general formula (1) are shown below, but the present invention is not limited thereto. Me represents a methyl group. Further, as a preferable example of the compound represented by the general formula (1), there can also be mentioned a compound in which the above-mentioned anion and the above-mentioned cation are combined.

The compound represented by general formula (1) can be synthesized, for example, by a method using a coupling reaction.

For the coupling reaction, for example, Suzuki coupling or the like can be applied. The counter cation can be converted into the desired cation M ⁺ by a known anion exchange method or a conversion method using an ion exchange resin, for example, as described in JP-A-6-184170.
Examples of the coupling reaction include the following.

X represents a halogen atom, and A represents an alkyl group. R represents a substituent.
Y represents a group that forms compound XY through a coupling reaction.

In the composition of the present invention, the mass ratio of the repeating unit (a) contained in the above-mentioned resin (A) to the compound represented by the general formula (1) (repeat unit (a)/general formula (1)) (compound represented) is preferably 0.75 or more, more preferably 1 or more, and even more preferably 2 or more. By setting the above ratio to 0.75 or more, the number of aromatic ring groups contained in the resin (A) and the number of aromatic ring groups contained in the compound represented by general formula (1) become close to each other, and the number of aromatic ring groups contained in the resin (A) becomes close. ) and the compound represented by the general formula (1) is further improved, and even better roughness performance and pattern shape can be obtained, which is preferable.
The upper limit of the ratio is not particularly limited, but is preferably 10 or less, more preferably 8 or less, and even more preferably 6 or less.

Examples of the compound (B) include, in addition to the compound represented by the above general formula (1), a compound represented by "M ⁺ X ^- " (onium salt), which generates an organic acid upon exposure to light. Preferably, it is a compound.
Examples of the organic acids include sulfonic acids (aliphatic sulfonic acids, aromatic sulfonic acids, camphorsulfonic acids, etc.), carboxylic acids (aliphatic carboxylic acids, aromatic carboxylic acids, aralkylcarboxylic acids, etc.), carbonylsulfonylimide. acids, bis(alkylsulfonyl)imidic acids, and tris(alkylsulfonyl)methide acids.

In the compound represented by "M ⁺ X ^- ", M ⁺ represents an organic cation.
The organic cation is not particularly limited. The valence of the organic cation may be one or more than two.
Among these, the organic cation is preferably a cation represented by the general formula (ZIA) or the general formula (ZIIA).

In the compound represented by "M ⁺ X ^- ", X ^- represents an organic anion.
The organic anion is not particularly limited, and includes mono- or divalent or higher-valent organic anions.
As the organic anion, an anion having a significantly low ability to cause a nucleophilic reaction is preferable, and a non-nucleophilic anion is more preferable.

Examples of non-nucleophilic anions include those described in paragraphs [0284] to [0289] of International Publication No. 2022/024928.
Further, as the compound (B), in addition to the compound represented by the above general formula (1), other photoacid generators described in paragraphs [0290] to [0291] of International Publication No. 2022/024928 can be used. can be mentioned.

The content of the photoacid generator (B) is not particularly limited, but it should be 0.5% by mass or more based on the total solid content of the composition of the present invention, since the cross-sectional shape of the formed pattern becomes more rectangular. is preferable, and 1.0% by mass or more is more preferable. The content is preferably 50.0% by mass or less, more preferably 30.0% by mass or less, and even more preferably 25.0% by mass or less, based on the total solid content of the composition of the present invention.
The photoacid generator (B) may be used alone or in combination of two or more.

<Acid diffusion control agent>
The composition of the present invention may also include an acid diffusion control agent.
The acid diffusion control agent traps the acid generated from the photoacid generator and the like during exposure, and acts as a quencher to suppress the reaction of the acid-decomposable resin in the unexposed area due to the excess generated acid.
The type of acid diffusion control agent is not particularly limited, and examples include a basic compound (CA), a low molecular compound (CB) having a nitrogen atom and a group that is eliminated by the action of an acid, and actinic rays or radiation. Examples include compounds (CC) whose acid diffusion control ability decreases or disappears when irradiated with.
Compounds (CC) include onium salt compounds (CD) that are relatively weak acids with respect to photoacid generators, and basic compounds (CE) whose basicity decreases or disappears when irradiated with actinic rays or radiation. Can be mentioned.
Specific examples of the basic compound (CA) include those described in paragraphs [0132] to [0136] of International Publication No. 2020/066824; Specific examples of basic compounds (CE) that disappear include those described in paragraphs [0137] to [0155] of International Publication No. 2020/066824, and those described in paragraph [0164] of International Publication No. 2020/066824. Specific examples of low-molecular compounds (CB) having a nitrogen atom and a group that is eliminated by the action of an acid include those described in paragraphs [0156] to [0163] of International Publication No. 2020/066824. ].
Specific examples of onium salt compounds (CD) that are weak acids relative to photoacid generators include those described in paragraphs [0305] to [0314] of International Publication No. 2020/158337. .

In addition to the above, for example, paragraphs [0627] to [0664] of US Patent Application Publication No. 2016/0070167A1, paragraphs [0095] to [0187] of US Patent Application Publication No. 2015/0004544A1, and US Patent Application Publication No. 2016/0237190A1. Known compounds disclosed in paragraphs [0403] to [0423] of No. 1, and paragraphs [0259] to [0328] of US Patent Application Publication No. 2016/0274458A1 can be suitably used as acid diffusion control agents.

When the composition of the present invention contains an acid diffusion control agent, the content of the acid diffusion control agent (if there are multiple types, the total amount) is 0.1 with respect to the total solid content of the composition of the present invention. It is preferably from 15.0% by weight, more preferably from 0.5 to 15.0% by weight.
In the composition of the present invention, one type of acid diffusion control agent may be used alone, or two or more types may be used in combination.

<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 to be unevenly distributed on the surface of the actinic ray-sensitive or radiation-sensitive film, but unlike a surfactant, it does not necessarily need to have a hydrophilic group in the molecule. It may not contribute to uniform mixing of polar and non-polar substances.
The effects of adding the hydrophobic resin (D) include controlling the static and dynamic contact angle of the surface of the actinic ray-sensitive or radiation-sensitive film with respect to water, and suppressing outgassing.

The hydrophobic resin (D) preferably has at least one of a fluorine atom, a silicon atom, and a _CH3 partial structure contained in the side chain portion of the resin, from the viewpoint of uneven distribution on the membrane surface layer. , it is more preferable to have two or more types. The hydrophobic resin preferably has a hydrocarbon group having 5 or more carbon atoms. These groups may be present in the main chain of the resin or may be substituted on the side chains.
Examples of the hydrophobic resin (D) include compounds described in paragraphs [0275] to [0279] of International Publication No. 2020/004306.

When the composition of the present invention contains a hydrophobic resin (D), the content of the hydrophobic resin (D) is 0.01 to 20.0% by mass based on 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 also contain a surfactant. When a surfactant is included, a pattern with better adhesion and fewer development defects can be formed.
The surfactant is preferably a fluorine-based and/or silicon-based surfactant.
Examples of the fluorine-based and/or silicon-based surfactants include the surfactants disclosed in paragraphs [0218] and [0219] of International Publication No. 2018/193954.

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, and 0.0005 to 2.0% by mass, based on the total solid content of the composition of the present invention. It is more preferably 1.0% by mass, and even more preferably 0.1 to 1.0% by mass.

<Solvent>
Preferably, the composition of the present invention contains a solvent.
The solvent consists of (M1) propylene glycol monoalkyl ether carboxylate, and (M2) propylene glycol monoalkyl ether, lactic acid ester, acetate ester, alkoxypropionic acid ester, chain ketone, cyclic ketone, lactone, and alkylene carbonate. It is preferable that at least one selected from the group is included. Note that the above solvent may further contain components other than components (M1) and (M2).

It is preferable to combine the above-mentioned solvent and the above-mentioned resin from the viewpoint of improving the coating properties of the composition of the present invention and reducing the number of pattern development defects. Since the above-mentioned solvent has a good balance between the solubility, boiling point and viscosity of the above-mentioned resin, it is possible to suppress uneven film thickness of actinic ray-sensitive or radiation-sensitive films and the occurrence of precipitates during spin coating. can.
Details of component (M1) and component (M2) are described in paragraphs [0218] to [0226] of International Publication No. 2020/004306, 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 based on the total amount of the solvent.

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

Note that the solid content refers to all components other than the solvent, and as described above, refers to components that form an actinic ray-sensitive or radiation-sensitive film.
The solid content concentration is the mass percentage of the mass of other components excluding the solvent with respect to the total mass of the composition of the present invention.
"Total solid content" refers to the total mass of the components excluding the solvent from the entire composition of the composition of the present invention. Further, as described above, the "solid content" refers to components excluding the solvent, and may be solid or liquid at 25° C., for example.

<Other additives>
The composition of the present invention includes a dissolution inhibiting compound, a dye, a plasticizer, a photosensitizer, a light absorber, and/or a compound that promotes solubility in a developer (for example, a phenol compound having a molecular weight of 1000 or less, or It may further contain an alicyclic or aliphatic compound containing a carboxyl group.

The above-mentioned "dissolution-inhibiting compound" is a compound with a molecular weight of 3000 or less that decomposes under the action of an acid and reduces its solubility in an organic developer.

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

[Actinic ray-sensitive or radiation-sensitive film, pattern formation method]
The invention also relates to actinic- or radiation-sensitive films formed with the compositions of the invention. The actinic ray-sensitive or radiation-sensitive film of the present invention is preferably a resist film.
The pattern obtained using the composition of the present invention may be positive or negative, but is preferably positive.
Although the procedure of the pattern forming method using the composition of the present invention is not particularly limited, it is preferable to include the following steps.
Step 1: Step of forming an actinic ray-sensitive or radiation-sensitive film on a substrate using the composition of the present invention Step 2: Step of exposing the above-mentioned actinic ray-sensitive or radiation-sensitive film Step 3: Step 3: Step of exposing the above-mentioned actinic ray-sensitive or radiation-sensitive film to light Step of developing an actinic ray-sensitive or radiation-sensitive film using a developer The procedure of each of the above steps will be described in detail below.

(Step 1: Actinic ray-sensitive or radiation-sensitive film formation step)
Step 1 is a step of forming an actinic ray-sensitive or radiation-sensitive film on a substrate using the composition of the present invention.

Examples of the method for forming an actinic ray-sensitive or radiation-sensitive film on a substrate using the composition of the present invention include a method of coating the composition of the present invention on a substrate.
In addition, it is preferable to filter the composition of the present invention through a filter 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. The filter is preferably made of polytetrafluoroethylene, polyethylene, or nylon.

The compositions of the present invention can be applied by any suitable application method, such as a spinner or coater, onto substrates (eg, silicon, silicon dioxide coated) such as those used in the manufacture of integrated circuit devices. The coating method is preferably spin coating using a spinner. The rotation speed during 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 an actinic ray-sensitive or radiation-sensitive film. Note that, if necessary, various base films (inorganic film, organic film, antireflection film) may be formed under the actinic ray-sensitive or radiation-sensitive film.

Examples of the drying method include a method of drying by heating. Heating can be carried out using a means provided in an ordinary exposure machine and/or developing machine, or 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.

The thickness of the actinic ray-sensitive or radiation-sensitive film is not particularly limited, but is preferably 10 to 120 nm from the viewpoint of forming fine patterns with higher precision. Among these, in the case of EUV exposure, the thickness of the actinic ray-sensitive or radiation-sensitive film is more preferably 10 to 65 nm, and even more preferably 15 to 50 nm. In the case of ArF immersion exposure, the thickness of the actinic ray-sensitive or radiation-sensitive film is more preferably 10 to 120 nm, and even more preferably 15 to 90 nm.

Note that a top coat may be formed on the actinic ray-sensitive or radiation-sensitive film using a top coat composition.
It is preferable that the top coat composition is not mixed with the actinic ray-sensitive or radiation-sensitive film and can be uniformly applied to the upper layer of the actinic ray-sensitive or radiation-sensitive film. The top coat is not particularly limited, and a conventionally known top coat can be formed by a conventionally known method. Can be formed.
For example, it is preferable to form a top coat containing a basic compound as described in JP-A-2013-61648 on the actinic ray-sensitive or radiation-sensitive film. Specific examples of basic compounds that may be included in the top coat include basic compounds that may be included in the composition of the present invention.
It is also preferable that the top coat 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 actinic ray-sensitive or radiation-sensitive film.
Examples of the exposure method include a method of irradiating the formed actinic ray-sensitive or radiation-sensitive film with actinic rays or radiation through a predetermined mask.
Examples of active light 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, and 1 to 200 nm. Particularly preferred are deep ultraviolet light of wavelengths, specifically KrF excimer laser (248 nm), ArF excimer laser (193 nm), F ₂ excimer laser (157 nm), EUV (13.5 nm), X-rays, and electron beams.

It is preferable to perform baking (heating) after exposure and 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, and even more preferably 30 to 120 seconds.
Heating can be carried out using a means provided in a normal exposure machine and/or developing machine, and may also be carried out using a hot plate or the like.
This step is also called post-exposure bake.

(Process 3: Development process)
Step 3 is a step of developing the exposed actinic ray-sensitive or radiation-sensitive 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). The developer is preferably an alkaline developer.

Development methods include, for example, a method in which the substrate is immersed in a tank filled with a developer for a certain period of time (dip method), a method in which the developer is raised on the surface of the substrate by surface tension and left to stand for a certain period of time (paddle method). method), a method in which the developer is sprayed onto the surface of the substrate (spray method), and a method in which the developer is continuously discharged while scanning a developer discharge nozzle at a constant speed onto a rotating substrate (dynamic dispensing method). ).
Furthermore, after the step of developing, a step of stopping the development may be carried out while substituting another solvent.
The development time is not particularly limited as long as the resin in the unexposed areas 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.

As the alkaline developer, it is preferable to use an alkaline aqueous solution containing an alkali. The type of alkaline aqueous solution is not particularly limited, but examples include quaternary ammonium salts represented by tetramethylammonium hydroxide, inorganic alkalis, primary amines, secondary amines, tertiary amines, alcohol amines, or cyclic amines. Examples include alkaline aqueous solutions containing. Among these, the alkaline developer is preferably an aqueous solution of a quaternary ammonium salt typified by tetramethylammonium hydroxide (TMAH). Appropriate amounts of alcohols, surfactants, etc. may be added to the alkaline developer. The alkaline concentration of the alkaline developer is usually preferably 0.1 to 20% by mass. The pH of the alkaline developer is usually preferably 10.0 to 15.0.

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. It is preferable that there be.

A plurality of the above-mentioned solvents may be mixed together, or may be mixed with a solvent other than the above-mentioned ones 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, based on the total amount of the developer. The following is more preferable, and 95% by mass or more and 100% by mass or less is particularly preferable.

(Other processes)
It is preferable that the pattern forming method includes a step of cleaning using a rinsing liquid after step 3.

Examples of the rinsing solution used in the rinsing step after the step of developing using an alkaline developer include pure water. Note that an appropriate amount of a surfactant may be added to the pure water.
An appropriate amount of surfactant may be added to the rinse liquid.

The rinsing solution used in the rinsing step after the development step using an organic developer is not particularly limited as long as it does not dissolve the pattern, and solutions containing common organic solvents can be used. The rinsing liquid 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 process is not particularly limited, and examples include a method in which the rinsing liquid is continuously discharged onto the substrate rotating at a constant speed (rotary coating method), and a method in which the substrate is immersed in a tank filled with the rinsing liquid for a certain period of time. (dip method) and a method of spraying a rinsing liquid onto the substrate surface (spray method).
Further, the pattern forming method may include a heating step (Post Bake) after the rinsing step. In this step, the developer and rinse solution remaining between patterns and inside the patterns due to baking are removed. This step also has the effect of smoothing the resist pattern and improving surface roughness 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).

Further, 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 lower film and the substrate) to form a pattern on the substrate.
The method of processing the substrate (or the lower layer film and the substrate) is not particularly limited, but by performing dry etching on the substrate (or the lower layer film and the substrate) using the pattern formed in step 3 as a mask, the substrate is processed. A method of forming a pattern is preferred. The 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, rinsing liquid, composition for forming an antireflective film, composition for forming a top coat, etc.) do not contain impurities such as metals. It is preferable not to include it. 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, and particularly 10 mass ppt or less. Preferably, 1 mass ppt or less is most preferable. 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, Examples include W and Zn.

Examples of methods for removing impurities such as metals from various materials include filtration using a filter. Details of filtration using a filter are described in paragraph [0321] of International Publication No. 2020/004306.

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

In addition to filter filtration, impurities may be removed using an adsorbent, or a combination of filter filtration and an adsorbent may be used. As the adsorbent, known adsorbents can be used, such as inorganic adsorbents such as silica gel and zeolite, and organic adsorbents such as activated carbon. In order to reduce impurities such as metals contained in the various materials mentioned above, it is necessary to prevent metal impurities from being mixed in during the manufacturing process. Whether metal impurities have been sufficiently removed from the manufacturing equipment can be confirmed by measuring the content of metal components contained in the cleaning liquid used to clean the manufacturing equipment. The content of metal components contained in the cleaning liquid after use is preferably 100 parts per trillion or less, more preferably 10 parts per trillion 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 contain conductive compounds to prevent damage to chemical piping and various parts (filters, O-rings, tubes, etc.) due to static electricity charging and subsequent electrostatic discharge. may be added. The conductive compound is not particularly limited, and for example, methanol may be mentioned. 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 favorable development characteristics or rinsing characteristics. The lower limit is not particularly limited, and is preferably 0.01% by mass or more.
Examples of chemical liquid piping include SUS (stainless steel), polyethylene or polypropylene treated with antistatic treatment, or various types of piping coated with fluororesin (polytetrafluoroethylene, perfluoroalkoxy resin, etc.). can be used. Similarly, for the filter and O-ring, antistatically treated polyethylene, polypropylene, or fluororesin (polytetrafluoroethylene, perfluoroalkoxy resin, etc.) can be used.

[Manufacturing method of electronic device]
The present specification also relates to an electronic device manufacturing method including the above-described pattern forming method, and an electronic device manufactured by this manufacturing method.
Preferred embodiments of the electronic device of this specification include embodiments in which it is installed in electrical and electronic equipment (home appliances, office automation (OA), media-related equipment, optical equipment, communication equipment, etc.).

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

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

<Resin (A)>
As the resin (A), A-1 to A-36 were used.
Further, AT-1 to AT-2 were used as resins other than resin (A). For convenience, AT-1 to AT-2 are also listed in the column of resin (A) in Table 1 below.
Resin (A) was synthesized according to the synthesis method for resin A-1 (Synthesis Example 1) described below.

Table 1 shows the composition ratio (mol% ratio; corresponding sequentially from the left), weight average molecular weight (Mw), and degree of dispersion (Mw/Mn) of each repeating unit shown below.
The weight average molecular weight (Mw) and dispersion degree (Pd=Mw/Mn) of the resin were measured by GPC (carrier: tetrahydrofuran (THF)) (the amount is in terms of polystyrene). Further, the content of repeating units was measured by ¹³ C-NMR (nuclear magnetic resonance).

Structure of each repeating unit a-1 to a-27, b-1 to b-12, c-1 to c-11, and d-1 to d-5, d-7 to d-15 shown in Table 1 is shown below. Regarding a-1 to a-27, the structures of the corresponding monomers are shown.

<Synthesis Example 1: Synthesis of Resin A-1>
A synthesis example of A-1 is shown below. Other resins (A) were also synthesized in the same manner.

(Synthesis of monomer (a-1))

- Synthesis of intermediate (a-1-1) 4-vinylbenzoic acid (20.0 g, 135 mmol) is dispersed in 100 mL of dichloromethane, dimethylformamide (10 μl) is added, and the mixture is heated to 40° C. and refluxed. After adding thionyl chloride (16.1 g, 135 mmol) dropwise, the mixture was stirred at 40°C for 2 hours. The solvent was distilled off from the reaction mixture under reduced pressure to obtain 22.1 g of intermediate (aa-1). Intermediate (aa-1) was used in the next reaction without further purification.

- Synthesis of monomer (a-1) Thiophene-2-carbaldehyde (15.7 g, 140 mmol) and 125 mL of tetrahydrofuran (THF) were mixed and cooled to -10° C. under a nitrogen atmosphere. 130 ml (130 mmol) of methylmagnesium bromide (1.0 M tetrahydrofuran solution) was added dropwise, and the mixture was further stirred at -10°C for 1 hour. Intermediate (a-1-1) (20.0 g, 120 mmol) was added dropwise to the reaction solution cooled to -10°C. After stirring at 65° C. for 1 hour, 500 mL of n-hexane and 500 mL of distilled water were added to perform a liquid separation operation. The solvent in the organic layer was distilled off under reduced pressure. The residue was purified by silica gel column chromatography (eluent: ethyl acetate/n-hexane = 3/97 (volume ratio)) to obtain 21.3 g of monomer (a-1). Compound identification was performed by electrospray ionization mass spectrometry (ESI-MS).
MS-ESI (positive) m/z=257.3 [M] ⁺

(Synthesis of resin A-1)

(M-1), (M-2), and (a-1) are used as monomers, and the mole of each monomer is (M-1):(M-2):(a-1)=55/10/35. Add cyclohexanone so that the monomer concentration is 30 wt%, add 8 mol% of initiator dimethyl 2,2'-azobis(2-methylpropionate), and adjust the monomer solution. did. 0.1 times the mass of cyclohexanone was heated to 85° C. under a nitrogen atmosphere, and the monomer solution was added dropwise over 2 hours, followed by further reaction at 85° C. for 2 hours. The obtained resin solution was dropped into a mixed solvent of ethyl acetate:n-heptane=1:9 (volume ratio) to precipitate the resin, filter it, collect it, and vacuum dry it to obtain Resin A- with a yield of 69%. I got 1.

The following resins (AX-1) to (AX-6) were used in comparative examples. The number at the bottom right of each repeating unit represents the content ratio (molar ratio) of each repeating unit.

<Photoacid generator (B)>
As the photoacid generator (B), among the compounds (B-1) to (B-80) shown in Table 2 below, compounds (B-2) to (B-6), (B-8), ( B-10), (B-17), (B-18), (B-23), (B-24), (B-29), (B-33), (B-38), (B- 39), (B-46), (B-48), (B-51) to (B-53), (B-56), (B-57), (B-62), (B-68) , (B-70), (B-77), (B-78), and (B-80) were used.
Compounds (B-1) to (B-80) are formed by combining the cations listed in Table 2 and the anions listed in Table 2.

Using the above software package 1, it was confirmed that the pKa of the acids generated by compounds (B-1) to (B-80) was -10 or more and 5 or less. Note that Me represents a methyl group.

The structures of the cations listed in Table 2 are shown below. Me represents a methyl group, and Bu represents an n-butyl group.

The structures of the anions listed in Table 2 are shown below. Me represents a methyl group, and Bu represents an n-butyl group.

The following compounds (BX-1) and (BX-2) were also used as photoacid generators (B).

<Acid diffusion control agent>
As acid diffusion control agents, the following C-1 to C-14 were used.

<Surfactant>
As surfactants, the following W-1 to W-4 were used.
W-1: Megafac R08 (manufactured by Dainippon Ink and Chemicals Co., Ltd.; fluorine and silicone-based)
W-2: Polysiloxane polymer KP-341 (manufactured by Shin-Etsu Chemical Co., Ltd.; silicone-based) W-3: Troysol S-366 (manufactured by Troy Chemical Co., Ltd.; fluorine-based)
W-4: PF6320 (manufactured by OMNOVA; fluorine-based)

<Solvent>
The solvents used are shown below.
S-1: Diacetone alcohol (DAA)
S-2: Propylene glycol monomethyl ether acetate (PGMEA)
S-3: Propylene glycol monomethyl ether (PGME)
S-4: Ethyl lactate (EL)
S-5: Ethyl 3-ethoxypropionate (EEP)
S-6: 2-heptanone (MAK)
S-7: Methyl 3-methoxypropionate (MMP)
S-8: 3-methoxybutyl acetate S-9: γ-butyrolactone

<Preparation of resist composition>
The components shown in Table 3 were dissolved in the solvent shown in the same table to prepare a solution at the solid content concentration shown in the same table, and this was filtered through a polyethylene filter having a pore size of 0.02 μm to prepare a resist composition R. -1 to R-44 and RX-1 to RX-6 were obtained.
Note that the solid content means all components other than the solvent. The obtained resist compositions were used in Examples and Comparative Examples.

<Coating of resist composition>
The prepared resist composition was applied onto a 6-inch Si (silicon) wafer that had been previously treated with hexamethyldisilazane (HMDS) using a spin coater Mark 8 manufactured by Tokyo Electron, and dried on a hot plate at 130° C. for 300 seconds. As a result, a resist film having a thickness of 100 nm was obtained.
Here, 1 inch is 0.0254 m.
Note that similar results can be obtained even if the Si wafer is replaced with a chromium substrate.

<Pattern formation method (1): EB exposure, alkaline development (positive)>
The wafer coated with the resist film obtained above was subjected to pattern irradiation using an electron beam drawing device (manufactured by Advantest Corporation; F7000S, acceleration voltage 50 keV). At this time, drawing was performed so that a 1:1 line and space was formed. After electron beam drawing, it was heated on a hot plate at 100°C for 60 seconds, immersed in a 2.38% by mass tetramethylammonium hydroxide (TMAH) aqueous solution for 60 seconds, rinsed with water for 30 seconds, and dried. . Thereafter, the wafer was rotated at a rotation speed of 4000 rpm for 30 seconds, and then baked at 95° C. for 60 seconds to dry it.

[evaluation]
The irradiation energy used to resolve a 1:1 line-and-space pattern with a line width of 50 nm was defined as the sensitivity (Eop).

<L/S resolution>
The critical resolving power (minimum line width at which lines and spaces (line:space=1:1) are separated and resolved) at the exposure amount showing the above sensitivity (Eop) was defined as the resolving power (nm).

<Line with roughness (LWR) performance>
Line width roughness is determined by measuring the line width at arbitrary 50 points of 0.5 μm in the longitudinal direction of a line and space pattern (line: space = 1:1) with a line width of 50 nm in the above Eop, and measuring the standard deviation ( σ) was determined, and 3σ (nm) was calculated. The smaller the value, the better the performance.

<Pattern shape>
The cross-sectional shape of a 1:1 line-and-space pattern with a line width of 50 nm at the irradiation dose exhibiting the above sensitivity was observed using a scanning electron microscope (S-4800, manufactured by Hitachi, Ltd.). In the cross-sectional shape of a line pattern, the ratio expressed by [line width at the top part (surface part) of the line pattern/line width at the middle part of the line pattern (at a height position half the height of the line pattern)] is 1. 1 or more is considered a "reverse taper", a ratio of 1.03 or more but less than 1.1 is considered a "slightly reverse taper", and a ratio of less than 1.03 is considered a "rectangle". Ta.

Table 4 below shows the resist compositions used and the results.

<Pattern formation method (2): EUV exposure, alkaline development (positive)>
The wafer coated with the resist film obtained above was exposed using an EUV exposure device (Exitech Micro Exposure Tool, NA (numerical aperture) 0.3, Quadrupole, outer sigma 0.68, inner sigma 0.36). , pattern exposure was performed using an exposure mask (line/space=1/1). After exposure, it was heated on a hot plate at 100° C. for 90 seconds, immersed in a 2.38% by mass tetramethylammonium hydroxide (TMAH) aqueous solution for 60 seconds, and then rinsed with water for 30 seconds. Thereafter, the wafer was rotated at a rotation speed of 4000 rpm for 30 seconds, and then baked at 95° C. for 60 seconds to dry it.

[evaluation]
Resolution, LWR performance, and pattern shape were evaluated using the same methods as described above.

Table 5 below shows the resist compositions used and the results.

From the results in Tables 4 and 5, it was found that the resist compositions used in the examples had excellent resolution and LWR performance, and that excellent pattern shapes could be obtained.

Although the 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. 2022-107408) filed on July 1, 2022, the contents of which are incorporated herein by reference.

Claims

An actinic ray-sensitive or radiation-sensitive resin composition containing the following (A) and (B).
(A) A resin containing a repeating unit (a) represented by the following general formula (a) that decomposes under the action of an acid and has a group whose polarity changes. (B) Generates an acid when irradiated with actinic rays or radiation. Compound

In general formula (a), R 101 to R 103 each independently represent a hydrogen atom, an organic group, or a halogen atom. However, R 102 may be combined with L 101 to form a ring, and in that case R 102 represents a single bond, an alkylene group, or an alkenylene group.
L 101 represents a divalent aromatic ring group. When bonded with R 102 to form a ring, it represents a trivalent aromatic ring group.
R 104 and R 105 each independently represent a hydrogen atom, an alkyl group, an aryl group, a heteroaryl group, an alkenyl group, or an alkynyl group.
R 106 represents an aromatic heterocyclic group in which lone pairs of heteroatoms constitute a conjugated system. R 104 to R 106 may be bonded to each other to form a ring.
2. The activity-sensitive compound according to claim 1, wherein in the general formula (a), R 106 is a monocyclic or polycyclic aromatic heterocyclic group having a 5-membered ring skeleton containing S, O, N, Se, or Te. Photosensitive or radiation sensitive resin composition.
The actinic ray-sensitive ray according to claim 1 or 2, wherein the repeating unit represented by the general formula (a) is a repeating unit represented by any of the following general formulas (a-2) to (a-7). radiation-sensitive resin composition.

In general formulas (a-2) to (a-7), R 111 to R 113 each independently represent a hydrogen atom, an organic group, or a halogen atom.
L 111 represents a divalent aromatic ring group.
R 114 and R 115 each independently represent a hydrogen atom, an alkyl group, an aryl group, a heteroaryl group, an alkenyl group, or an alkynyl group.
R 114 and R 115 may be combined with each other to form a ring.
R 117 to R 121 each independently represent a hydrogen atom or a substituent. R 117 to R 121 may be bonded to each other to form a ring.
A represents S, O, N(R), Se, or Te. R represents a hydrogen atom or a substituent.
Actinic ray-sensitive or sensitive material according to claim 3, wherein the repeating unit represented by the general formula (a) is a repeating unit represented by the general formula (a-2) or the general formula (a-3). Radioactive resin composition.
The actinic ray-sensitive or radiation-sensitive resin composition according to claim 3, wherein the repeating unit represented by the general formula (a) is a repeating unit represented by the general formula (a-2).
The actinic ray-sensitive or radiation-sensitive resin composition according to claim 1 or 2, wherein L 101 in the general formula (a) is a phenylene group.
The actinic ray-sensitive or radiation-sensitive resin composition according to claim 1 or 2, wherein the total number of carbon atoms contained in R 104 and R 105 in the general formula (a) is 1 or more.
The actinic ray-sensitive or radiation-sensitive resin composition according to claim 1 or 2, wherein the resin (A) further contains a repeating unit (c) represented by the following general formula (c).

In general formula (c), R 61 to R 63 each independently represent a hydrogen atom, an organic group, or a halogen atom. However, R 62 may combine with Ar to form a ring, and in that case R 62 represents a single bond or an alkylene group.
L represents a single bond or a divalent linking group.
Ar represents a (k+1)-valent aromatic ring, and when bonded with R 62 to form a ring, represents a (k+2)-valent aromatic ring group.
k represents an integer from 1 to 5.
The actinic ray-sensitive or radiation-sensitive resin composition according to claim 1 or 2, wherein the content of the repeating unit (a) is 10% by mass or more based on the total mass of the resin (A).
The actinic ray-sensitive or radiation-sensitive resin composition according to claim 1 or 2, wherein the compound (B) is a compound represented by the following general formula (1).

In general formula (1), R 1 and R 5 each independently represent an aryl group or a heteroaryl group.
R 2 to R 4 each independently represent a hydrogen atom or a substituent.
M n+ represents a cation.
n represents an integer of 1 or more.
The actinic ray-sensitive or radiation-sensitive resin composition according to claim 10, wherein R 3 in the general formula (1) represents an aryl group.
In the general formula (1), at least one of R 1 to R 5 is a group containing a polar group, a group containing a group whose polarity increases when decomposed by the action of an acid, or a group which decomposes by the action of an alkaline developer. The actinic ray-sensitive or radiation-sensitive resin composition according to claim 10, which is a group containing a group that increases solubility in an alkaline developer.
The actinic ray-sensitive or radiation-sensitive resin composition according to claim 10, wherein R 1 , R 3 , and R 5 in the general formula (1) are each a group represented by the following general formula (Ar). .

In the general formula (Ar), R 6 to R 10 each independently represent a hydrogen atom or a substituent. At least one of R 6 to R 10 is a group containing a polar group, a group containing a group whose polarity increases when decomposed by the action of an acid, or a group which decomposes by the action of an alkaline developer and has solubility in the alkaline developer. It is a group containing a group in which . * represents a bond to the benzene ring in general formula (1).
The actinic ray-sensitive or radiation-sensitive resin composition according to claim 10, wherein R 1 , R 3 , and R 5 in the general formula (1) are each a group represented by the following general formula (Ar1). .

In the general formula (Ar1), R 11 to R 15 each independently represent a hydrogen atom or a substituent, and at least one of R 11 to R 15 represents the following substituent Y. * represents a bond to the benzene ring in general formula (1).
Substituent Y: hydroxy group, carboxyl group, group having a carbonyl bond, acyloxy group, alkoxycarbonyloxy group, aryloxycarbonyloxy group, aryloxycarbonyl group, alkoxycarbonyl group, carbamoyl group, or imido group
An actinic ray-sensitive or radiation-sensitive film formed from the actinic ray-sensitive or radiation-sensitive resin composition according to claim 1 or 2.
An actinic ray-sensitive or radiation-sensitive film forming step of forming an actinic ray-sensitive or radiation-sensitive film on a substrate using the actinic ray-sensitive or radiation-sensitive resin composition according to claim 1 or 2;
an exposure step of exposing the actinic ray-sensitive or radiation-sensitive film;
A pattern forming method comprising a developing step of developing the exposed actinic ray-sensitive or radiation-sensitive film using a developer.
A method for manufacturing an electronic device, comprising the pattern forming method according to claim 16.