KR20240031384A - Actinic ray-sensitive or radiation-sensitive resin composition, actinic ray-sensitive or radiation-sensitive film, pattern formation method, and electronic device manufacturing method - Google Patents

Abstract

An actinic ray-sensitive or radiation-sensitive resin composition that has excellent EL performance and LWR performance and can reduce development defects, an actinic ray-sensitive or radiation-sensitive film using the composition, a pattern formation method, and the production of an electronic device Provides a method. The actinic ray-sensitive or radiation-sensitive resin composition includes a resin (A) whose polarity is increased by the action of an acid, and a compound represented by the general formula (DA1) described in the specification.

Description

Actinic ray-sensitive or radiation-sensitive resin composition, actinic ray-sensitive or radiation-sensitive film, pattern formation 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 formation method, and a manufacturing method of an electronic device. More specifically, the present invention relates to ultra-microlithography processes applicable to ultra-LSI (Large Scale Integration) and high-capacity microchip manufacturing processes, nanoimprint mold creation processes and high-density information recording media manufacturing processes, and other photo It relates to an actinic ray-sensitive or radiation-sensitive resin composition suitably used in a fabrication process, an actinic ray-sensitive or radiation-sensitive film, a pattern formation method, and a manufacturing method of an electronic device.

Conventionally, in the manufacturing process of semiconductor devices such as IC (Integrated Circuit) and LSI, microprocessing by lithography using a photoresist composition is performed. Recently, with the high integration of integrated circuits, the formation of ultra-fine patterns in the submicron or quarter micron region has become required. Accordingly, the exposure wavelength also shows a tendency to become shorter, such as from the g-line to the i-line and back to the KrF excimer laser light, and currently, an exposure machine using an ArF excimer laser with a 193 nm wavelength as a light source is being developed. In addition, as a technology to further increase resolution, the development of the so-called liquid immersion method, in which the space between the projection lens and the sample is filled with a high refractive index liquid (hereinafter also referred to as “immersion liquid”), is in progress.

Additionally, in addition to excimer laser light, lithography using electron beams (EB), X-rays, extreme ultraviolet rays (EUV), etc. is currently being developed. Accordingly, chemically amplified resist compositions that effectively respond to various types of radiation and have excellent sensitivity and resolution are being developed.

For example, Patent Documents 1 and 2 describe a resist composition containing a nitrogen-containing compound having an iodine atom as a resist.

Patent Document 1: Japanese Patent Publication No. 2018-97356 Patent Document 2: Japanese Patent Publication No. 2020-27297

However, the resist compositions described in Patent Documents 1 and 2 have problems in that they are inferior in exposure latitude (EL) performance and line width roughness (LWR) performance and have many development defects. LWR performance refers to the ability to reduce the LWR of a pattern.

The object of the present invention is to provide an actinic ray-sensitive or radiation-sensitive resin composition that is excellent in EL performance and LWR performance and can reduce development defects. Additionally, the present invention aims to provide an actinic ray-sensitive or radiation-sensitive film, a pattern formation method, and an electronic device manufacturing method using the actinic ray-sensitive or radiation-sensitive resin composition.

The present inventors have found that the above-mentioned problem can be achieved by the following configuration.

[One]

An actinic ray-sensitive or radiation-sensitive resin composition comprising a resin (A) whose polarity increases by the action of an acid, and a compound represented by the following general formula (DA1).

[Formula 1]

In the general formula (DA1),

X ¹ represents a sulfur atom or NQ ³ .

Q ³ represents a hydrogen atom, an organic group, -OH, or -NH ₂ .

Q ¹ represents a hydrogen atom or a substituent.

X ² represents a linking group Xz or a single bond.

The linking group Xz is a divalent linking group consisting of at least one atom selected from the group consisting of a carbon atom, an oxygen atom, a nitrogen atom, and a sulfur atom. However, the nitrogen atom may be bonded to a hydrogen atom, an alkyl group, an aryl group, or an aromatic heterocyclic group, and the sulfur atom may be bonded to a hydrocarbon group.

Ar ^a1 represents an aromatic group.

Q ² represents a hydrogen atom or an alkyl group.

Q ¹ and Q ² may be combined to form a ring.

At least one selected from the group consisting of Q ¹ and Q ² and Q ³ may combine to form a ring.

k represents an integer from 1 to 5.

m represents an integer from 1 to 3.

n and p each independently represent an integer of 0 to 2.

However, m+n+p=3.

When there are multiple X ¹ , X ² , Q ¹ , Q ² , Q ³ and Ar ^a1 , they may be the same or different.

However, when n represents 0, the following condition (i) or (ii) is satisfied.

Condition (i): X ² represents a single bond, and Ar ^a1 represents an aromatic heterocyclic group.

Condition (ii): X ² represents the linking group Xz.

[2]

The actinic light-sensitive or radiation-sensitive product described in [ ¹ ], wherein Resin composition.

[Formula 2]

In the above formula, Q ⁴ and Q ⁵ each independently represent a hydrogen atom, an alkyl group, an aryl group, or an aromatic heterocyclic group. X ³ and X ⁴ each independently represent a single bond, a hydrocarbon group, an oxygen atom, or NQ ⁶ . Q ⁶ represents a hydrogen atom, an alkyl group, an aryl group, or an aromatic heterocyclic group. X ⁵ represents an oxygen atom, a sulfur atom, or NG ¹ . X ⁶ represents -SG ² or -NG ³ G ⁴ . G ¹ , G ³ and G ⁴ each independently represent a hydrogen atom, an alkyl group, an aryl group, or an aromatic heterocyclic group. G ² represents a hydrocarbon group. *1 represents the bonding position with the nitrogen atom in general formula (DA1), and *2 represents the bonding position with Ar ^a1 in general formula (DA1).

[3]

[ The actinic ray-sensitive or radiation-sensitive resin composition according to [1] or [2].

[Formula 3]

In general formula (3),

R ₅ to R ₇ each independently represent a hydrogen atom, an alkyl group, a cycloalkyl group, a halogen atom, a cyano group, or an alkoxycarbonyl group.

L ₂ represents a divalent linking group.

R ₈ to R ₁₀ each independently represent an alkyl group, cycloalkyl group, aryl group, aralkyl group, or alkenyl group. Two of R ₈ to R ₁₀ may combine with each other to form a ring.

[Formula 4]

In general formula (6),

R ₂₂ to R ₂₄ each independently represent a hydrogen atom, an alkyl group, a cycloalkyl group, a halogen atom, a cyano group, or an alkoxycarbonyl group.

L ₄ represents a single bond or a divalent linking group.

Ar ₁ represents an aromatic group.

R ₂₅ to R ₂₇ each independently represent a hydrogen atom, an alkyl group, a cycloalkyl group, an aryl group, an aralkyl group, or an alkenyl group.

R ₂₆ and R ₂₇ may be combined to form a ring.

R ₂₄ or R ₂₅ may be combined with Ar ₁ .

[Formula 5]

In general formula (7),

R ₂₈ to R ₃₀ each independently represent a hydrogen atom, an alkyl group, a cycloalkyl group, a halogen atom, a cyano group, or an alkoxycarbonyl group.

L ₅ represents a single bond or a divalent linking group.

R ₃₁ and R ₃₂ each independently represent a hydrogen atom, an alkyl group, a cycloalkyl group, an aryl group, an aralkyl group, or an alkenyl group.

R ₃₃ represents an alkyl group, cycloalkyl group, aryl group, aralkyl group, or alkenyl group.

R ₃₂ and R ₃₃ may be combined to form a ring.

[4]

The actinic ray-sensitive or radiation-sensitive resin composition according to any one of [1] to [3], wherein the resin (A) has a repeating unit represented by the following general formula (A2).

[Formula 6]

In general formula (A2),

R ₁₀₁ , R ₁₀₂ and R ₁₀₃ each independently represent a hydrogen atom, an alkyl group, a cycloalkyl group, a halogen atom, a cyano group or an alkoxycarbonyl group.

L _A represents a single bond or a divalent linking group.

Ar _A represents an aromatic group.

k represents an integer of 1 to 5.

However, R ₁₀₂ may be bonded to Ar _A , and when R ₁₀₂ and Ar _A are bonded, R ₁₀₂ represents a single bond or an alkylene group.

[5]

The actinic ray-sensitive or radiation-sensitive resin composition according to any one of [1] to [4], wherein n in the general formula (DA1) represents 1 or 2.

[6]

The actinic ray-sensitive or radiation-sensitive resin composition according to [5], wherein Q ¹ in the general formula (DA1) represents a substituent containing a nitrogen atom.

[7]

In the general formula (DA1), n represents 0, satisfies the above condition (i), and Ar ^a1 represents an aromatic heterocyclic group containing a nitrogen atom, according to any one of [1] to [4]. Actinic ray-sensitive or radiation-sensitive resin composition.

[8]

The actinic ray-sensitive or radiation-sensitive resin composition according to any one of [1] to [7], wherein the pKa of the conjugate acid of the compound represented by the general formula (DA1) is 2 or more.

[9]

The actinic ray-sensitive or radiation-sensitive resin composition according to any one of [1] to [8], wherein the compound represented by the general formula (DA1) is a nonionic compound.

[10]

An actinic ray-sensitive or radiation-sensitive film formed using the actinic ray-sensitive or radiation-sensitive resin composition according to any one of [1] to [9].

[11]

A process of forming a resist film using the actinic ray-sensitive or radiation-sensitive resin composition according to any one of [1] to [9];

A process of exposing the resist film;

A pattern forming method comprising a step of developing the exposed resist film using a developer.

[12]

A method of manufacturing an electronic device including the pattern forming method described in [11].

According to the present invention, an actinic ray-sensitive or radiation-sensitive resin composition that has excellent EL performance and LWR performance and can reduce development defects can be provided. Furthermore, according to the present invention, an actinic ray-sensitive or radiation-sensitive film, a pattern formation method, and an electronic device manufacturing method using the actinic ray-sensitive or radiation-sensitive resin composition can be provided.

Figure 1 is an NMR chart of compound (D-1) obtained in Synthesis Example 2.

Hereinafter, the present invention will be described in detail.

The description of the structural requirements described below may be based on representative embodiments of the present invention, but the present invention is not limited to such embodiments.

“Active rays” or “radiation” in this specification include, for example, the bright line spectrum of a mercury lamp, deep ultraviolet rays represented by excimer lasers, extreme ultraviolet (EUV) rays, X-rays, soft X-rays, and electron rays. (EB: Electron Beam), etc. “Light” in this specification means actinic rays or radiation. In this specification, unless otherwise specified, “exposure” refers to exposure not only to bright line spectrum of a mercury lamp, deep ultraviolet rays represented by excimer lasers, extreme ultraviolet rays, X-rays, and EUV, but also to particles such as electron beams and ion beams. It also includes drawing with lines.

In this specification, "~" is used to mean that the numerical values written before and after it are included as the lower limit and the upper limit.

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

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

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

Regarding the notation of groups (atomic groups) in this specification, notations that do not describe substitution or unsubstitution include groups that have a substituent as well as groups that do not have a substituent. For example, “alkyl group” includes not only an alkyl group without a substituent (unsubstituted alkyl group) but also an alkyl group with a substituent (substituted alkyl group).

“Organic group” in this specification refers to a group containing at least one carbon atom.

In addition, in this specification, when “may have a substituent”, the type of substituent, the position of the substituent, and the number of substituents are not particularly limited. The number of substituents may be, for example, 1, 2, 3, or more. Examples of the substituent include a monovalent non-metallic atom group excluding a hydrogen atom, and can be selected from the following substituents T, for example.

(substituent T)

Examples of the substituent T include halogen atoms such as fluorine atom, chlorine atom, bromine atom, and iodine atom; Alkoxy groups such as methoxy group, ethoxy group, and tert-butoxy group; Aryloxy groups such as phenoxy group and p-tolyloxy group; Alkoxycarbonyl groups such as methoxycarbonyl group, butoxycarbonyl group, and phenoxycarbonyl group; Acyloxy groups such as acetoxy group, propionyloxy group, and benzoyloxy group; Acyl groups such as acetyl group, benzoyl group, isobutyryl group, acryloyl group, methacryloyl group, and methoxyl group; alkylsulfanyl groups such as methylsulfanyl group and tert-butylsulfanyl group; Arylsulfanyl groups such as phenylsulfanyl group and p-tolylsulfanyl group; Alkyl group (eg, carbon number 1 to 10); Cycloalkyl group (for example, 3 to 20 carbon atoms); Aryl group (e.g., carbon atoms 6 to 20); heteroaryl group; hydroxyl group; carboxylic acid; form diary; tongue group; Cyano group; Alkylaminocarbonyl group; Arylaminocarbonyl group; sulfonamide group; silyl group; amino group; monoalkylamino group; dialkylamino group; Arylamino group, nitro group; and combinations thereof.

In this specification, the acid dissociation constant (pKa) refers to pKa in an aqueous solution, and specifically, using the following software package 1, a value based on a database of Hammett's substituent constants and known literature values is obtained by calculation. It is a price to lose. All pKa values described in this specification represent values obtained by calculation using this software package.

Software Package 1: Advanced Chemistry Development (ACD/Labs) Software V8.14 for Solaris (1994-2007 ACD/Labs).

On the other hand, pKa is also determined by molecular orbital calculation. This specific method includes a method of calculating the H ⁺ dissociation free energy in the solvent based on the thermodynamic cycle. In addition, in this specification, water is usually used as the solvent, and when pKa cannot be determined with water, DMSO (dimethyl sulfoxide) is used.

The method for calculating the H ⁺ dissociation free energy can be calculated by, for example, DFT (density functional method), but various other methods have been reported in the literature and are not limited thereto. Additionally, there are multiple pieces of software that can perform DFT, for example, Gaussian16.

As described above, pKa in this specification refers to a value obtained by calculating a value based on a database of Hammett's substituent constants and known literature values using software package 1. However, pKa can be determined by this method. If it cannot be calculated, the value obtained by Gaussian16 based on DFT (density functional method) is adopted.

(Active ray-sensitive or radiation-sensitive resin composition)

The actinic ray-sensitive or radiation-sensitive resin composition of the present invention (also referred to as “the composition of the present invention”) includes a resin (A) whose polarity is increased by the action of an acid, and a compound represented by the following general formula (DA1) It is an actinic ray-sensitive or radiation-sensitive resin composition containing.

[Formula 7]

In the general formula (DA1),

X ¹ represents a sulfur atom or NQ ³ .

Q ³ represents a hydrogen atom, an organic group, -OH, or -NH ₂ .

Q ¹ represents a hydrogen atom or a substituent.

X ² represents a linking group Xz or a single bond.

The linking group Xz is a divalent linking group consisting of at least one atom selected from the group consisting of a carbon atom, an oxygen atom, a nitrogen atom, and a sulfur atom. However, the nitrogen atom may be bonded to a hydrogen atom, an alkyl group, an aryl group, or an aromatic heterocyclic group, and the sulfur atom may be bonded to a hydrocarbon group.

Ar ^a1 represents an aromatic group.

Q ² represents a hydrogen atom or an alkyl group.

Q ¹ and Q ² may be combined to form a ring.

At least one selected from the group consisting of Q ¹ and Q ² and Q ³ may combine to form a ring.

k represents an integer from 1 to 5.

m represents an integer from 1 to 3.

n and p each independently represent an integer of 0 to 2.

However, m+n+p=3.

When there are multiple X ¹ , X ² , Q ¹ , Q ² , Q ³ and Ar ^a1 , they may be the same or different.

However, when n represents 0, the following condition (i) or (ii) is satisfied.

Condition (i): X ² represents a single bond, and Ar ^a1 represents an aromatic heterocyclic group.

Condition (ii): X ² represents the linking group Xz.

The composition of the present invention is preferably a resist composition, and may be a positive resist composition or a negative resist composition. Moreover, the resist composition for alkali development may be sufficient, or the resist composition for organic solvent development may be used.

The composition of the present invention is preferably a positive resist composition.

The composition of the present invention is preferably a resist composition for alkaline development.

Additionally, the composition of the present invention is preferably a chemically amplified resist composition, and more preferably is a chemically amplified positive resist composition.

Although the reason why the composition of the present invention is excellent in EL performance and LWR performance and can reduce development defects is not completely clear, the present inventor estimates as follows.

The composition of the present invention contains a compound represented by general formula (DA1). The compound represented by the general formula (DA1) is a nitrogen-containing compound having an aromatic group in which an iodine atom is substituted, and has a polar group around the nitrogen atom that does not lower the basicity of the nitrogen atom. Due to this structure, the compound represented by the general formula (DA1) is considered to have good LWR performance because it has a high basicity and a sufficiently high ability to quench the generated acid. In addition, it is thought that by having a polar group, the effect of suppressing acid diffusion by hydrogen bonding is high and the EL performance is good. In addition, it is believed that the hydrophilicity of the polar group improves solubility in aqueous developers such as alkaline developers, which are typical developers, thereby suppressing development defects.

[Compound represented by general formula (DA1)]

The compound represented by general formula (DA1) will be described.

The compound represented by general formula (DA1) can function as an acid diffusion controller.

In general formula (DA1), X ¹ represents a sulfur atom or NQ ³ .

X ¹ preferably represents NQ ³ .

Q ³ represents a hydrogen atom, an organic group, -OH, or -NH ₂ .

When Q ³ represents an organic group, the organic group is not particularly limited, but it is preferably an organic group with 1 to 20 carbon atoms, and more preferably an organic group with 1 to 10 carbon atoms.

When Q ³ represents an organic group, the organic group is preferably an alkyl group, cycloalkyl group, alkenyl group, aryl group, heterocyclic group, -OQ ^3a or -NQ ^3b Q ^3c . Q ^3a represents an organic group. Q ^3b represents an organic group. Q ^3c represents a hydrogen atom or an organic group.

When Q ³ represents an alkyl group, the alkyl group may be linear or branched. Additionally, the alkyl group may have a substituent. As the alkyl group, alkyl groups with 1 to 10 carbon atoms such as methyl, ethyl, n-propyl, isopropyl, n-butyl, isobutyl, and t-butyl groups are preferable, and alkyl groups with 1 to 6 carbon atoms are more preferred. desirable.

When Q ³ represents a cycloalkyl group, the cycloalkyl group may be a monocyclic cycloalkyl group or a polycyclic cycloalkyl group. The number of carbon atoms of the cycloalkyl group is preferably 3 to 20, more preferably 4 to 15, and even more preferably 5 to 10. Additionally, the cycloalkyl group may have a substituent. As the cycloalkyl group, monocyclic cycloalkyl groups such as cyclopentyl group and cyclohexyl group, and polycyclic cycloalkyl groups such as norbornyl group, tetracyclodecanyl group, tetracyclododecanyl group, and adamantyl group are preferable.

When Q ³ represents an aryl group, the aryl group may be a monocyclic aryl group or a polycyclic aryl group. Additionally, the aryl group may have a substituent. As the aryl group, an aryl group having 6 to 20 carbon atoms is preferable, and an aryl group having 6 to 10 carbon atoms is more preferable, and examples include phenyl group, naphthyl group, and anthryl group.

When Q ³ represents an alkenyl group, the alkenyl group may be linear or branched. Additionally, the alkenyl group may have a substituent. As the alkenyl group, an alkenyl group having 2 to 10 carbon atoms, such as a vinyl group, is preferable, and an alkenyl group having 2 to 6 carbon atoms is more preferable.

When Q ³ represents a heterocyclic group, the heterocyclic group is preferably an aromatic heterocyclic group or a non-aromatic heterocyclic group.

When Q ³ represents an aromatic heterocyclic group (heteroaryl group), the aromatic heterocyclic group is preferably an aromatic heterocyclic group containing at least one hetero atom selected from the group consisting of a nitrogen atom, a sulfur atom, and an oxygen atom, and a nitrogen atom is preferable. An aromatic heterocyclic group containing one or more is more preferable.

Examples of aromatic heterocyclic groups include 5-membered ring aromatic heterocyclic compounds containing one or more nitrogen atoms such as pyrrole, imidazole, pyrazole, oxazole, isoxazole, thiazole, isothiazole, and triazole. One hydrogen atom is removed from a group from which one hydrogen atom has been removed and a six-membered aromatic heterocyclic compound containing one or more nitrogen atoms such as pyridine, pyrazine, pyrimidine, pyridazine, triazine, thiazine, and oxazine. A removed group, etc. can be mentioned.

In addition, the aromatic heterocyclic group is a 5-membered ring aromatic heterocyclic compound or a 6-membered ring aromatic heterocyclic compound. naphthalene, etc.), cycloalkanes (e.g., cyclopentane, cyclohexane, etc.), and non-aromatic heterocyclic compounds (e.g., 5-membered ring non-aromatic heterocyclic compounds and 6-membered ring non-aromatic heterocyclic compounds described later) It is also possible to remove one hydrogen atom from a compound fused with at least one selected from the group consisting of (e.g., indole, quinoline, isoquinoline, etc.).

The aromatic heterocyclic group may have a substituent.

The carbon atom contained as a reduction in the aromatic heterocyclic group may be substituted with an oxo group (=O).

When Q ³ represents a non-aromatic heterocyclic group (aliphatic heterocyclic group), the non-aromatic heterocyclic group is preferably a non-aromatic heterocyclic group containing at least one hetero atom selected from the group consisting of a nitrogen atom, a sulfur atom, and an oxygen atom. , a non-aromatic heterocyclic group containing one or more nitrogen atoms is more preferable.

Examples of non-aromatic heterocyclic groups include groups obtained by removing one hydrogen atom from a five-membered ring non-aromatic heterocyclic compound containing one or more nitrogen atoms such as pyrrolidine, pyrroline, and 2-oxazolidone, and Examples include groups obtained by removing one hydrogen atom from a 6-membered ring non-aromatic heterocyclic compound containing one or more nitrogen atoms, such as morpholine, piperidine, and piperazine.

In addition, the non-aromatic heterocyclic group is a 5-membered ring non-aromatic heterocyclic compound or a 6-membered ring non-aromatic heterocyclic compound, the 5-membered ring non-aromatic heterocyclic compound, the 6-membered ring non-aromatic heterocyclic compound, and a cycloalkane For example, it may be a contribution of removing one hydrogen atom from a compound fused with at least one selected from the group consisting of cyclopentane, cyclohexane, etc.

The non-aromatic heterocyclic group may have a substituent.

The carbon atom contained as a reduction in the non-aromatic heterocyclic group may be substituted with an oxo group (=O).

Q ³ preferably represents a hydrogen atom or an organic group, and more preferably represents a hydrogen atom, an alkyl group, an alkenyl group, or an aryl group.

The description, specific examples, and preferred range of the organic group represented by Q ^3a are the same as those described when Q ³ represents an organic group.

The description, specific examples, and preferred range of the organic group represented by Q ^3b are the same as those described when Q ³ represents an organic group.

When Q ^3c represents an organic group, the description, specific examples and preferred range of the organic group are the same as those described when Q ³ represents an organic group.

In general formula (DA1), Q ¹ represents a hydrogen atom or a substituent.

When Q ¹ represents a substituent, there is no particular limitation on the substituent, but an alkyl group, cycloalkyl group, alkenyl group, aryl group, heterocyclic group, cyano group, nitro group or amino group is preferable.

When Q ¹ represents an alkyl group, cycloalkyl group, alkenyl group, aryl group, or heterocyclic group, the description, specific examples, and preferred range of each group are those where Q ³ represents an alkyl group, cycloalkyl group, alkenyl group, aryl group, or heterocyclic group. It is the same as described for each period in the case.

When Q ¹ represents an amino group, the amino group may have a substituent.

When Q ¹ represents an amino group, the amino group is preferably represented by -NQ ^1a Q ^1b . Q ^1a and Q ^1b each independently represent a hydrogen atom or a substituent, and Q ^1a and Q ^1b may combine to form a ring.

When Q ^1a and Q ^1b represent a substituent, the substituent is not particularly limited, but an organic group is preferable. Examples of the organic group include an alkyl group, cycloalkyl group, alkenyl group, aryl group, heterocyclic group, or a group represented by the following general formula (na1). The description, specific examples and preferred ranges of the alkyl group, cycloalkyl group, alkenyl group, aryl group and heterocyclic group are the same as those described for each group when Q ³ represents an alkyl group, cycloalkyl group, alkenyl group, aryl group or heterocyclic group. same.

[Formula 8]

In the general formula (na1), * represents the bonding position with the nitrogen atom of the amino group represented by Q ¹ . Xq represents O, S or NQ ⁷ . Q ⁷ , Q ⁸ and Q ⁹ each independently represent a hydrogen atom, an amino group, an alkyl group, a cycloalkyl group, an alkenyl group, an aryl group or a heterocyclic group. At least two selected from the group consisting of Q ⁷ , Q ⁸ and Q ⁹ may be combined to form a ring.

Xq preferably represents NQ ⁷ .

When Q ⁷ , Q ⁸ and Q ⁹ represent an alkyl group, cycloalkyl group, alkenyl group, aryl group or heterocyclic group, descriptions, specific examples and preferred ranges of each group include that Q ³ is an alkyl group, cycloalkyl group, alkenyl group or aryl group. It is the same as described for each group when it represents a group or heterocyclic group.

The description, specific examples and preferred range when Q ⁷ , Q ⁸ and Q ⁹ represent an amino group are the same as those described when Q ¹ represents an amino group.

When at least two selected from the group consisting of Q ⁷ , Q ⁸ and Q ⁹ combine to form a ring (for example, when Q ⁷ and Q ⁸ combine to form a ring, or Q ⁸ and Q ⁹ combine to form a ring), the ring formed may be an aromatic ring or a non-aromatic ring. The ring may be a monocyclic ring (for example, a 5-membered ring or a 6-membered ring) or a polycyclic ring. The ring may contain at least one selected from the group consisting of an oxygen atom and a sulfur atom as a reduction. The ring may have a substituent.

Q ⁷ , Q ⁸ and Q ⁹ preferably represent a hydrogen atom or an alkyl group.

The description of the ring when Q ^1a and Q ^1b combine to form a ring is the same as that described when at least two selected from the group consisting of Q ⁷ , Q ⁸ and Q ⁹ combine to form a ring.

Q ¹ preferably represents a substituent containing a nitrogen atom.

In general formula (DA1), X ² represents a linking group Xz or a single bond.

The linking group Xz is a divalent linking group consisting of at least one atom selected from the group consisting of a carbon atom, an oxygen atom, a nitrogen atom, and a sulfur atom. However, the nitrogen atom may be bonded to a hydrogen atom, an alkyl group, an aryl group, or an aromatic heterocyclic group, and the sulfur atom may be bonded to a hydrocarbon group.

X ² does not consist solely of divalent hydrocarbons.

Moreover, X ² does not consist of at least one type selected from a divalent hydrocarbon group and an ester bond and an ether bond.

X ² preferably represents a divalent linking group or a single bond represented by any of the following formulas (X2-1) to (X2-11).

[Formula 9]

In the above formula, Q ⁴ and Q ⁵ each independently represent a hydrogen atom, an alkyl group, an aryl group, or an aromatic heterocyclic group. X ³ and X ⁴ each independently represent a single bond, a hydrocarbon group, an oxygen atom, or NQ ⁶ . Q ⁶ represents a hydrogen atom, an alkyl group, an aryl group, or an aromatic heterocyclic group. X ⁵ represents an oxygen atom, a sulfur atom, or NG ¹ . X ⁶ represents -SG ² or -NG ³ G ⁴ . G ¹ , G ³ and G ⁴ each independently represent a hydrogen atom, an alkyl group, an aryl group, or an aromatic heterocyclic group. G ² represents a hydrocarbon group. *1 represents the bonding position with the nitrogen atom in general formula (DA1), and *2 represents the bonding position with Ar ^a1 in general formula (DA1).

In the above formulas (X2-2) and (X2-5), Q ⁴ and Q ⁵ each independently represent a hydrogen atom, an alkyl group, an aryl group, or an aromatic heterocyclic group.

The description, specific examples, and preferred range of each group when Q ⁴ and Q ⁵ represent an alkyl group, an aryl group, or an aromatic heterocyclic group are described for each group when Q ³ represents an alkyl group, an aryl group, or an aromatic heterocyclic group. It is the same as

In the above formulas (X2-9) and (X2-10), X ³ and X ⁴ each independently represent a single bond, a hydrocarbon group, an oxygen atom, or NQ ⁶ .

The hydrocarbon group is preferably a hydrocarbon group having 1 to 20 carbon atoms, and is preferably a hydrocarbon group having 1 to 10 carbon atoms. The hydrocarbon group is preferably an alkyl group, cycloalkyl group, alkenyl group, or aryl group. The description, specific examples, and preferred range of the alkyl group, cycloalkyl group, alkenyl group, or aryl group are the same as those described for each group when Q ³ represents an alkyl group, cycloalkyl group, alkenyl group, or aryl group.

Q ⁶ represents a hydrogen atom, an alkyl group, an aryl group, or an aromatic heterocyclic group.

The description, specific examples, and preferred range of each group when Q ⁶ represents an alkyl group, an aryl group, or an aromatic heterocyclic group are the same as those described for each group when Q ³ represents an alkyl group, an aryl group, or an aromatic heterocyclic group. .

In the above formula (X2-11), X ⁵ represents an oxygen atom, a sulfur atom, or NG ¹ . G ¹ represents a hydrogen atom, an alkyl group, an aryl group, or an aromatic heterocyclic group.

The description, specific examples, and preferred range of each group when G ¹ represents an alkyl group, an aryl group, or an aromatic heterocyclic group are the same as those described for each group when Q ³ represents an alkyl group, an aryl group, or an aromatic heterocyclic group. .

X ⁵ preferably represents an oxygen atom.

In the above formula (X2-11), X ⁶ represents -SG ² or -NG ³ G ⁴ . G ² represents a hydrocarbon group. G ³ and G ⁴ each independently represent a hydrogen atom, an alkyl group, an aryl group, or an aromatic heterocyclic group.

The description, specific examples, and preferred range of the hydrocarbon group represented by G ² are the same as those described in the case where X ³ and X ⁴ represent a hydrocarbon group.

The description, specific examples, and preferred range of each group when G ³ and G ⁴ represent an alkyl group, an aryl group, or an aromatic heterocyclic group are described for each group when Q ³ represents an alkyl group, an aryl group, or an aromatic heterocyclic group. It is the same as

X ⁶ preferably represents -NG ³ G ⁴ .

It ^is more preferable that .

In general formula (DA1), Ar ^a1 represents an aromatic group.

As the aromatic group represented by Ar ^a1 , an aryl group or an aromatic heterocyclic group is preferable.

Specific examples and preferred ranges when Ar ^a1 represents an aryl group or an aromatic heterocyclic group are the same as those described for each group when Q ³ represents an aryl group or an aromatic heterocyclic group.

As shown in general formula (DA1), the aromatic group represented by Ar ^a1 has k iodine atoms as substituents. The aromatic group represented by Ar ^a1 may further have a substituent in addition to k iodine atoms. Examples of the substituent include the substituent T.

When n in general formula (DA1) represents 0, the following condition (i) or (ii) is satisfied.

Condition (i): X ² represents a single bond, and Ar ^a1 represents an aromatic heterocyclic group.

Condition (ii): X ² represents the linking group Xz.

When n in the general formula (DA1) represents 0 and satisfies the above condition (i), Ar ^a1 preferably represents an aromatic heterocyclic group containing a nitrogen atom.

When n in the general formula (DA1) represents 0 and satisfies the above condition (ii), the description, specific examples and preferred range of the linking group ^{Xz represented} by It is particularly preferable to represent a divalent linking group represented by 11).

In general formula (DA1), Q ² represents a hydrogen atom or an alkyl group.

Specific examples and preferred ranges when Q ² represents an alkyl group are the same as those described when Q ³ represents an alkyl group.

In general formula (DA1), Q ¹ and Q ² may combine to form a ring.

When Q ¹ and Q ² combine to form a ring, the ring is also called “ring Qr.”

Ring Qr may be monocyclic or polycyclic. In the case of a single ring, a 5-membered ring or a 6-membered ring is preferable.

Ring Qr contains at least one nitrogen atom as a reduction, but may further contain at least one selected from the group consisting of a nitrogen atom, an oxygen atom, and a sulfur atom as a reduction.

Ring Qr may be an aromatic ring or a non-aromatic ring.

Examples of the aromatic ring in the case where ring Qr is an aromatic ring include, for example, a 5-membered aromatic heterocyclic compound containing one or more nitrogen atoms as described in the case where Q ³ represents an aromatic heterocyclic group, or a five-membered ring aromatic heterocyclic compound containing one or more nitrogen atoms. The 6-membered ring aromatic heterocyclic compound, the 5-membered ring aromatic heterocyclic compound, or the 6-membered ring aromatic heterocyclic compound may be selected from the group consisting of the 5-membered ring aromatic heterocyclic compound, the 6-membered ring aromatic heterocyclic compound, an aromatic hydrocarbon, a cycloalkane, and A ring structure having a compound fused with at least one selected from the group consisting of aromatic heterocyclic compounds, etc. may be mentioned.

Examples of the non-aromatic ring when ring Qr is a non-aromatic ring include, for example, a 5-membered ring non-aromatic heterocyclic compound containing one or more nitrogen atoms as described in the case where Q ³ represents a non-aromatic heterocyclic group, and 1 nitrogen atom. The 6-membered ring non-aromatic heterocyclic compound, the 5-membered ring non-aromatic heterocyclic compound, or the 6-membered ring non-aromatic heterocyclic compound comprising at least 5-membered ring non-aromatic heterocyclic compound, the 6-membered ring non-aromatic heterocyclic compound, and Examples include ring structures of compounds fused with at least one selected from the group consisting of cycloalkanes.

Ring Qr may have a substituent.

In general formula (DA1), at least one selected from the group consisting of Q ¹ and Q ² and Q ³ may combine to form a ring. For example, Q ¹ and Q ³ may combine to form a ring, or Q ² and Q ³ may combine to form a ring.

When at least one selected from the group consisting of Q ¹ and Q ² and Q ³ combine to form a ring, the ring is also called “ring Qs.”

The description, specific examples, and preferred range of ring Qs are the same as those described for ring Qr.

In general formula (DA1), k represents an integer of 1 to 5, and preferably represents an integer of 1 to 3. In addition, I in I _k in general formula (DA1) is an iodine atom.

In general formula (DA1), m represents an integer of 1 to 3, and preferably represents 1 or 2.

In general formula (DA1), n and p each independently represent an integer of 0 to 2.

For the reason that development defects can be further reduced, n represents 1 or 2, or n represents 0, satisfies the above condition ( ⁱⁱ ), and It is preferable to represent a divalent linking group.

m, n and p in general formula (DA1) satisfy the relationship m+n+p=3.

The pKa of the conjugate acid of the compound represented by the general formula (DA1) is preferably 0.1 or more, and from the viewpoint of naming the acid, it is more preferably 2 or more, more preferably 3 to 15, and especially 3.5 to 12. desirable.

It is particularly preferable that n in the general formula (DA1) represents 1 or 2, and that the pKa of the conjugate acid of the compound represented by the general formula (DA1) is 2 or more.

The molecular weight of the compound represented by general formula (DA1) is not particularly limited, but is preferably 2000 or less, more preferably 1500 or less, and especially preferably 1000 or less.

The compound represented by general formula (DA1) is preferably a nonionic compound.

Specific examples of the compound represented by general formula (DA1) are shown below, but the present invention is not limited to these.

[Formula 10]

Among the compositions of the present invention, the compounds represented by general formula (DA1) may be used individually or in combination of two or more types.

In the composition of the present invention, the content of the compound represented by general formula (DA1) (sum if multiple types exist) is preferably 0.001 to 40% by mass, based on the total solid content of the composition of the present invention, and is preferably 0.01% by mass. ~30% by mass is more preferred, and 0.1~20% by mass is more preferred.

In addition, solid content refers to components other than the solvent in the composition, and any component other than the solvent is considered solid content even if it is a liquid component.

The method of synthesizing the compound represented by the general formula (DA1) is not particularly limited, but for example, condensation of nitrogen-containing compounds corresponding to iodine-containing aromatic carboxylic acid derivatives, sulfonic acid derivatives, isocyanate, or isothiocyanate, etc. (Examples of synthesis routes are shown below. ^{X 1} , Q ¹ , n, Q ² , ^p , Ar ^a1 and k are respectively Q represents the same meaning as ² , p, Ar ^a1 and k. Y represents a hydroxy group, an alkoxy group, an aryloxy group, an acyloxy group, a sulfooxy group or a halogen atom. Z represents an oxygen atom or a sulfur atom. indicates).

Additionally, it can also be synthesized by iodination of the corresponding aromatic compound. For iodination, see, for example, "Reagents and synthesis methods for organic synthesis of bromine and iodine compounds, supervised by Fumi Suzuki, Manac Co., Ltd. Laboratory, (2017). Maruzen Publishing."

[Formula 11]

[Resin (A) whose polarity increases due to the action of acid]

Resin (A) (also referred to as "resin (A)"), whose polarity is increased by the action of acid, will be described.

<Repeating unit having an acid-decomposable group>

Resin (A) is a resin that is decomposed by the action of an acid and its polarity increases.

The resin (A) preferably contains a group (also referred to as “acid-decomposable group”) that is decomposed by the action of an acid to increase polarity, and more preferably contains a repeating unit having an acid-decomposable group.

The polarity of the resin (A) increases due to the action of acid, so its solubility in an alkaline developer increases, and its solubility in an organic solvent decreases.

In pattern formation using the composition of the present invention containing the resin (A), typically, when an alkaline developer is used as the developer, a positive pattern is formed, and when an organic developer is used as the developer, a negative pattern is formed. is formed

The acid-decomposable group is preferably a group that is decomposed by the action of an acid to generate a polar group. The acid-decomposable group is a leaving group that is desorbed by the action of an acid, and preferably has a structure in which the polar group is protected. That is, the resin (A) preferably has a repeating unit having a group that is decomposed by the action of an acid and generates a polar group.

As the polar group, an alkali-soluble group is preferable, and examples include carboxyl group, phenolic hydroxyl group, fluorinated alcohol group, sulfonic acid group, phosphoric acid group, sulfonamide group, sulfonylimide group, (alkyl sulfonyl) (alkyl carbonyl) Methylene group, (alkyl sulfonyl) (alkyl carbonyl) imide group, bis (alkyl carbonyl) methylene group, bis (alkyl carbonyl) imide group, bis (alkyl sulfonyl) methylene group, bis (alkyl sulfonyl) imide group. acid groups, such as tris(alkylcarbonyl)methylene group, and tris(alkylsulfonyl)methylene group, and alcoholic hydroxyl groups.

As the polar group, a carboxy group, a phenolic hydroxyl group, a fluorinated alcohol group (preferably a hexafluoroisopropanol group), or a sulfonic acid group is preferable, and a carboxy group or a phenolic hydroxyl group is more preferable. That is, the acid-decomposable group is preferably a group that is decomposed by the action of an acid to generate a carboxy group, or a group that is decomposed by the action of an acid to generate a phenolic hydroxyl group.

The resin (A) has a repeating unit having at least one acid-decomposable group selected from the group consisting of a group that is decomposed by the action of an acid to generate a carboxyl group and a group that is decomposed by the action of an acid to generate a phenolic hydroxyl group. desirable.

Examples of the leaving group that is released by the action of an acid include groups represented by formulas (Y1) to (Y4).

Equation (Y1): -C(Rx ₁ )(Rx ₂ )(Rx ₃ )

Formula (Y2): -C(=O)OC(Rx ₁ )(Rx ₂ )(Rx ₃ )

Formula (Y3): -C(R ₃₆ )(R ₃₇ )(OR ₃₈ )

Formula (Y4): -C(Rn)(H)(Ar)

In formulas (Y1) and (Y2), Rx ₁ to Rx ₃ each independently represent an alkyl group (linear or branched), a cycloalkyl group (monocyclic or polycyclic), an aryl group (monocyclic or polycyclic), or an aralkyl group ( It represents a linear or branched chain), or an alkenyl group (linear or branched). Additionally, when all of Rx ₁ to Rx ₃ are alkyl groups (linear or branched), it is preferable that at least two of Rx ₁ to Rx ₃ are methyl groups.

Among them, it is preferable that Rx ₁ to Rx ₃ each independently represent a linear or branched alkyl group, and it is more preferable that Rx ₁ to Rx ₃ each independently represent a linear alkyl group.

Two of Rx ₁ to Rx ₃ may be bonded to each other to form a ring (either monocyclic or polycyclic may be used).

The alkyl group for Rx ₁ to Rx ₃ is preferably an alkyl group having 1 to 5 carbon atoms, such as methyl, ethyl, n-propyl, isopropyl, n-butyl, isobutyl, and t-butyl.

The cycloalkyl groups of Rx ₁ to Rx ₃ include monocyclic cycloalkyl groups such as cyclopentyl group and cyclohexyl group, and polycyclic cycloalkyl groups such as norbornyl group, tetracyclodecanyl group, tetracyclododecanyl group, and adamantyl group. is desirable.

The aryl group of Rx ₁ to Rx ₃ is preferably an aryl group having 6 to 10 carbon atoms, and examples include phenyl group, naphthyl group, and anthryl group.

The aralkyl group of Rx ₁ to Rx ₃ is preferably a group in which one hydrogen atom of the alkyl groups of Rx ₁ to Rx ₃ is replaced with an aryl group having 6 to 10 carbon atoms (preferably a phenyl group), for example, benzyl. etc. can be mentioned.

As the alkenyl group of Rx ₁ to Rx ₃ , a vinyl group is preferable.

As the ring formed by combining two of Rx ₁ to Rx ₃ , a cycloalkyl group is preferable. The cycloalkyl group formed by combining two of Rx ₁ to Rx ₃ is a monocyclic cycloalkyl group such as cyclopentyl group or cyclohexyl group, or norbornyl group, tetracyclodecanyl group, tetracyclododecanyl group, or A polycyclic cycloalkyl group such as a damantyl group is preferable, and a monocyclic cycloalkyl group having 5 to 6 carbon atoms is more preferable.

The cycloalkyl group formed by combining two of Rx ₁ to Rx ₃ is, for example, a group in which one of the methylene groups constituting the ring has a hetero atom such as an oxygen atom, a hetero atom such as a carbonyl group, or a vinyl group. It may be substituted with den group. In addition, in these cycloalkyl groups, one or more of the ethylene groups constituting the cycloalkane ring may be substituted with a vinylene group.

As for the group represented by formula (Y1) or formula (Y2), for example, Rx ₁ is preferably a methyl group or ethyl group, and Rx ₂ and Rx ₃ are combined to form the above-mentioned cycloalkyl group.

In formula (Y3), R ₃₆ to R ₃₈ each independently represent a hydrogen atom or a monovalent organic group. R ₃₇ and R ₃₈ may be combined with each other to form a ring. Examples of the monovalent organic group include an alkyl group, cycloalkyl group, aryl group, aralkyl group, and alkenyl group. R ₃₆ is also preferably a hydrogen atom.

In addition, the alkyl group, cycloalkyl group, aryl group, and aralkyl group may contain a group having a hetero atom such as an oxygen atom and/or a hetero atom such as a carbonyl group. For example, in the alkyl group, cycloalkyl group, aryl group, and aralkyl group, for example, one or more of the methylene groups may be substituted with a group having a hetero atom such as an oxygen atom and/or a hetero atom such as a carbonyl group. do.

Additionally, R ₃₈ may be combined with other substituents of the main chain of the repeating unit to form a ring. The group formed by combining R ₃₈ with other substituents of the main chain of the repeating unit is preferably an alkylene group such as a methylene group.

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

[Formula 12]

Here, L ₁ and L ₂ each independently represent a hydrogen atom, an alkyl group, a cycloalkyl group, an aryl group, or a combination thereof (for example, a group combining an alkyl group and an aryl group).

M represents a single bond or a divalent linking group.

Q is an alkyl group which may contain a hetero atom, a cycloalkyl group which may contain a hetero atom, an aryl group which may contain a hetero atom, an amino group, an ammonium group, a mercapto group, a cyano group, an aldehyde group, or a combination thereof. It represents a group (for example, a group combining an alkyl group and a cycloalkyl group).

In the alkyl group and cycloalkyl group, for example, one of the methylene groups may be substituted with a hetero atom such as an oxygen atom or a group having a hetero atom such as a carbonyl group.

Moreover, it is preferable that one of L ₁ and L ₂ is a hydrogen atom, and the other is an alkyl group, a cycloalkyl group, an aryl group, or a combination of an alkylene group and an aryl group.

At least two of Q, M, and L ₁ may be combined to form a ring (preferably a 5-membered or 6-membered ring).

In terms of miniaturization of the pattern, it is preferable that L ₂ is a secondary or tertiary alkyl group, and it is more preferable that it is a tertiary alkyl group. Examples of the secondary alkyl group include isopropyl group, cyclohexyl group, or norbornyl group, and examples of the tertiary alkyl group include tert-butyl group or adamantane group. In these modes, Tg (glass transition temperature) and activation energy are increased, so in addition to ensuring film strength, fogging can be suppressed.

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

Since the acid-decomposability of the repeating unit is excellent, in the leaving group that protects the polar group, when the non-aromatic ring is directly bonded to the polar group (or its residue), the non-aromatic ring is directly bonded to the polar group (or its residue). It is also preferable that the reducing atom adjacent to the reducing atom does not have a halogen atom such as a fluorine atom as a substituent.

The leaving group that is released by the action of acid includes, in addition, 2-cyclopentenyl group having a substituent (alkyl group, etc.) such as 3-methyl-2-cyclopentenyl group, and 1,1,4,4-tetramethylcyclo A cyclohexyl group having a substituent (alkyl group, etc.) such as a hexyl group may be used.

The resin (A) preferably has at least one selected from the group consisting of a repeating unit represented by the following general formula (3), a repeating unit represented by the following general formula (6), and a repeating unit represented by the following general formula (7) do.

[Formula 13]

In general formula (3),

R ₅ to R ₇ each independently represent a hydrogen atom, an alkyl group, a cycloalkyl group, a halogen atom, a cyano group, or an alkoxycarbonyl group.

L ₂ represents a divalent linking group.

R ₈ to R ₁₀ each independently represent an alkyl group, cycloalkyl group, aryl group, aralkyl group, or alkenyl group. Two of R ₈ to R ₁₀ may combine with each other to form a ring.

[Formula 14]

In general formula (6),

R ₂₂ to R ₂₄ each independently represent a hydrogen atom, an alkyl group, a cycloalkyl group, a halogen atom, a cyano group, or an alkoxycarbonyl group.

L ₄ represents a single bond or a divalent linking group.

Ar ₁ represents an aromatic group.

R ₂₅ to R ₂₇ each independently represent a hydrogen atom, an alkyl group, a cycloalkyl group, an aryl group, an aralkyl group, or an alkenyl group.

R ₂₆ and R ₂₇ may be combined to form a ring.

R ₂₄ or R ₂₅ may be combined with Ar ₁ .

[Formula 15]

In general formula (7),

R ₂₈ to R ₃₀ each independently represent a hydrogen atom, an alkyl group, a cycloalkyl group, a halogen atom, a cyano group, or an alkoxycarbonyl group.

L ₅ represents a single bond or a divalent linking group.

R ₃₁ and R ₃₂ each independently represent a hydrogen atom, an alkyl group, a cycloalkyl group, an aryl group, an aralkyl group, or an alkenyl group.

R ₃₃ represents an alkyl group, cycloalkyl group, aryl group, aralkyl group, or alkenyl group.

R ₃₂ and R ₃₃ may be combined to form a ring.

Hereinafter, the repeating unit represented by general formula (3) will be described.

The repeating unit represented by General Formula (3) is a repeating unit having an acid-decomposable group.

The alkyl groups represented by R ₅ , R ₆ , and R ₇ may be either linear or branched. The number of carbon atoms in the alkyl group is not particularly limited, but is preferably 1 to 5, and more preferably 1 to 3.

The cycloalkyl groups represented by R ₅ , R ₆ , and R ₇ include monocyclic cycloalkyl groups such as cyclopentyl group and cyclohexyl group, norbornyl group, tetracyclodecanyl group, tetracyclododecanyl group, and adamantyl group. A polycyclic cycloalkyl group is preferred.

Halogen atoms represented by R ₅ , R ₆ , and R ₇ include a fluorine atom, a chlorine atom, a bromine atom, and an iodine atom, with a fluorine atom or an iodine atom being preferable.

The alkyl group contained in the alkoxycarbonyl group represented by R ₅ , R ₆ , and R ₇ may be either linear or branched. The number of carbon atoms of the alkyl group contained in the alkoxycarbonyl group is not particularly limited, but is preferably 1 to 5, and more preferably 1 to 3.

As the divalent linking group represented by L ₂ , -CO-, -O-, -S-, -SO-, -SO ₂ -, hydrocarbon group (for example, alkylene group, cycloalkylene group, alkenylene group, aryl len group, etc.), and a linking group in which a plurality of these are connected.

The alkyl group represented by R ₈ to R ₁₀ may be either linear or branched. The number of carbon atoms in the alkyl group is not particularly limited, but is preferably 1 to 5, and more preferably 1 to 3. The methylene group of the alkyl group represented by R ₈ to R ₁₀ may be substituted by at least one of -CO- and/or -O-.

The cycloalkyl groups represented by R ₈ to R ₁₀ include monocyclic cycloalkyl groups such as cyclopentyl group and cyclohexyl group, and polycyclic cycloalkyl groups such as norbornyl group, tetracyclodecanyl group, tetracyclododecanyl group, and adamantyl group. Alkyl groups are preferred.

As the aryl group represented by R ₈ to R ₁₀ , a phenyl group is preferable.

The aralkyl group represented by R ₈ to R ₁₀ is preferably a group in which one hydrogen atom of the alkyl groups represented by _R 8 to R ₁₀ is replaced with an aryl group having 6 to 10 carbon atoms (preferably a phenyl group), for example. , benzyl group, etc.

As the alkenyl group represented by R ₈ to R ₁₀ , a vinyl group is preferable.

The ring formed by combining two of R ₈ to R ₁₀ is preferably a cycloalkyl group. As a cycloalkyl group formed by combining two of R ₈ to R ₁₀ , a cyclopentyl group, a monocyclic cycloalkyl group such as cyclohexyl group, norbornyl group, tetracyclodecanyl group, tetracyclododecanyl group, or a A polycyclic cycloalkyl group such as a damantyl group is preferable, and a monocyclic cycloalkyl group having 5 to 6 carbon atoms is more preferable.

A cycloalkyl group formed by combining two of R ₈ to R ₁₀ is, for example, a group in which one of the methylene groups constituting the ring has a hetero atom such as an oxygen atom, a hetero atom such as a carbonyl group, or a vinyl group. It may be substituted with den group. In addition, in these cycloalkyl groups, one or more of the ethylene groups constituting the cycloalkane ring may be substituted with a vinylene group.

Each of the above groups in General Formula (3) may have a substituent, and examples of the substituent include the substituent T above.

Hereinafter, the repeating unit represented by general formula (6) will be described.

The repeating unit represented by General Formula (6) is a repeating unit having an acid-decomposable group.

R ₂₂ , R ₂₃ , and R ₂₄ have the same meaning as R ₅ , R ₆ , and R ₇ in General Formula (3), and their applicable modes are also the same.

When L ₄ represents a divalent linking group, examples of the divalent linking group include -CO-, -O-, -S-, -SO-, -SO ₂ -, hydrocarbon group (for example, alkylene group, cycloalkylene group) , alkenylene group, arylene group, etc.), and linking groups where a plurality of these are connected.

The aromatic group represented by Ar ₁ is not particularly limited, and examples include a phenylene group or a naphthylene group, with a phenylene group being preferable.

Examples of the alkyl group, cycloalkyl group, aryl group, aralkyl group, and alkenyl group represented by R _{25 to} R ₂₇ include the alkyl group, cycloalkyl group, aryl group, aralkyl _group , and The same groups as alkenyl groups can be mentioned.

The alkyl group, cycloalkyl group, aryl group, aralkyl group, and alkenyl group represented by R ₂₅ to R ₂₇ may have a substituent, and examples of the substituent include the substituent T above.

The ring formed by combining R ₂₆ and R ₂₇ , Ar ₁ and R ₂₄ , and R ₂₅ and Ar ₁ is preferably a cycloalkyl group. The cycloalkyl group formed by combining R ₂₆ and R ₂₇ , Ar ₁ and R ₂₄ , and R ₂₅ and Ar ₁ is a cyclopentyl group, a monocyclic cycloalkyl group such as cyclohexyl group, or a norbornyl group or tetracyclodecane. A polycyclic cycloalkyl group such as a monocyclic group, tetracyclododecanyl group, or adamantyl group is preferable, and a monocyclic cycloalkyl group having 5 to 6 carbon atoms is more preferable.

The cycloalkyl group formed by combining R ₂₆ and R ₂₇ , Ar ₁ and R ₂₄ , and R ₂₅ and Ar ₁ is, for example, one of the methylene groups constituting the ring, a hetero atom such as an oxygen atom, or a carbonyl group. It may be substituted by a group having a hetero atom such as a vinylidene group. In addition, in these cycloalkyl groups, one or more of the ethylene groups constituting the cycloalkane ring may be substituted with a vinylene group.

Hereinafter, the repeating unit represented by general formula (7) will be described.

The repeating unit represented by General Formula (7) is a repeating unit having an acid-decomposable group.

R ₂₈ , R ₂₉ , R ₃₀ , and L ₅ have the same meaning as R ₂₂ , R ₂₃ , R ₂₄ , and L ₄ in General Formula (6), and the applicable modes are also the same.

Examples of the alkyl group, cycloalkyl group, aryl group, aralkyl group, and alkenyl group represented by R ₃₁ , R ₃₂ , and R ₃₃ include the alkyl group, cycloalkyl group, and aryl group represented by R ₈ to R ₁₀ in the above-mentioned general formula (3), Groups similar to aralkyl groups and alkenyl groups can be mentioned.

The alkyl group, cycloalkyl group, aryl group, aralkyl group, and alkenyl group represented by R ₃₁ , R ₃₂ , and R ₃₃ may have a substituent, and examples of the substituent include the substituent T above.

The ring formed by combining R ₃₂ and R ₃₃ is preferably a cycloalkyl group. The cycloalkyl group formed by combining R ₃₂ and R ₃₃ is a monocyclic cycloalkyl group such as cyclopentyl group or cyclohexyl group, or norbornyl group, tetracyclodecanyl group, tetracyclododecanyl group, or adamantyl group. Polycyclic cycloalkyl groups such as these are preferable, and monocyclic cycloalkyl groups having 5 to 6 carbon atoms are more preferable.

The cycloalkyl group formed by combining R ₃₂ and R ₃₃ is, for example, a group in which one of the methylene groups constituting the ring is a hetero atom such as an oxygen atom, a group having a hetero atom such as a carbonyl group, or a vinylidene group. It may be substituted. In addition, in these cycloalkyl groups, one or more of the ethylene groups constituting the cycloalkane ring may be substituted with a vinylene group.

The repeating unit having an acid-decomposable group may or may not contain a halogen atom, but it is preferable that it does not contain a halogen atom.

The content of the repeating unit having an acid-decomposable group is preferably 5 mol% or more, more preferably 10 mol% or more, and still more preferably 15 mol% or more relative to all repeating units in the resin (A). Moreover, the content of the repeating unit having an acid-decomposable group is preferably 95 mol% or less, more preferably 90 mol% or less, and especially preferably 85 mol% or less relative to all repeating units in the resin (A).

Specific examples of repeating units having an acid-decomposable group are shown below, but are not limited to these. In _{the structural} formula _{below ,}

[Formula 16]

[Formula 17]

[Formula 18]

[Formula 19]

[Formula 20]

[Formula 21]

[Formula 22]

[Formula 23]

<Repeating unit represented by general formula (A2)>

Resin (A) preferably has a repeating unit represented by the following general formula (A2).

[Formula 24]

In general formula (A2),

R ₁₀₁ , R ₁₀₂ and R ₁₀₃ each independently represent a hydrogen atom, an alkyl group, a cycloalkyl group, a halogen atom, a cyano group or an alkoxycarbonyl group.

L _A represents a single bond or a divalent linking group.

Ar _A represents an aromatic group.

k represents an integer of 1 to 5.

However, R ₁₀₂ may be bonded to Ar _A , and when R ₁₀₂ and Ar _A are bonded, R ₁₀₂ represents a single bond or an alkylene group.

When R ₁₀₁ , R ₁₀₂ and R ₁₀₃ in general formula (A2) represent an alkyl group, the alkyl group is not particularly limited, but an alkyl group with 1 to 20 carbon atoms is preferable, an alkyl group with 1 to 8 carbon atoms is more preferable, and an alkyl group with 1 to 8 carbon atoms is more preferable. An alkyl group of ~3 is more preferred. Specific examples of the alkyl group include methyl group, ethyl group, propyl group, isopropyl group, n-butyl group, sec-butyl group, hexyl group, 2-ethylhexyl group, octyl group, dodecyl group, etc.

When R ₁₀₁ , R ₁₀₂ and R ₁₀₃ in General Formula (A2) represent a cycloalkyl group, the cycloalkyl group may be monocyclic or polycyclic. As the cycloalkyl group, a monocyclic cycloalkyl group having 3 to 8 carbon atoms such as cyclopropyl group, cyclopentyl group, and cyclohexyl group is preferable.

When R ₁₀₁ , R ₁₀₂ and R ₁₀₃ in General Formula (A2) represent a halogen atom, examples of the halogen atom include a fluorine atom, a chlorine atom, a bromine atom, and an iodine atom, with a fluorine atom being preferred. .

In the case where R ₁₀₁ , R ₁₀₂ and R ₁₀₃ in General Formula (A2) represent an alkoxycarbonyl group, specific examples and preferred ranges of the alkyl group contained in the alkoxycarbonyl group include the above-described R ₁ , R ₂ and R ₃ being an alkyl group. It is the same as the alkyl group in the case where .

In cases where each of the above groups can further have one or more substituents, it may have one or more additional substituents. Additional substituents are not particularly limited, but include, for example, alkyl group, cycloalkyl group, aryl group, amino group, amide group, ureido group, urethane group, hydroxyl group, carboxyl group, halogen atom, alkoxy group, thioether group, Examples include a real group, an acyloxy group, an alkoxycarbonyl group, a cyano group, and a nitro group. The number of carbon atoms of the additional substituent is preferably 8 or less.

R ₁₀₁ and R ₁₀₂ in general formula (A2) are preferably hydrogen atoms.

R ₁₀₃ in general formula (A2) is preferably a hydrogen atom or a methyl group, and more preferably a hydrogen atom.

Ar _A in general formula (A2) represents an aromatic group, and more specifically represents a (k+1) valent aromatic group. When k is 1, the divalent aromatic group is, for example, an arylene group having 6 to 18 carbon atoms such as a phenylene group, tolylene group, naphthylene group, or anthracenylene group, or a thiophene ring, a furan ring, or a thiophene ring. Divalent aromatics including heterocycles such as roll ring, benzothiophene ring, benzofuran ring, benzopyrrole ring, triazine ring, imidazole ring, benzimidazole ring, triazole ring, thiadiazole ring, and thiazole ring. Gi is preferable. Additionally, the aromatic group may have a substituent.

Specific examples of the (k+1) valent aromatic group when k is an integer of 2 or more include groups formed by removing (k-1) arbitrary hydrogen atoms from the above-mentioned specific examples of the divalent aromatic group. .

The (k+1)-valent aromatic group may further have a substituent.

The substituents that the (k+1)-valent aromatic group may have are not particularly limited, but examples include methyl group, ethyl group, propyl group, isopropyl group, n-butyl group, sec-butyl group, hexyl group, and 2-ethyl group. Alkyl groups such as hexyl group, octyl group, and dodecyl group; Alkoxy groups such as methoxy group, ethoxy group, hydroxyethoxy group, propoxy group, hydroxypropoxy group, and butoxy group; Aryl groups such as phenyl groups; etc. can be mentioned.

Ar _A preferably represents an aromatic group having 6 to 18 carbon atoms, and more preferably represents a benzene ring group, a naphthalene ring group, or a biphenylene ring group.

L _A in general formula (A2) represents a single bond or a divalent linking group.

When L _A represents a divalent linking group, the divalent linking group is not particularly limited, but examples include -COO-, -CONR ₆₄ -, an alkylene group, or a group formed by combining two or more types of these groups. there is. Said R ₆₄ represents a hydrogen atom or an alkyl group.

The alkylene group is not particularly limited, but alkylene groups having 1 to 8 carbon atoms such as methylene group, ethylene group, propylene group, butylene group, hexylene group, and octylene group are preferable.

When R ₆₄ represents an alkyl group, examples of the alkyl group include methyl, ethyl, propyl, isopropyl, n-butyl, sec-butyl, hexyl, 2-ethylhexyl, octyl, and dodecyl. and alkyl groups having 20 or less carbon atoms, and alkyl groups with 8 or less carbon atoms are preferable.

The repeating unit represented by general formula (A2) preferably has a hydroxystyrene structure. That is, Ar _A preferably represents a benzene ring group.

It is preferable that k represents an integer of 1 to 3, and it is more preferable that it represents 1 or 2.

Specific examples of repeating units represented by general formula (A2) are shown below. In the structural formulas of the following specific examples, a represents 1, 2, or 3. In addition, as specific examples of the repeating unit represented by general formula (A2), the descriptions in paragraphs [0068] to [0072] of International Publication No. 2018/193954 can be referred to, and these contents are incorporated in this specification.

[Formula 25]

When the resin (A) contains a repeating unit represented by the general formula (A2), the content of the repeating unit represented by the general formula (A2) is not particularly limited, but is 5 mol% or more relative to all repeating units in the resin (A). It is preferable, it is more preferable that it is 10 mol% or more, and it is more preferable that it is 20 mol% or more. Moreover, the content of the repeating unit represented by the general formula (A2) is preferably 90 mol% or less, more preferably 85 mol% or less, and even more preferably 80 mol% or less relative to all repeating units in the resin (A). .

<Other repetition units>

Resin (A) may contain repeating units other than those described above.

When the resin (A) contains repeating units other than the above-mentioned repeating units, the content of the other repeating units is not particularly limited, but is 1 mol% or more and 60 mol% based on all repeating units in the resin (A). It is preferable that it is 3 mol% or more and 50 mol% or less, and it is more preferable that it is 5 mol% or more and 40 mol% or less.

(Repeating unit with acid group)

Resin (A) may further have a repeating unit having an acid group in addition to the above-described repeating units.

As the acid group, for example, a carboxy group, a fluorinated alcohol group (preferably a hexafluoroisopropanol group), a sulfonic acid group, a sulfonamide group, an isopropanol group, etc. are preferable.

In addition, in the hexafluoroisopropanol group, one or more (preferably 1 to 2) fluorine atoms may be substituted with groups other than fluorine atoms (for example, an alkyloxycarbonyl group, etc.). -C(CF ₃ )(OH)-CF ₂ - formed in this way is also preferable as an acid group. Additionally, one or more fluorine atoms may be substituted with a group other than a fluorine atom to form a ring containing -C(CF ₃ )(OH)-CF ₂ -.

As a specific example of a repeating unit having an acid group, for example, the description in paragraph [0205] of International Publication No. 2019/054282 can be referred to, and these contents are incorporated in this specification. However, repeating units having acid groups are not limited to these.

(Repeating unit that has a fluorine atom or iodine atom and is not acid-decomposable)

In addition to the above-mentioned repeating units, the resin (A) may further have a repeating unit that has a fluorine atom or an iodine atom and does not exhibit acid decomposability.

Repeating units that have a fluorine atom or an iodine atom and do not exhibit acid decomposability are exemplified below, but are not limited to these.

[Formula 26]

(Repeating unit with lactone group, sultone group or carbonate group)

Resin (A) may further have a repeating unit having a lactone group, a sultone group, or a carbonate group in addition to the above-described repeating units.

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 them, those in which another ring structure is condensed to a 5- to 7-membered ring lactone structure in the form of a bicyclo or spiro structure, or a 5- to 7-membered ring sultone structure in the form of a bicyclo or spiro structure. It is more preferable that the other ring structure is fused.

Resin (A) is a reduction of a lactone structure represented by any of the following general formulas (LC1-1) to (LC1-21), or a sultone structure represented by any of the following general formulas (SL1-1) to (SL1-3). It is preferable to have a repeating unit having a lactone group or sultone group formed by removing one or more hydrogen atoms from the atom.

Additionally, the lactone group or sultone group may be directly bonded to the main chain. For example, the reducing atom of the lactone group or sultone group may constitute the main chain of the resin (A).

[Formula 27]

The lactone structure or sultone structure portion may have a substituent (Rb ₂ ). Preferred substituents (Rb ₂ ) include an alkyl group with 1 to 8 carbon atoms, a cycloalkyl group with 4 to 7 carbon atoms, an alkoxy group with 1 to 8 carbon atoms, an alkoxycarbonyl group with 1 to 8 carbon atoms, a carboxyl group, a halogen atom, a hydroxyl group, and An ano group, an acid-decomposable group, etc. are mentioned. n ₂ represents an integer of 0 to 4. When n ₂ is 2 or more, a plurality of Rb ₂ may be different, or a plurality of Rb ₂ may be bonded to each other to form a ring.

As a specific example of a repeating unit having a lactone structure, for example, the description in paragraph [0088] of International Publication No. 2018/193954 can be referred to, and these contents are incorporated in this specification. However, repeating units having a lactone structure are not limited to these.

As the carbonate group, a cyclic carbonate ester group is preferable.

(repeating unit with mine generator)

Resin (A) may have a repeating unit having a photoacid generator. As a repeating unit having a photoacid generator, reference may be made to the descriptions in paragraphs [0090] to [0096] of International Publication No. 2018/193954, the contents of which are incorporated herein by reference.

(Other repeat units)

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

For other repeating units other than the above, reference can be made to the descriptions in paragraphs [0097] to [0100] and [0102] to [0133] of International Publication No. 2018/193954, and these contents are incorporated in this specification.

Resin (A) can be synthesized according to a conventional method (for example, radical polymerization).

The weight average molecular weight of the resin (A) is not particularly limited, but is preferably 1,000 to 200,000, more preferably 2,000 to 30,000, and even more preferably 3,000 to 20,000.

The dispersion degree (molecular weight distribution) of the resin (A) is usually 1.0 to 5.0, preferably 1.0 to 3.0, more preferably 1.0 to 2.5, and still more preferably 1.0 to 2.0.

The content of resin (A) in the composition of the present invention is not particularly limited, but is preferably 50 to 99.9% by mass, and more preferably 60 to 99.0% by mass, based on the total solid content of the composition of the present invention.

In addition, solid content refers to components other than the solvent in the composition, and any component other than the solvent is considered solid content even if it is a liquid component.

Moreover, the number of resins (A) contained in the composition of the present invention may be one, or two or more types may be used.

[Compounds that generate acids by irradiation of actinic rays or radiation (acid generators)]

The actinic ray-sensitive or radiation-sensitive resin composition of the present invention preferably contains a compound (acid generator) that generates an acid upon irradiation of actinic rays or radiation.

Compounds that generate acids when irradiated with actinic light or radiation are also called “compounds (B)” or “acid generators (B).”

Compound (B) may be in the form of a low-molecular-weight compound or may be in the form introduced into a part of a polymer (for example, resin (A)). In addition, a form of a low molecular compound and a form introduced into a part of a polymer (for example, resin (A)) may be used together.

When compound (B) is in the form of a low molecular weight compound, the molecular weight of compound (B) is preferably 3000 or less, more preferably 2000 or less, and still more preferably 1000 or less. The lower limit is not particularly limited, but is preferably 100 or more.

When the compound (B) is introduced into a part of the polymer, it may be introduced into a part of the resin (A), or it may be introduced into a resin different from the resin (A).

Compound (B) is preferably a low molecular weight compound.

Examples of the compound ( ^B ) include a compound (onium salt) represented by "M ⁺

Examples of the organic acids include sulfonic acids (aliphatic sulfonic acid, aromatic sulfonic acid, camphorsulfonic acid, etc.), carboxylic acids (aliphatic carboxylic acid, aromatic carboxylic acid, and aralkylcarboxylic acid, etc.), carbonylsulfonylimide acid, Bis(alkylsulfonyl)imidic acid and tris(alkylsulfonyl)methideic acid can be mentioned.

The molecular weight of the generated acid of compound (B) is preferably 240 or more, more preferably 250 or more, more preferably 260 or more, particularly preferably 270 or more, and most preferably 280 or more.

<Organic cations>

In the compound represented by "M ⁺ X ^- ", M ⁺ represents an organic cation.

The structure of the organic cation is not particularly limited. Additionally, the valence of the organic cation may be 1 or 2 or higher.

As the organic cation, a cation represented by the following general formula (ZaI) (hereinafter also referred to as "cation (ZaI)"), or a cation represented by the following general formula (ZaII) (hereinafter also referred to as "cation (ZaII)") desirable.

[Formula 28]

In general formula (ZaI), R ²⁰¹ , R ²⁰² , and R ²⁰³ each independently represent an organic group.

In general formula (ZaII), R ²⁰⁴ and R ²⁰⁵ each independently represent an organic group.

The general formulas (ZaI) and (ZaII) will be described in detail below, but at least one of R ²⁰¹ , R ²⁰² , and R ²⁰³ in the general formula (ZaI) is an aryl group, or ) It is preferable that at least one of R ²⁰⁴ and R ²⁰⁵ is an aryl group. The aryl group may have a substituent, and as the substituent, a halogen atom (preferably a fluorine atom or an iodine atom) or an organic group is preferable.

In addition, at least one of R ²⁰¹ , R ²⁰² , and R ²⁰³ in the general formula (ZaI) has an acid-decomposable group, or at least one of R ²⁰⁴ and R ²⁰⁵ in the general formula (ZaII) has an acid-decomposable group. It is also desirable. The acid-decomposable group is the same as that for resin (A). Examples of forms in which at least one of R ²⁰¹ , R ²⁰² , and R ²⁰³ in the general formula (ZaI) has an acid-decomposable group include aryl in which at least one of R ²⁰¹ , R ²⁰² , and R ²⁰³ is substituted with an organic group containing an acid-decomposable group; It is desirable to have As a form in which at least one of R ²⁰⁴ and R ²⁰⁵ in the general formula (ZaII) has an acid-decomposable group, it is preferable that at least one of R ²⁰⁴ and R ²⁰⁵ is an aryl group substituted with an organic group containing an acid-decomposable group.

The cation (ZaI) will be explained.

The carbon number of the organic groups as R ²⁰¹ , R ²⁰² , and R ²⁰³ is usually 1 to 30, and is preferably 1 to 20. Additionally, 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 group, an amide group, or a carbonyl group. Examples of groups formed by combining two of R ²⁰¹ to R ²⁰³ include alkylene groups (for example, butylene groups and pentylene groups), and -CH ₂ -CH ₂ -O-CH ₂ -CH ₂ - I can hear it.

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

First, the cation (ZaI-1) will be described.

The cation (ZaI-1) is an arylsulfonium cation in which at least one of R ²⁰¹ to R ²⁰³ in the formula (ZaI) is an aryl group.

As for the arylsulfonium cation, all of R ₂₀₁ to R ₂₀₃ may be an aryl group, some of R ₂₀₁ to R ₂₀₃ may be an aryl group, and the remainder may be an alkyl group or a cycloalkyl group.

Additionally, one of R ₂₀₁ to R ₂₀₃ is an aryl group, and the remaining two of R ²⁰¹ to R ²⁰³ may be combined to form a ring structure, and an oxygen atom, a sulfur atom, an ester group, an amide group, or a carbonyl group may be present in the ring. It may contain a flag. The group formed by combining two of R ²⁰¹ to R ²⁰³ is, for example, an alkylene group (e.g. For example, butylene group, pentylene group, and -CH ₂ -CH ₂ -O-CH ₂ -CH ₂ -).

Examples of the arylsulfonium cation include triarylsulfonium cation, diarylalkylsulfonium cation, aryldialkylsulfonium cation, diarylcycloalkylsulfonium cation, and aryldicycloalkylsulfonium cation. .

As an aryl group contained in an arylsulfonium cation, a phenyl group or a naphthyl group is preferable, and a phenyl group is more preferable. The aryl group may be an aryl group having a heterocyclic structure containing an oxygen atom, a nitrogen atom, or a sulfur atom. Examples of the heterocyclic structure include pyrrole residues, furan residues, thiophene residues, indole residues, benzofuran residues, and benzothiophene residues. When the arylsulfonium cation has two or more aryl groups, the two or more aryl groups present may be the same or different.

The alkyl group or cycloalkyl group that the arylsulfonium cation has as needed is preferably a linear alkyl group with 1 to 15 carbon atoms, a branched alkyl group with 3 to 15 carbon atoms, or a cycloalkyl group with 3 to 15 carbon atoms, and is preferably a methyl group, ethyl group, Propyl group, n-butyl group, sec-butyl group, t-butyl group, cyclopropyl group, cyclobutyl group, or cyclohexyl group is more preferable.

The substituents that the aryl group, alkyl group, and cycloalkyl group of R ²⁰¹ to R ²⁰³ may each independently be an alkyl group (for example, having 1 to 15 carbon atoms), a cycloalkyl group (for example, having 3 to 15 carbon atoms), Aryl group (e.g., 6 to 14 carbon atoms), alkoxy group (e.g., 1 to 15 carbon atoms), cycloalkylalkoxy group (e.g., 1 to 15 carbon atoms), halogen atom (e.g., fluorine and iodine), hydroxyl group, carboxy group, ester group, sulfinyl group, sulfonyl group, alkylthio group, and phenylthio group are preferred.

The substituent may further have a substituent if possible, and it is also preferable that the alkyl group has a halogen atom as a substituent and is a halogenated alkyl group such as a trifluoromethyl group.

Moreover, it is also preferable that the above substituents form an acid-decomposable group by any combination.

In addition, the acid-decomposable group refers to a group that is decomposed by the action of an acid to generate a polar group, and is preferably a structure in which the polar group is protected by a leaving group that is desorbed by the action of the acid. The above polar group and leaving group are as described above.

Next, the cation (ZaI-2) will be explained.

The cation (ZaI-2) is a cation in which R ²⁰¹ to R ²⁰³ in the formula (ZaI) each independently represent an organic group without an aromatic ring. An aromatic ring also 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, and preferably has 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, and more preferably a linear or branched 2-oxoalkyl group, a 2-oxocycloalkyl group, or an alkoxycarbonylmethyl group. And a linear or branched 2-oxoalkyl group is more preferable.

The alkyl group and cycloalkyl group of R ²⁰¹ to R ²⁰³ are, for example, a straight-chain alkyl group having 1 to 10 carbon atoms or a branched alkyl group having 3 to 10 carbon atoms (for example, methyl group, ethyl group, propyl group, butyl group, and phene group) tyl group), and cycloalkyl groups having 3 to 10 carbon atoms (for example, cyclopentyl group, cyclohexyl group, and norbornyl group).

R ²⁰¹ to R ²⁰³ may be further substituted by a halogen atom, an alkoxy group (for example, having 1 to 5 carbon atoms), a hydroxyl group, a cyano group, or a nitro group.

Moreover, it is also preferable that the substituents of R ²⁰¹ to R ²⁰³ each independently form an acid-decomposable group by any combination of substituents.

Next, the cation (ZaI-3b) will be explained.

Cation (ZaI-3b) is a cation represented by the following formula (ZaI-3b).

[Formula 29]

In formula (ZaI-3b),

R _1c to R _5c are each independently a hydrogen atom, an alkyl group, a cycloalkyl group, an aryl group, an alkoxy group, an aryloxy group, an alkoxycarbonyl group, an alkylcarbonyloxy group, a cycloalkylcarbonyloxy group, a halogen atom, a hydroxyl group, It represents a nitro group, an alkylthio group, or an arylthio group.

R _6c and R _7c each independently represent a hydrogen atom, an alkyl group (eg, t-butyl group, etc.), a cycloalkyl group, a halogen atom, a cyano group, or an aryl group.

R _x and R _y each independently represent an alkyl group, cycloalkyl group, 2-oxoalkyl group, 2-oxocycloalkyl group, alkoxycarbonylalkyl group, allyl group, or vinyl group.

Moreover, it is also preferable that the substituents of R _1c to R _7c , R _x and R _y each independently form an acid-decomposable group by any combination of substituents.

Any two or more of R _1c to R _5c , R _5c and R _6c , R _6c and R _7c , R _5c and R _x , and R _x and R _y may be combined with each other to form a ring, and this ring is: Each may independently contain an oxygen atom, a sulfur atom, a ketone group, an ester bond, or an amide bond.

Examples of the ring include aromatic or non-aromatic hydrocarbon rings, aromatic or non-aromatic heterocycles, and polycyclic condensed rings formed by combining two or more of these rings. Examples of the ring include a 3- to 10-membered ring, a 4- to 8-membered ring is preferable, and a 5- or 6-membered ring is more preferable.

Groups formed by combining any two or more of R _1c to R _5c , R _6c and R _7c , and R _x and R _y include alkylene groups such as butylene groups and pentylene groups. The methylene group in this alkylene group may be substituted with a hetero atom such as an oxygen atom.

The group formed by combining R _5c with R _6c and R _5c with R _x is preferably a single bond or an alkylene group. Examples of the alkylene group include methylene group and ethylene group.

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

Next, the cation (ZaI-4b) will be explained.

Cation (ZaI-4b) is a cation represented by the following formula (ZaI-4b).

[Formula 30]

In formula (ZaI-4b),

l represents an integer from 0 to 2.

r represents an integer from 0 to 8.

R ₁₃ is a group containing a hydrogen atom, a halogen atom (for example, a fluorine atom and an iodine atom, etc.), a hydroxyl group, an alkyl group, a halogenated alkyl group, an alkoxy group, a carboxy group, an alkoxycarbonyl group, or a cycloalkyl group. (It may be a cycloalkyl group itself, or it may be a group containing a part of a cycloalkyl group). These groups may have a substituent.

R ₁₄ is a hydroxyl group, a halogen atom (for example, a fluorine atom and an iodine atom, etc.), an alkyl group, a halogenated alkyl group, an alkoxy group, an alkoxycarbonyl group, an alkylcarbonyl group, an alkylsulfonyl group, a cycloalkylsulfonyl group, Or it represents a group containing a cycloalkyl group (it may be a cycloalkyl group itself, or it may be a group containing a part of a cycloalkyl group). These groups may have a substituent. When there are two or more R ₁₄ , each independently represents the above-mentioned group such as a hydroxyl group.

R ₁₅ each independently represents an alkyl group, a cycloalkyl group, or a naphthyl group. Two R ₁₅ may be bonded to each other to form a ring. When two R ₁₅ are bonded to each other to form a ring, hetero atoms such as an oxygen atom or a nitrogen atom may be included in the ring skeleton. In one aspect, two R ₁₅ 's are alkylene groups, and it is preferable that they combine with each other to form a ring structure. In addition, the alkyl group, the cycloalkyl group, and the naphthyl group, and the ring formed by two R ₁₅ bonds to each other may have a substituent.

In formula (ZaI-4b), the alkyl groups of R ₁₃ , R ₁₄ , and R ₁₅ may be linear or branched. The number of carbon atoms of the alkyl group is preferably 1 to 10. The alkyl group is more preferably a methyl group, ethyl group, n-butyl group, or t-butyl group.

Moreover, it is also preferable that each of the substituents of R ₁₃ to R ₁₅ , R _x and R _y each independently forms an acid-decomposable group by any combination of substituents.

Next, the formula (ZaII) will be explained.

In formula (ZaII), R ²⁰⁴ and R ²⁰⁵ each independently represent an organic group, preferably 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 heterocycle containing an oxygen atom, a nitrogen atom, or a sulfur atom. Examples of the skeleton of an aryl group having a heterocycle include pyrrole, furan, thiophene, indole, benzofuran, and benzothiophene.

The alkyl group and cycloalkyl group of R ²⁰⁴ and R ²⁰⁵ are a straight-chain alkyl group having 1 to 10 carbon atoms or a branched alkyl group having 3 to 10 carbon atoms (for example, a methyl group, ethyl group, propyl group, butyl group, or pentyl group), or A cycloalkyl group having 3 to 10 carbon atoms (e.g., cyclopentyl group, cyclohexyl group, or norbornyl group) is preferable.

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

Specific examples of the organic cation represented by M ⁺ are shown below, but the present invention is not limited to these.

[Formula 31]

[Formula 32]

[Formula 33]

[Formula 34]

<Organic anion>

In the compound represented by "M ⁺ X ^- ", X ^- represents an organic anion.

The organic anion is not particularly limited and includes organic anions of 1 or 2 or higher valence.

As the organic anion, an anion with a significantly low ability to cause a nucleophilic reaction is preferable, and a non-nucleophilic anion is more preferable.

Non-nucleophilic anions include, for example, sulfonic acid anions (aliphatic sulfonic acid anions, aromatic sulfonic acid anions, camphorsulfonic acid anions, etc.), carboxylic acid anions (aliphatic carboxylic acid anions, aromatic carboxylic acid anions, and aralkyl carboxylic acid anions, etc. ), sulfonyl imide anion, bis(alkylsulfonyl)imide anion, and tris(alkylsulfonyl)methide anion.

The aliphatic moiety in the aliphatic sulfonic acid anion and the aliphatic carboxylic acid anion may be a linear or branched alkyl group, a cycloalkyl group, a linear or branched alkyl group with 1 to 30 carbon atoms, or a linear or branched alkyl group with 3 to 30 carbon atoms. Cycloalkyl groups are preferred.

The alkyl group may be, for example, a fluoroalkyl group (it may have a substituent other than a fluorine atom. It may be a perfluoroalkyl group).

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

The alkyl group, cycloalkyl group, and aryl group mentioned above may have a substituent. The substituent is not particularly limited, but specifically includes a nitro group, a halogen atom such as a fluorine atom or a chlorine atom, a carboxyl group, a hydroxyl group, an amino group, a cyano group, an alkoxy group (preferably having 1 to 15 carbon atoms), and an alkyl group. (preferably having 1 to 10 carbon atoms), cycloalkyl group (preferably having 3 to 15 carbon atoms), aryl group (preferably having 6 to 14 carbon atoms), alkoxycarbonyl group (preferably having 2 to 7 carbon atoms), acyl group ( 2 to 12 carbon atoms are preferred), alkoxycarbonyloxy group (preferably 2 to 7 carbon atoms), alkylthio group (preferably 1 to 15 carbon atoms), alkyl sulfonyl group (preferably 1 to 15 carbon atoms), alkyl Iminosulfonyl group (preferably having 1 to 15 carbon atoms) and aryloxysulfonyl group (preferably having 6 to 20 carbon atoms).

As the aralkyl group in the aralkyl carboxylic acid anion, an aralkyl group having 7 to 14 carbon atoms is preferable.

Examples of aralkyl groups having 7 to 14 carbon atoms include benzyl group, phenethyl group, naphthylmethyl group, naphthylethyl group, and naphthylbutyl group.

Examples of the sulfonylimide anion include saccharin anion.

As the alkyl group in the bis(alkylsulfonyl)imide anion and tris(alkylsulfonyl)methide anion, an alkyl group having 1 to 5 carbon atoms is preferable. Substituents for these alkyl groups include halogen atoms, alkyl groups substituted with halogen atoms, alkoxy groups, alkylthio groups, alkyloxysulfonyl groups, aryloxysulfonyl groups, and cycloalkylaryloxysulfonyl groups. A fluorine atom or an alkyl group substituted with a fluorine atom is preferred.

Additionally, the alkyl groups in the bis(alkylsulfonyl)imide anion may be bonded to each other to form a ring structure. Thereby, the acid strength increases.

Other non-nucleophilic anions include, for example, phosphorus fluoride (for example, PF ₆ ^- ), boron fluoride (for example, BF ₄ ^- ), and antimony fluoride (for example, SbF ₆ ^- ). I can hear it.

Non-nucleophilic anions include aliphatic sulfonic acid anions in which at least the α position of the sulfonic acid is substituted with a fluorine atom, aromatic sulfonic acid anions in which the alkyl group is substituted with a fluorine atom, and bis(alkylsulfonyl)imide in which the alkyl group is substituted with a fluorine atom. An anion or a tris(alkylsulfonyl)methide anion in which an alkyl group is substituted with a fluorine atom is preferable. Among them, perfluoroaliphatic sulfonic acid anion (preferably having 4 to 8 carbon atoms) or benzenesulfonic acid anion having a fluorine atom are more preferable, nonafluorobutanesulfonic acid anion, and perfluorooctanesulfonic acid. The anion, pentafluorobenzenesulfonic acid anion, or 3,5-bis(trifluoromethyl)benzenesulfonic acid anion is more preferable.

Preferred examples of non-nucleophilic anions include the anions represented by the following formula (AN4).

[Formula 35]

In formula (AN4), R ¹ to R ³ each independently represent an organic group or a hydrogen atom. L represents a divalent linking group.

In formula (AN4), L represents a divalent linking group.

When there are two or more Ls, the Ls may be the same or different.

As a divalent linking group, for example, -O-CO-O-, -COO-, -CONH-, -CO-, -O-, -S-, -SO-, -SO ₂ -, alkylene group (carbon number 1 to 6 are preferred), cycloalkylene groups (preferably 3 to 15 carbon atoms), alkenylene groups (preferably 2 to 6 carbon atoms), and divalent linking groups combining a plurality of these. Among them, divalent linking groups include -O-CO-O-, -COO-, -CONH-, -CO-, -O-, -SO ₂ -, -O-CO-O-alkylene group-, -COO- An alkylene group-, or -CONH-alkylene group- is preferred, -O-CO-O-, -O-CO-O-alkylene group-, -COO-, -CONH-, -SO ₂ -, or, -COO-alkylene group- is more preferable.

L is preferably a group represented by the following formula (AN4-2), for example.

* ^a -(CR ^2a ₂ ) _X -Q-(CR ^2b ₂ ) _Y -* ^b (AN4-2)

In formula (AN4-2), * ^a represents the bonding position with R ³ in formula (AN4).

* ^b represents the bonding position with -C(R ¹ )(R ² )- in the formula (AN4).

X and Y each independently represent an integer of 0 to 10, and an integer of 0 to 3 is preferable.

R ^2a and R ^2b each independently represent a hydrogen atom or a substituent.

When R ^2a and R ^2b each exist in plural, the plural R ^2a and R ^2b may be the same or different.

However, when Y is 1 or more, R ^2b in CR ^2b ₂ directly bonded to -C(R ¹ )(R ² )- in formula (AN4) is other than a fluorine atom.

Q is * ^A -O-CO-O-* ^B , * ^A -CO-* ^B , * ^A -CO-O-* ^B , * ^A -O-CO-* ^B , * ^A -O-* ^B , * ^A -S-* ^B , or * ^A -SO ₂ -* ^B .

However, when X+Y in formula (AN4-2) is 1 or more and both R ^2a and R ^2b in formula (AN4-2) are all hydrogen atoms, Q is * ^A -O-CO-O- It represents * ^B , * ^A -CO-* ^B , * ^A -O-CO-* ^B , * ^A -O-* ^B , * ^A -S-* ^B , or * ^A -SO ₂ -* ^B .

* ^A represents the bonding position on the R ³ side in the formula (AN4), and * ^B represents the bonding position on the -SO ₃ ^- side in the formula (AN4).

In formula (AN4), R ¹ to R ³ each independently represent an organic group.

The organic group is not limited as long as it has one or more carbon atoms, and may be a straight-chain group (for example, a straight-chain alkyl group) or a branched-chain group (for example, a branched chain group such as a t-butyl group). It can be an alkyl group), and it can also be an annular group. The organic group may or may not have a substituent. The organic group may or may not have heteroatoms (oxygen atoms, sulfur atoms, and/or nitrogen atoms, etc.).

Examples of the organic group include substituents that are not electron-withdrawing groups.

Examples of the substituent that is not the electron withdrawing group include a hydrocarbon group, a hydroxyl group, an oxyhydrocarbon group, an oxycarbonyl hydrocarbon group, an amino group, a hydrocarbon-substituted amino group, and a hydrocarbon-substituted amide group.

Moreover, as the substituent that is not an electron withdrawing group, each independently, -R', -OH, -OR', -OCOR', -NH ₂ , -NR' ₂ , -NHR', or -NHCOR' are preferred. . R' is a monovalent hydrocarbon group.

Examples of the monovalent hydrocarbon group represented by R' include alkyl groups such as methyl, ethyl, propyl, and butyl groups; Alkenyl groups such as ethenyl group, propenyl group, and buteneyl group; Monovalent linear or branched hydrocarbon groups such as alkyne groups such as ethyne group, propyne group, and butyne group; cycloalkyl groups such as cyclopropyl group, cyclobutyl group, cyclopentyl group, cyclohexyl group, norbornyl group, and adamantyl group; Monovalent alicyclic hydrocarbon groups such as cycloalkenyl groups such as cyclopropenyl group, cyclobutenyl group, cyclopentenyl group, and norbornenyl group; Aryl groups such as phenyl group, tolyl group, xylyl group, mesityl group, naphthyl group, methylnaphthyl group, anthryl group, and methylanthryl group; and monovalent aromatic hydrocarbon groups such as aralkyl groups such as benzyl group, phenethyl group, phenylpropyl group, naphthylmethyl group, and anthrylmethyl group.

Among them, R ¹ and R ² are each independently preferably a hydrocarbon group (preferably a cycloalkyl group) or a hydrogen atom.

Among them, it is preferable that R ³ is an organic group having a cyclic structure. The cyclic structure may be monocyclic or polycyclic, and may have a substituent. The ring in the organic group containing a cyclic structure is preferably directly bonded to L in the formula (AN4).

For example, the organic group having the cyclic structure may or may not have heteroatoms (oxygen atoms, sulfur atoms, and/or nitrogen atoms, etc.). The hetero atom may be substituted with one or more carbon atoms forming a cyclic structure.

The organic group having the cyclic structure is preferably, for example, a cyclic hydrocarbon group, a lactone ring group, and a sultone ring group. Among them, the organic group having the above-mentioned cyclic structure is preferably a hydrocarbon group having a cyclic structure.

The cyclic hydrocarbon group is preferably a monocyclic or polycyclic cycloalkyl group. These groups may have a substituent.

The cycloalkyl group may be monocyclic (cyclohexyl group, etc.) or polycyclic (adamantyl group, etc.), and preferably has 5 to 12 carbon atoms.

Examples of the lactone group and sultone group include structures represented by the above-mentioned formulas (LC1-1) to (LC1-21) and structures represented by formulas (SL1-1) to (SL1-3). In this case, a group formed by removing one hydrogen atom from the reducing atom constituting the lactone structure or sultone structure is preferable.

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

[Formula 36]

In formula (AN1), o represents an integer of 1 to 3. p represents an integer from 0 to 10. q represents an integer of 0 to 10.

Xf represents a fluorine atom or an organic group. The organic group may be an organic group substituted with at least one fluorine atom, or may be an organic group without a fluorine atom. The number of carbon atoms of the organic group (preferably an alkyl group) is preferably 1 to 10, and more preferably 1 to 4. Additionally, as the organic group (preferably an alkyl group) substituted with at least one fluorine atom, a perfluoroalkyl group is preferable.

It is preferable _that at least one

R ₄ and R ₅ each independently represent a hydrogen atom, a fluorine atom, an alkyl group, or an alkyl group substituted with at least one fluorine atom. When two or more R ₄ and R ₅ exist, R ₄ and R ₅ may be the same or different, respectively.

The alkyl group represented by R ₄ and R ₅ preferably has 1 to 4 carbon atoms. The alkyl group may have a substituent. As R ₄ and R ₅ , a hydrogen atom is preferable.

Specific examples and suitable aspects of the alkyl group substituted with at least one fluorine atom are the same as those of Xf in formula (AN1).

L represents a divalent linking group.

When there are two or more Ls, the Ls may be the same or different.

As a divalent linking group, for example, -O-CO-O-, -COO-, -CONH-, -CO-, -O-, -S-, -SO-, -SO ₂ -, alkylene group (carbon number 1 to 6 are preferred), cycloalkylene groups (preferably 3 to 15 carbon atoms), alkenylene groups (preferably 2 to 6 carbon atoms), and divalent linking groups combining a plurality of these. Among them, divalent linking groups include -O-CO-O-, -COO-, -CONH-, -CO-, -O-, -SO ₂ -, -O-CO-O-alkylene group-, -COO- An alkylene group-, or -CONH-alkylene group- is preferred, -O-CO-O-, -O-CO-O-alkylene group-, -COO-, -CONH-, -SO ₂ -, or, -COO-alkylene group- is more preferable.

W represents an organic group containing a cyclic structure. Among them, it is preferable that it is a cyclic organic group.

Examples of cyclic organic groups include alicyclic groups, aryl groups, and heterocyclic groups.

The alicyclic group may be monocyclic or polycyclic. Examples of the monocyclic alicyclic group include monocyclic cycloalkyl groups such as cyclopentyl group, cyclohexyl group, and cyclooctyl group. Examples of the polycyclic alicyclic group include polycyclic cycloalkyl groups such as norbornyl group, tricyclodecanyl group, tetracyclodecanyl group, tetracyclododecanyl group, and adamantyl group. Among them, alicyclic groups having a bulky structure of 7 or more carbon atoms, such as norbornyl group, tricyclodecanyl group, tetracyclodecanyl group, tetracyclododecanyl group, and adamantyl group, are preferable.

The aryl group may be monocyclic or polycyclic. Examples of the aryl group include phenyl group, naphthyl group, phenanthryl group, and anthryl group.

The heterocyclic group may be monocyclic or polycyclic. Among them, in the case of a polycyclic heterocyclic group, diffusion of the acid can be further suppressed. Additionally, the heterocyclic group may have aromaticity or may not have aromaticity. Examples of heterocycles having aromaticity include furan rings, thiophene rings, benzofuran rings, benzothiophene rings, dibenzofuran rings, dibenzothiophene rings, and pyridine rings. Examples of heterocycles that do not have aromaticity include tetrahydropyran rings, lactone rings, sultone rings, and decahydroisoquinoline rings. As the heterocyclic ring in the heterocyclic group, a furan ring, a thiophene ring, a pyridine ring, or a decahydroisoquinoline ring is preferable.

The cyclic organic group may have a substituent. Examples of the substituent include an alkyl group (which may be linear or branched, preferably having 1 to 12 carbon atoms), a cycloalkyl group (which may be any of monocyclic, polycyclic, and spirocyclic, and having 3 carbon atoms). ~20 is preferred), aryl group (carbon number 6-14 is preferred), hydroxyl group, alkoxy group, ester group, amide group, urethane group, ureido group, thioether group, sulfonamide group, and sulfonic acid ester. You can raise your flag. Additionally, the carbon constituting the cyclic organic group (carbon contributing to ring formation) may be carbonyl carbon. Additionally, two or more substituents may be combined with each other to form a ring. For example, two alkoxy groups, or a hydroxyl group and an alkoxy group, are bonded to each other to form a ring having a cyclic acetal structure. This ring may have a substituent. Examples of the substituent include an alkyl group (1 to 4 carbon atoms), a halogen atom, a hydroxyl group, an alkoxy group (1 to 4 carbon atoms), a carboxyl group, and an alkoxycarbonyl group (2 to 6 carbon atoms).

As an anion represented by formula (AN1), SO ₃ ^- -CF ₂ -CH ₂ -OCO-(L) _q' -W, SO ₃ ^- -CF ₂ -CHF-CH ₂ -OCO-(L) _q' -W , SO ₃ ^- -CF ₂ -COO-(L) _q' -W, SO ₃ ^- -CF ₂ -CF ₂ -CH ₂ -CH ₂ -(L) _q -W, or, SO ₃ ^- -CF ₂ - CH(CF ₃ )-OCO-(L) _q' -W is preferred. Here, L, q and W are the same as equation (AN1). q' represents an integer from 0 to 10.

As an anion represented by formula (AN1), the following forms (AN2) and (AN3) are also preferable.

Mode (AN2): In formula (AN1), o represents 2, p represents 0, and a carbon atom directly bonded to -SO ₃ ^- (hereinafter, this carbon atom is also called "carbon atom Z1"). The two Xfs bonded to each independently represent a hydrogen atom or an organic group without a fluorine atom, and are connected to a carbon atom adjacent to the carbon atom (hereinafter, this carbon atom is also referred to as “carbon atom Z2”). The two bonded Xf's each independently represent a hydrogen atom or an organic group. Preferred aspects of q, L, and W are the same as those described above.

It is preferable that the two Xfs bonded to the carbon atom Z1 are hydrogen atoms.

It is preferable that at least one of the two It is more desirable.

Embodiment (AN3): In formula (AN1), one of the two Xf each independently represents a fluorine atom or an alkyl group substituted with at least one fluorine atom, and the other independently represents a hydrogen atom, or It represents an organic group that does not have a fluorine atom. Preferred embodiments of o, p, q, R ₄ , R ₅ , L, and W are the same as those described above.

The non-nucleophilic anion may be a benzenesulfonic acid anion, but is preferably a benzenesulfonic acid anion substituted by a branched alkyl group or cycloalkyl group.

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

[Formula 37]

In formula (AN5), Ar represents an aryl group (phenyl group, etc.) and may further have a substituent other than a sulfonic acid anion and -(D-B) group. Examples of the substituent that may be further included include a fluorine atom and a hydroxyl group.

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

D represents a single bond or a divalent linking group. Examples of divalent linking groups include ether groups, thioether groups, carbonyl groups, sulfoxide groups, sulfone groups, sulfonic acid ester groups, ester groups, and groups consisting of combinations of two or more of these groups.

B represents a hydrocarbon group.

B is preferably an aliphatic hydrocarbon structure. B is more preferably an isopropyl group, a cyclohexyl group, or an aryl group (such as a tricyclohexyl phenyl group) which may further have a substituent.

Additionally, B may further have a substituent represented by "-(L) _q -W". L, q and W have the same meaning as L, q and W in the above formula (AN1), and the specific examples and preferred ranges are the same.

As a non-nucleophilic anion, disulfonamide anion is also preferable.

The disulfonamide anion is, for example, an anion represented by N ^- (SO ₂ -R ^q ) ₂ .

Here, R ^q represents an alkyl group which may have a substituent, and a fluoroalkyl group is preferable, and a perfluoroalkyl group is more preferable. Two R ^q may be combined with each other to form a ring. The group formed by two R ^q bonds to each other is preferably an alkylene group that may have a substituent, preferably a fluoroalkylene group, and more preferably a perfluoroalkylene group. The carbon number of the alkylene group is preferably 2 to 4.

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

[Formula 38]

[Formula 39]

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

In formula (d1-2), Z ^2c represents a hydrocarbon group having 1 to 30 carbon atoms which may have a substituent (however, the carbon atom adjacent to S is not substituted with a fluorine atom).

The hydrocarbon group in Z ^2c may be linear or branched, and may have a cyclic structure. Additionally, the carbon atom in the hydrocarbon group (preferably a carbon atom that is a reducing atom when the hydrocarbon group has a cyclic structure) may be carbonyl carbon (-CO-). Examples of the hydrocarbon group include a group having a norbornyl group which may have a substituent. The carbon atom forming the norbornyl group may be carbonyl carbon.

Moreover, "Z ^2c -SO ₃ ^- " in formula (d1-2) is preferably different from the anion represented by formula (AN4), (AN1) or (AN5) described above. For example, Z ^2c is preferably other than an aryl group. Also, for example, the atoms in the α position and the β position with respect to -SO ₃ ^- in Z ^2c are preferably atoms other than a carbon atom having a fluorine atom as a substituent. For example, for Z ^2c -SO ₃ ^- , it is preferable that the atom on α and/or the atom on β are reduction atoms in a cyclic group.

In formula (d1-3), R ⁵² represents an organic group (preferably a hydrocarbon group having a fluorine atom), and Y ³ represents a straight-chain, branched-chain, or cyclic alkylene group, arylene group, or carbo-chain. represents a nyl group, and Rf represents a hydrocarbon group.

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

Organic anions may be used individually or in combination of two or more.

The resist composition preferably contains two or more types of compound (B), or the compound (B) is at least one type selected from the group consisting of the following compound (I) and the following compound (II).

<Compound (I) and Compound (II)>

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

(Compound (I))

Compound (I) is a compound having at least one structural site It is a compound that generates an acid containing the following second acidic moiety derived from site Y.

_Structural ^site _​ ^​ _​

Structural site Y: A structural site consisting of an anionic site A ₂ ^- and a cationic site M ₂ ⁺ and forming a second acidic site represented by HA ₂ upon irradiation of actinic rays or radiation.

It is preferable that the cationic moiety M ₁₊ and ^the cationic moiety M ₂₊ each independently represent ^an organic cation, and specific examples and preferred ranges are the same as those of the organic cation represented by M ⁺ described above.

Additionally, the compound (I) satisfies the following condition I.

^Condition I: In the compound ⁽ I), _{the compound PI obtained by substituting the cationic site M 1+} ⁱⁿ _the structural site An acid dissociation constant _{a1 derived from an acidic moiety represented by HA 1 formed} by substituting the cationic moiety M 1 ⁺ with H ⁺ and an acidic moiety represented by HA ₂ formed by substituting the cationic moiety M ₂ ⁺ with H ⁺ in the structural site Y. It has an acid dissociation constant a2 derived from , and the acid dissociation constant a2 is larger than the acid dissociation constant a1.

Below, Condition I is explained in more detail.

When compound (I) is, for example, a compound that generates an acid having one first acidic moiety derived from the structural site X and one second acidic site derived from the structural site Y, Compound PI corresponds to “a compound having HA ₁ and HA ₂ ”.

To explain the acid dissociation constant a1 and a2 of compound PI more specifically, when the acid dissociation constant of compound PI is determined, the pKa when compound PI becomes "a compound having A ₁ ^- and HA ₂ " is the acid dissociation constant a1, and the pKa when the "compound having A ₁ ^- and HA ₂ " becomes "the compound having A ₁ ^- and A ₂ ^- " is the acid dissociation constant a2.

In addition, compound (I) is, for example, a compound that generates an acid having two first acidic moieties derived from the structural site X and one second acidic moiety derived from the structural site Y. In this case, compound PI corresponds to “a compound having two HA ₁ and one HA ₂ ”.

When the acid dissociation constant of such a compound PI is determined, the acid dissociation constant when the compound PI is "a compound having one A ₁ ^- and one HA ₁ and one HA ₂ ", and "the compound having one A ₁ ^- and 1 HA 2" The acid dissociation constant when “a compound having two HA _1s and one HA ₂ ” becomes “a compound having two A ₁ ^- and one HA ₂ ” corresponds to the acid dissociation constant a1 described above. Additionally, the acid dissociation constant when "a compound having two A ₁ ^- and one HA ₂ " becomes a "compound having two A ₁ ^- and A ₂ ^- " corresponds to the acid dissociation constant a2. That is, in the case of such a compound PI, when it has _{a plurality of acid dissociation constants derived from acidic sites represented by HA 1} ^formed by replacing the cation site M ₁ ⁺ in the structural site The value of the acid dissociation constant a2 is larger than the larger value. In addition, the acid dissociation constant when compound PI becomes "a compound having one A ₁ ^- and one HA ₁ and one HA ₂ " is set to aa, and the acid dissociation constant is aa, and "a compound having one A ₁ ^- and one HA ₁ and one HA 2 When the acid dissociation constant when “a compound having HA ₂ ” becomes “a compound having two A ₁ ^- and one HA ₂ ” as ab, the relationship between aa and ab satisfies aa<ab.

The acid dissociation constant a1 and the acid dissociation constant a2 are determined by the acid dissociation constant measurement method described above.

The above compound PI corresponds to an acid generated when compound (I) is irradiated with actinic light or radiation.

When compound (I) has two or more structural sites X, the structural sites X may be the same or different. Moreover, two or more of the above A ₁ ^- and two or more of the above M ₁ ⁺ may be the same or different, respectively.

In addition, in compound (I), A ₁ ^- and A ₂ ^- , and M ₁ ⁺ and M ₂ ⁺ may be the same or different, but A ₁ ^- and A ₂ ^- are, It is preferable that each is different.

In the above compound PI, the difference (absolute value) between the acid dissociation constant a1 (maximum value when multiple acid dissociation constants a1 exists) and the acid dissociation constant a2 is preferably 0.1 or more, more preferably 0.5 or more, and even more 1.0 or more. desirable. Additionally, the upper limit of the difference (absolute value) between the acid dissociation constant a1 (maximum value when there is more than one acid dissociation constant a1) and the acid dissociation constant a2 is not particularly limited, but is, for example, 16 or less.

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

Moreover, in the compound PI, the acid dissociation constant a1 is preferably 2.0 or less, and more preferably 0 or less. Additionally, the lower limit of the acid dissociation constant a1 is preferably -20.0 or more.

Anionic moiety A ₁ ^- and anionic moiety A ₂ ^- are structural moieties containing a negatively charged atom or atomic group, for example, formulas (AA-1) to (AA-3) and formula (BB) shown below. A structural moiety selected from the group consisting of -1) to (BB-6) can be mentioned.

As the anionic moiety A ₁ ^- , one that can form an acidic moiety with a small acid dissociation constant is preferable, and among them, one of formulas (AA-1) to (AA-3) is more preferable, and formula (AA-1) ) and (AA-3), whichever one is more preferable.

In addition, the anionic site A ₂ ^- is preferably one that can form an acidic site with a larger acid dissociation constant than the anionic site A ₁ ^- , and is more preferably one of formulas (BB-1) to (BB-6). , any one of formulas (BB-1) and (BB-4) is more preferable.

In addition, in the following formulas (AA-1) to (AA-3) and formulas (BB-1) to (BB-6), * represents the binding position.

[Formula 40]

[Formula 41]

The specific structure of compound (I) is not particularly limited, but examples include compounds represented by formulas (Ia-1) to (Ia-5) described later.

-Compound represented by formula (Ia-1)-

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

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

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

In formula (Ia-1), M ₁₁ ⁺ and M ₁₂ ⁺ each independently represent an organic cation.

A ₁₁ ^- and A ₁₂ ^- each independently represent a monovalent anionic functional group.

L ₁ represents a divalent linking group.

M ₁₁ ⁺ and M ₁₂ ⁺ may be the same or different, respectively.

A ₁₁ ^- and A ₁₂ ^- may be the same or different, but are preferably different from each other.

However, in the above formula (Ia-1), in the compound PIa (HA ₁₁ -L ₁ -A ₁₂ H), which is obtained by substituting the cations represented by M ₁₁ ⁺ and M ₁₂ ⁺ with H ⁺ , the cation represented by A ₁₂ H The acid dissociation constant a2 derived from the acidic site is greater than the acid dissociation constant a1 derived from the acidic site represented by HA ₁₁ . Additionally, the appropriate values of the acid dissociation constant a1 and the acid dissociation constant a2 are as described above. In addition, compound PIa and the acid generated from the compound represented by formula (Ia-1) upon irradiation with actinic light or radiation are the same.

Moreover, at least one of M ₁₁ ⁺ , M ₁₂ ⁺ , A ₁₁ ^- , A ₁₂ ^- , and L ₁ may have an acid-decomposable group as a substituent.

In formula (Ia-1), the organic cations represented by M ₁ ⁺ and M ₂ ⁺ are as described above.

The monovalent anionic functional group represented by A ₁₁ ^- is intended to be a monovalent group containing the anion moiety A ₁ ^- described above. In addition, the monovalent anionic functional group represented by A ₁₂ ^- is intended to be a monovalent group containing the anionic moiety A ₂ ^- described above.

As the monovalent anionic functional group represented by A ₁₁ ^- and A ₁₂ ^- , an anionic moiety of any one of the above-mentioned formulas (AA-1) to (AA-3) and formulas (BB-1) to (BB-6) is selected. It is preferable that it is a monovalent anionic functional group containing, and is a monovalent anionic functional group selected from the group consisting of formulas (AX-1) to (AX-3) and formulas (BX-1) to (BX-7). It is more preferable. As the monovalent anionic functional group represented by A ₁₁ ^- , a monovalent anionic functional group represented by any of formulas (AX-1) to (AX-3) is particularly preferable. In addition, as the monovalent anionic functional group represented by A ₁₂ ^- , the monovalent anionic functional group represented by any of the formulas (BX-1) to (BX-7) is preferable, and the monovalent anionic functional group represented by any of the formulas (BX-1) to (BX-7) is preferable. A monovalent anionic functional group represented by any one of -6) is more preferable.

[Formula 42]

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

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

As the monovalent organic group represented by R ^A2 , a linear, branched, or cyclic alkyl group or an aryl group is preferable.

The number of carbon atoms of the alkyl group is preferably 1 to 15, more preferably 1 to 10, and still more preferably 1 to 6.

The alkyl group may have a substituent. As a substituent, a fluorine atom or a cyano group is preferable, and a fluorine atom is more preferable. When the alkyl group has a fluorine atom as a substituent, it may be a perfluoroalkyl group.

As the aryl group, a phenyl group or a naphthyl group is preferable, and a phenyl group is more preferable.

The aryl group may have a substituent. The substituent is preferably a fluorine atom, an iodine atom, a perfluoroalkyl group (for example, carbon atoms of 1 to 10 are preferable, and carbon atoms of 1 to 6 are more preferable), or a cyano group, and a fluorine atom or iodine is preferable. Atoms and perfluoroalkyl groups are more preferable.

In formulas (BX-1) to (BX-4) and (BX-6), R ^B represents a monovalent organic group. * indicates the binding position.

As the monovalent organic group represented by R ^B , a linear, branched, or cyclic alkyl group or an aryl group is preferable.

The number of carbon atoms of the alkyl group is preferably 1 to 15, more preferably 1 to 10, and still more preferably 1 to 6.

The alkyl group may have a substituent. The substituent is not particularly limited, but the substituent is preferably a fluorine atom or a cyano group, and more preferably a fluorine atom. When the alkyl group has a fluorine atom as a substituent, it may be a perfluoroalkyl group.

In addition, in the case of the carbon atom serving as the bonding position in the alkyl group (for example, in the case of formulas (BX-1) and (BX-4), the carbon atom directly bonded to -CO- specified in the formula in the alkyl group corresponds, and the formula In the case of (BX-2) and (BX-3), the carbon atom directly bonded to -SO ₂ - specified in the formula in the alkyl group corresponds, and in the case of formula (BX-6), N ^- specified in the formula in the alkyl group corresponds. (e.g., a carbon atom directly bonded with) has a substituent, and it is also preferable that it is a substituent other than a fluorine atom or a cyano group.

Additionally, the carbon atom of the alkyl group may be substituted with carbonyl carbon.

As the aryl group, a phenyl group or a naphthyl group is preferable, and a phenyl group is more preferable.

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

In formula (Ia-1), the divalent linking group represented by L ₁ is not particularly limited and includes -CO-, -NR-, -CO-, -O-, -S-, -SO-, -SO ₂ -, Alkylene group (preferably having 1 to 6 carbon atoms; may be linear or branched), cycloalkylene group (preferably having 3 to 15 carbon atoms), alkenylene group (preferably having 2 to 6 carbon atoms), divalent aliphatic Heterocyclic group (a 5- to 10-membered ring having at least one N atom, O atom, S atom, or Se atom in the ring structure is preferable, a 5- to 7-membered ring is more preferable, and a 5- to 6-membered ring is more preferable.) , a divalent aromatic heterocyclic group (a 5- to 10-membered ring having at least one N atom, an O atom, an S atom, or a Se atom in the ring structure is preferable, a 5- to 7-membered ring is more preferable, and a 5- to 6-membered ring is more preferable). preferred), a divalent aromatic hydrocarbon ring group (6- to 10-membered rings are preferred, and 6-membered rings are more preferred), and divalent linking groups combining a plurality of these. The above R may be a hydrogen atom or a monovalent organic group. The monovalent organic group is not particularly limited, but for example, an alkyl group (preferably having 1 to 6 carbon atoms) is preferable.

In addition, the alkylene group, the cycloalkylene group, the alkenylene group, the divalent aliphatic heterocyclic group, the divalent aromatic heterocyclic group, and the divalent aromatic hydrocarbon ring group may have a substituent. Examples of the substituent include a halogen atom (preferably a fluorine atom).

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

[Formula 43]

In formula (L1), L ₁₁₁ represents a single bond or a divalent linking group.

The divalent linking group represented by L ₁₁₁ is not particularly limited and includes, for example, -CO-, -NH-, -O-, -SO-, -SO ₂ -, and an alkylene group (preferably carbon number) which may have a substituent. 1 to 6 are more preferable. They may be either linear or branched), cycloalkylene groups may have a substituent (preferably 3 to 15 carbon atoms), and aryl groups may have a substituent (preferably 3 to 15 carbon atoms). 6 to 10), and a divalent linking group combining a plurality of these. The substituent is not particularly limited, and examples include halogen atoms.

p represents an integer of 0 to 3, and preferably represents an integer of 1 to 3.

v represents an integer of 0 or 1.

Xf ₁ each independently represents a fluorine atom or an alkyl group substituted with at least one fluorine atom. The number of carbon atoms of this alkyl group is preferably 1 to 10, and more preferably 1 to 4. Moreover, as the alkyl group substituted with at least one fluorine atom, a perfluoroalkyl group is preferable.

Xf ₂ each independently represents a hydrogen atom, an alkyl group which may have a fluorine atom as a substituent, or a fluorine atom. The number of carbon atoms of this alkyl group is preferably 1 to 10, and more preferably 1 to 4. As _for

Among them, it is preferable that Xf ₁ and Xf ₂ are each independently a fluorine atom or a perfluoroalkyl group having 1 to 4 carbon atoms, and more preferably a fluorine atom or CF ₃ . In particular, it is more preferable that both Xf ₁ and Xf ₂ are fluorine atoms.

* indicates binding position.

When L ₁₁ in formula (Ia-1) represents a divalent linking group represented by formula (L1), the bond (*) on the side of L ₁₁₁ in formula (L1) is A ₁₂ ^- in formula (Ia-1) It is desirable to combine.

-Compounds represented by formulas (Ia-2) to (Ia-4)-

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

[Formula 44]

In formula (Ia-2), A _21a ^- and A _21b ^- each independently represent a monovalent anionic functional group. Here, the monovalent anionic functional group represented by A _21a ^- and A _21b ^- is intended to be a monovalent group containing the anion moiety A ₁ ^- described above. The monovalent anionic functional group represented by A _21a ^- and A _21b ^- is not particularly limited, but for example, a monovalent anionic functional group selected from the group consisting of the formulas (AX-1) to (AX-3) described above. I can hear it.

A ₂₂ ^- represents a divalent anionic functional group. Here, the divalent anionic functional group represented by A ₂₂ ^- is intended to be a divalent group containing the anionic moiety A ₂ ^- described above. Examples of the divalent anionic functional group represented by A ₂₂ ^- include divalent anionic functional groups represented by the formulas (BX-8) to (BX-11) shown below.

[Formula 45]

M _21a ⁺ , M _21b ⁺ , and M ₂₂ ⁺ each independently represent an organic cation. The organic cations represented by M _21a ⁺ , M _21b ⁺ , and M ₂₂ ⁺ have the same meaning as the above-mentioned M ₁ ⁺ and also have the same suitable embodiments.

L ₂₁ and L ₂₂ each independently represent a divalent organic group.

In addition, in the above formula (Ia-2), in the compound PIa-2, which is obtained by substituting the organic cations represented by M _21a ⁺ , M _21b ⁺ and M ₂₂ ⁺ with H ⁺ , A ₂₂ is derived from the acidic moiety represented by H The acid dissociation constant a2 is greater than the acid dissociation constant a1-1 derived from A _21a H and the acid dissociation constant a1-2 derived from the acidic site represented by A _21b H. Additionally, the acid dissociation constant a1-1 and the acid dissociation constant a1-2 correspond to the acid dissociation constant a1 described above.

In addition, A _21a ^- and A _21b ^- may be the same or different from each other. Additionally, M _21a ⁺ , M _21b ⁺ , and M ₂₂ ⁺ may be the same or different from each other.

Moreover, at least one of M _21a ⁺ , M _21b ⁺ , M ₂₂ ⁺ , A _21a ^- , A _21b ^- , L ₂₁ , and L ₂₂ may have an acid-decomposable group as a substituent.

In formula (Ia-3), A _31a ^- and A ₃₂ ^- each independently represent a monovalent anionic functional group. In addition, the definition of the monovalent anionic functional group represented by A _31a ^- is the same as that of A _21a ^- and A _21b ^- in the above-mentioned formula (Ia-2), and the applicable modes are also the same.

The monovalent anionic functional group represented by A ₃₂ ^- is intended to be a monovalent group containing the anionic moiety A ₂ ^- described above. The monovalent anionic functional group represented by A ₃₂ ^- is not particularly limited, and examples include monovalent anionic functional groups selected from the group consisting of formulas (BX-1) to (BX-7) described above.

A _31b ^- represents a divalent anionic functional group. Here, the divalent anionic functional group represented by A _31b ^- is intended to be a divalent group containing the anionic moiety A ₁ ^- described above. Examples of the divalent anionic functional group represented by A _31b ^- include a divalent anionic functional group represented by the formula (AX-4) shown below.

[Formula 46]

M _31a ⁺ , M _31b ⁺ , and M ₃₂ ⁺ each independently represent a monovalent organic cation. The organic cations represented by M _31a ⁺ , M _31b ⁺ , and M ₃₂ ⁺ have the same meaning as the above-mentioned M ₁ ⁺ and also have the same suitable embodiments.

L ₃₁ and L ₃₂ each independently represent a divalent organic group.

However, in the above formula (Ia-3), in the compound PIa-3, which is obtained by replacing the organic cations represented by M _31a ⁺ , M _31b ⁺ , and M ₃₂ ⁺ with H ⁺ , in the acidic site represented by A ₃₂ H The resulting acid dissociation constant a2 is greater than the acid dissociation constant a1-3 derived from the acidic moiety represented by A _31a H and the acid dissociation constant a1-4 derived from the acidic moiety represented by A _31b H. Additionally, the acid dissociation constant a1-3 and the acid dissociation constant a1-4 correspond to the acid dissociation constant a1 described above.

Additionally, A _31a ^- and A ₃₂ ^- may be the same or different from each other. Additionally, M _31a ⁺ , M _31b ⁺ , and M ₃₂ ⁺ may be the same or different from each other.

Moreover, at least one of M _31a ⁺ , M _31b ⁺ , M ₃₂ ⁺ , A _31a ^- , A ₃₂ ^- , L ₃₁ , and L ₃₂ may have an acid-decomposable group as a substituent.

In formula (Ia-4), A _41a ^- , A _41b ^- , and A ₄₂ ^- each independently represent a monovalent anionic functional group. In addition, the definition of the monovalent anionic functional group represented by A _41a ^- and A _41b ^- is the same as that of A _21a ^- and A _21b ^- in the above-mentioned formula (Ia-2). In addition, the definition of the monovalent anionic functional group represented by A ₄₂ ^- has the same meaning as A ₃₂ ^- in the above-mentioned formula (Ia-3), and the applicable aspects are also the same.

M _41a ⁺ , M _41b ⁺ , and M ₄₂ ⁺ each independently represent an organic cation.

L ₄₁ represents a trivalent organic group.

In addition, in the compound PIa-4, which is obtained by substituting H ⁺ for the organic cations represented by M _41a ⁺ , M _41b ⁺ , and M ₄₂ ⁺ in the above formula (Ia-4), at the acidic site represented by A ₄₂ H The resulting acid dissociation constant a2 is greater than the acid dissociation constant a1-5 derived from the acidic moiety represented by A _41a H and the acid dissociation constant a1-6 derived from the acidic moiety represented by A _41b H. Additionally, the acid dissociation constant a1-5 and the acid dissociation constant a1-6 correspond to the acid dissociation constant a1 described above.

Additionally, A _41a ^- , A _41b ^- , and A ₄₂ ^- may be the same or different from each other. Additionally, M _41a ⁺ , M _41b ⁺ , and M ₄₂ ⁺ may be the same or different from each other.

Moreover, at least one of M _41a ⁺ , M _41b ⁺ , M ₄₂ ⁺ , A _41a ^- , A _41b ^- , A ₄₂ ^- , and L ₄₁ may have an acid-decomposable group as a substituent.

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

In addition, the alkylene group, the cycloalkylene group, the alkenylene group, the divalent aliphatic heterocyclic group, the divalent aromatic heterocyclic group, and the divalent aromatic hydrocarbon ring group may have a substituent. Examples of the substituent include a halogen atom (preferably a fluorine atom).

Examples of the divalent organic groups represented by L ₂₁ and L ₂₂ in formula (Ia-2) and L ₃₁ and L ₃₂ in formula (Ia-3) include, for example, a divalent organic group represented by the following formula (L2): It is also desirable.

[Formula 47]

In formula (L2), q represents an integer of 1 to 3. * indicates binding position.

Xf each independently represents a fluorine atom or an alkyl group substituted with at least one fluorine atom. The number of carbon atoms of this alkyl group is preferably 1 to 10, and more preferably 1 to 4. Moreover, as the alkyl group substituted with at least one fluorine atom, a perfluoroalkyl group is preferable.

Xf is preferably a fluorine atom or a perfluoroalkyl group having 1 to 4 carbon atoms, and more preferably a fluorine atom or CF ₃ . In particular, it is more preferable that both Xf are fluorine atoms.

L _A represents a single bond or a divalent linking group.

The divalent linking group represented by L _A is not particularly limited, and examples include -CO-, -O-, -SO-, -SO ₂ -, and an alkylene group (preferably having 1 to 6 carbon atoms. It may be linear or branched). may be chain-shaped), a cycloalkylene group (preferably having 3 to 15 carbon atoms), a divalent aromatic hydrocarbon ring group (6- to 10-membered rings are preferable, and 6-membered rings are more preferable), and 2 combining a plurality of these. A linking group can be mentioned.

In addition, the alkylene group, the cycloalkylene group, and the divalent aromatic hydrocarbon ring group may have a substituent. Examples of the substituent include a halogen atom (preferably a fluorine atom).

Examples of the divalent organic group represented by formula (L2) include *-CF ₂ -*, *-CF ₂ -CF ₂ -*, *-CF ₂ -CF ₂ -CF ₂ -*, *-Ph- O-SO ₂ -CF ₂ -*, *-Ph-O-SO ₂ -CF ₂ -CF ₂ -*, *-Ph-O-SO ₂ -CF ₂ -CF ₂ -CF ₂ -*, and, * -Ph-OCO-CF ₂ -* can be mentioned. In addition, Ph is a phenylene group which may have a substituent, and is preferably a 1,4-phenylene group. The substituent is not particularly limited, but includes an alkyl group (for example, preferably 1 to 10 carbon atoms, more preferably 1 to 6 carbon atoms), an alkoxy group (for example, preferably 1 to 10 carbon atoms, more preferably 1 to 6 carbon atoms), 6 is more preferable), or an alkoxycarbonyl group (for example, preferably 2 to 10 carbon atoms, more preferably 2 to 6 carbon atoms).

When L ₂₁ and L ₂₂ in formula (Ia-2) represent a divalent organic group represented by formula (L2), the bond (*) on the side of L _A in formula (L2) is A in formula (Ia-2) It is preferred to combine with _21a ^- and A _21b ^- .

Additionally, when L ₃₁ and L ₃₂ in formula (Ia-3) represent a divalent organic group represented by formula (L2), the bond (*) on the side of L _A in formula (L2) is It is preferable to combine with A _31a ^- and A ₃₂ ^- .

-Compound represented by formula (Ia-5)-

Next, equation (Ia-5) will be explained.

[Formula 48]

In formula (Ia-5), A _51a ^- , A _51b ^- , and A _51c ^- each independently represent a monovalent anionic functional group. Here, the monovalent anionic functional group represented by A _51a ^- , A _51b ^- , and A _51c ^- is intended to be a monovalent group containing the anion moiety A ₁ ^- described above. The monovalent anionic functional group represented by A _51a ^- , A _51b ^- , and A _51c ^- is not particularly limited, but for example, 1 selected from the group consisting of the above-mentioned formulas (AX-1) to (AX-3). An anionic functional group may be mentioned.

A _52a ^- and A _52b ^- represent a divalent anionic functional group. Here, the divalent anionic functional group represented by A _52a ^- and A _52b ^- is intended to be a divalent group containing the anion moiety A ₂ ^- described above. Examples of the divalent anionic functional group represented by A ₂₂ ^- include divalent anionic functional groups selected from the group consisting of formulas (BX-8) to (BX-11) described above.

M _51a ⁺ , M _51b ⁺ , M _51c ⁺ , M _52a ⁺ , and M _52b ⁺ each independently represent an organic cation. The organic cations represented by M _51a ⁺ , M _51b ⁺ , M _51c ⁺ , M _52a ⁺ , and M _52b ⁺ have the same meaning as the above-mentioned M ₁ ⁺ and have the same applicable aspects.

L ₅₁ and L ₅₃ each independently represent a divalent organic group. The divalent organic groups represented by L ₅₁ and L ₅₃ have the same meaning as L ₂₁ and L ₂₂ in the above-mentioned formula (Ia-2), and the applicable aspects are also the same.

L ₅₂ represents a trivalent organic group. The trivalent organic group represented by L ₅₂ has the same meaning as L ₄₁ in the above-mentioned formula (Ia-4), and the applicable aspects are also the same.

In addition, in the compound PIa-5, which is obtained by substituting the organic cations represented by M _51a ⁺ , M _51b ⁺ , M _51c ⁺ , M _52a ⁺ , and M _52b ⁺ in the above formula (Ia-5) with H ⁺ , The acid dissociation constant a2-1 derived from the acidic site represented by A _52a H and the acid dissociation constant a2-2 derived from the acidic site represented by A _52b H are the acid dissociation constants a1-1 derived from A _51a H and represented by A _51b H. It is greater than the acid dissociation constant a1-2 derived from the acidic site, and the acid dissociation constant a1-3 derived from the acidic site represented by A _51c H. Additionally, the acid dissociation constants a1-1 to a1-3 correspond to the acid dissociation constant a1 described above, and the acid dissociation constants a2-1 and a2-2 correspond to the acid dissociation constant a2 described above.

Additionally, A _51a ^- , A _51b ^- , and A _51c ^- may be the same or different from each other. Additionally, A _52a ^- and A _52b ^- may be the same or different from each other. Additionally, M _51a ⁺ , M _51b ⁺ , M _51c ⁺ , M _52a ⁺ , and M _52b ⁺ may be the same or different from each other.

In addition, at least one of M _51b ⁺ , M _51c ⁺ , M _52a ⁺ , M _52b ⁺ , A _51a ^- , A _51b ^- , A _51c ^- , L ₅₁ , L ₅₂ , and L ₅₃ represents an acid-decomposable group as a substituent. You can have it.

(Compound (II))

Compound (II) is a compound having two or more structural regions and an acid-generating compound containing the structural site Z.

Structural region Z: Nonionic region capable of neutralizing acids

^{In compound} ( _II ⁾ , _{the definition} of ^structural _site The meaning is the same, and the fitting mode is also the same.

In compound PII ^{, which} is obtained by substituting _the cationic site M ₁ ⁺ in ^the structural _site The appropriate range of the acid dissociation constant a1 derived from the acidic moiety represented by is the same as the acid dissociation constant a1 in the compound PI.

In addition, if compound (II) is, for example, a compound that generates an acid having two first acidic sites derived _from structural site It corresponds to “compound having.” When the acid dissociation constant of this compound PII is determined, the acid dissociation constant when compound PII becomes "a compound having one A ₁ ^- and one HA ₁ ", and the acid dissociation constant when compound PII becomes "a compound having one A ₁ ^- and one HA ₁ " The acid dissociation constant when it becomes "this "compound having two A ₁ ^- " corresponds to the acid dissociation constant a1.

The acid dissociation constant a1 is determined by the acid dissociation constant measurement method described above.

The above compound PII corresponds to an acid generated when compound (II) is irradiated with actinic light or radiation.

Additionally, the two or more structural regions X may be the same or different. Additionally, two or more pieces of A ₁ ^- and two or more pieces of M ₁ ⁺ may be the same or different.

The nonionic site capable of neutralizing the acid in the structural site Z is not particularly limited, and is preferably a site containing, for example, a group capable of electrostatically interacting with a proton, or a functional group having electrons.

Examples of the group capable of electrostatically interacting with a proton or the functional group having electrons include a functional group having a macrocyclic structure such as a cyclic polyether, or a functional group having a nitrogen atom having a lone pair of electrons that does not contribute to π conjugation. I can hear it. A nitrogen atom having a lone pair that does not contribute to π conjugation is, for example, a nitrogen atom having a partial structure shown in the following formula.

[Formula 49]

lone pair of electrons

Partial structures of functional groups having groups or electrons capable of electrostatically interacting with protons include, for example, crown ether structures, aza crown ether structures, primary to tertiary amine structures, pyridine structures, imidazole structures, and pyrazine structures. Among them, primary to tertiary amine structures are preferable.

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

[Formula 50]

In the above formula (IIa-1), A _61a ^- and A _61b ^- each have the same meaning as A ₁₁ ^- in the above-mentioned formula (Ia-1), and the applicable modes are also the same. In addition, M _61a ⁺ and M _61b ⁺ each have the same meaning as M ₁₁ ⁺ in the above-mentioned formula (Ia-1), and the applicable modes are also the same.

In the above formula (IIa-1), L ₆₁ and L ₆₂ each have the same meaning as L ₁ in the above-mentioned formula (Ia-1), and the applicable modes are also the same.

In formula (IIa-1), R _2X represents a monovalent organic group. _{The monovalent} organic group represented by R ₂ An alkyl group (preferably having 1 to 10 carbon atoms, which may be linear or branched), which may be substituted with one or a combination of two or more selected from the group consisting of a cycloalkyl group (preferably having 3 to 15 carbon atoms), Or an alkenyl group (preferably having 2 to 6 carbon atoms).

Moreover, the alkylene group, the cycloalkylene group, and the alkenylene group may have a substituent. The substituent is not particularly limited, but examples include a halogen atom (preferably a fluorine atom).

In addition, in the above formula (IIa-1), in the compound PIIa-1 obtained by substituting H ⁺ for the organic cations represented by M _61a ⁺ and M _61b ⁺ , the acid dissociation constant a1 derived from the acidic moiety represented by A _61a H The acid dissociation constant a1-8 derived from the acidic moiety represented by -7 and A _61b H corresponds to the acid dissociation constant a1 described above.

In addition ^, the compound PIIa-1 obtained by substituting the cationic sites M _61a ⁺ _{and M 61b} ⁺ in the structural _region -L ₆₂ -A _61b H corresponds to this. In addition, compound PIIa-1 and the acid generated from the compound represented by formula (IIa-1) upon irradiation with actinic light or radiation are the same.

Moreover, at least one of M _61a ⁺ , M _61b ⁺ , A _61a ^- , A _61b ^- , L ₆₁ , L ₆₂ , and R _2X may have an acid-decomposable group as a substituent.

In the above formula (IIa-2), A _71a ^- , A _71b ^- and A _71c ^- each have the same meaning as A ₁₁ ^- in the above-mentioned formula (Ia-1), and the applicable modes are also the same. In addition, M _71a ⁺ , M _71b ⁺ , and M _71c ⁺ each have the same meaning as M ₁₁ ⁺ in the above-mentioned formula (Ia-1), and the fitting modes are also the same.

In the above formula (IIa-2), L ₇₁ , L ₇₂ and L ₇₃ each have the same meaning as L ₁ in the above-mentioned formula (Ia-1), and the applicable modes are also the same.

In addition, in the above formula (IIa-2), in compound PIIa-2, which is obtained by substituting the organic cation represented by M _71a ⁺ , M _71b ⁺ , and M _71c ⁺ with H ⁺ , the acidic moiety represented by A _71a H The acid dissociation constant a1-9 derived from, the acid dissociation constant a1-10 derived from the acidic site represented by A _71b H, and the acid dissociation constant a1-11 derived from the acidic site represented by A _71c H correspond to the acid dissociation constant a1 described above. do.

In addition, compound PIIa-2, which is obtained by substituting H ⁺ for the cationic sites M _71a ⁺ , M _71b ⁺ , and M _71c ⁺ in the structural region X in the compound (IIa-1), is HA _71a -L ₇₁ -N(L ₇₃ -A _71c H)-L ₇₂ -A _71b H corresponds to this. In addition, compound PIIa-2 and the acid generated from the compound represented by formula (IIa-2) upon irradiation with actinic light or radiation are the same.

Moreover, at least one of M _71a ⁺ , M _71b ⁺ , M _71c ⁺ , A _71a ^- , A _71b ^- , A _71c ^- , L ₇₁ , L ₇₂ , and L ₇₃ may have an acid-decomposable group as a substituent.

The anionic moieties that Compound (I) and Compound (II) may have are exemplified, but the present invention is not limited to these.

[Formula 51]

[Formula 52]

Compound (B) includes, for example, paragraphs [0135] to [0171] of International Publication No. 2018/193954, paragraphs [0077] to [0116] of International Publication No. 2020/066824, and paragraphs of International Publication No. 2017/154345. It is also preferable to use the photo acid generator disclosed in [0018] to [0075], and [0334] to [0335].

The content of compound (B) in the composition of the present invention is not particularly limited, but is preferably 0.1% by mass or more, more preferably 1% by mass or more, and even more preferably 5% by mass or more, based on the total solid content of the composition of the present invention. desirable. Moreover, the content of compound (B) is preferably 70% by mass or less, more preferably 60% by mass or less, and still more preferably 50% by mass or less, based on the total solid content of the composition of the present invention.

Compound (B) may be used individually or in combination of two or more.

[Other acid diffusion control agents]

In addition to the compound represented by general formula (DA1), the composition of the present invention may further contain other acid diffusion control agents. The acid diffusion control agent traps the acid generated from the photoacid generator or the like during exposure and acts as an agent to suppress the reaction of the resin (A) in the unexposed area due to the excess acid generated.

As an acid diffusion control agent, for example, a basic compound (DA), a basic compound whose basicity is reduced or lost by irradiation with actinic light or radiation (DB), and a photoacid generator (B) are relatively effective against the acid generated. An onium salt (DC) that generates a weak acid, a low-molecular-weight compound (DD) that has a nitrogen atom and a group that is released by the action of an acid, or an onium salt compound (DE) that has a nitrogen atom in the cation portion can be used as an acid. It can be used as a diffusion control agent. In the composition of the present invention, known acid diffusion control agents can be appropriately used. 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 paragraphs of US Patent Application Publication No. 2016/0237190A1. Known compounds disclosed in [0403] to [0423] and paragraphs [0259] to [0328] of US Patent Application Publication No. 2016/0274458A1 can be suitably used as an acid diffusion controller.

As the basic compound (DA), a compound having a structure represented by the following general formulas (A) to (E) is preferable.

[Formula 53]

Among general formulas (A) and (E),

R ²⁰⁰ , R ²⁰¹ and R ²⁰² may be the same or different, and each independently represents a hydrogen atom, an alkyl group (preferably having 1 to 20 carbon atoms), a cycloalkyl group (preferably having 3 to 20 carbon atoms), or an aryl group ( It represents carbon number 6~20). R ²⁰¹ and R ²⁰² may be combined with each other to form a ring.

R ²⁰³ , R ²⁰⁴ , R ²⁰⁵ and R ²⁰⁶ may be the same or different, and each independently represents an alkyl group having 1 to 20 carbon atoms.

The alkyl groups in general formulas (A) and (E) may have a substituent or may be unsubstituted.

Regarding the above alkyl group, the alkyl group having a substituent is preferably an aminoalkyl group with 1 to 20 carbon atoms, a hydroxyalkyl group with 1 to 20 carbon atoms, or a cyanoalkyl group with 1 to 20 carbon atoms.

It is more preferable that the alkyl groups in general formulas (A) and (E) are unsubstituted.

Basic compounds (DA) include thiazole, benzothiazole, oxazole, benzoxazole, guanidine, aminopyrrolidine, pyrazole, pyrazoline, piperazine, aminomorpholine, aminoalkylmorpholine, piperidine, Or compounds having these structures are preferred, thiazole structure, benzothiazole structure, oxazole structure, benzoxazole structure, imidazole structure, diazabicyclo structure, onium hydroxide structure, onium carboxylate structure, trialkyl More preferred are compounds having an amine structure, an aniline structure, or a pyridine structure, an alkylamine derivative having a hydroxyl group and/or an ether bond, or an aniline derivative having a hydroxyl group and/or an ether bond.

A basic compound (DB) (hereinafter also referred to as “compound (DB)”) whose basicity is reduced or lost by irradiation of actinic rays or radiation has a proton acceptor functional group and is irradiated with actinic rays or radiation. It is a compound that decomposes and its proton acceptor property decreases or disappears, or changes from proton acceptor property to acidic.

A proton acceptor functional group is a functional group having a group or electron that can electrostatically interact with a proton, for example, a functional group having a macrocyclic structure such as a cyclic polyether, or a non-covalent group that does not contribute to π conjugation. It refers to a functional group having a nitrogen atom with an electron pair. A nitrogen atom having a lone pair that does not contribute to π conjugation is, for example, a nitrogen atom having a partial structure shown in the following formula.

[Formula 54]

lone pair of electrons

Preferred partial structures of the proton acceptor functional group include, for example, crown ether structure, azacrown ether structure, primary to tertiary amine structure, pyridine structure, imidazole structure, and pyrazine structure.

Compound (DB) is decomposed by irradiation of actinic light or radiation, and the proton acceptor property decreases or disappears, or a compound that changes from proton acceptor property to acidic is generated. Here, the decrease or loss of proton acceptor property, or the change from proton acceptor property to acidity refers to a change in proton acceptor property due to the addition of a proton to a proton acceptor functional group, and specifically, the proton acceptor property. This means that when a proton adduct is generated from a compound having a sexual functional group (DB) and a proton, the equilibrium constant in the chemical equilibrium decreases.

Proton acceptor property can be confirmed by measuring pH.

The acid dissociation constant pKa of the compound generated when the compound (DB) is decomposed by irradiation of actinic light or radiation preferably satisfies pKa<-1, and more preferably satisfies -13<pKa<-1, It is more preferable to satisfy -13<pKa<-3.

When a mixture of the photoacid generator (B) and an onium salt (DC) that generates an acid that is relatively weak to the acid generated from the photoacid generator (B) is used, the photoacid generator (B) may be formed by irradiation with actinic rays or radiation. When the acid generated from the generator (B) collides with the onium salt (DC) having an unreacted weak acid anion, the weak acid is released through salt exchange to generate an onium salt having a strong acid anion. In this process, the strong acid is exchanged for a weak acid with a lower catalytic ability, so the acid appears to be deactivated and acid diffusion can be controlled.

As the onium salt (DC), compounds represented by the following general formulas (d1-1) to (d1-3) are preferable.

[Formula 55]

In the formula, R ⁵¹ is a hydrocarbon group that may have a substituent, and Z ^2c is a hydrocarbon group of 1 to 30 carbon atoms that may have a substituent (however, the fluorine atom is not substituted on the carbon adjacent to S). ), R ⁵² is an organic group, Y ³ is a linear, branched or cyclic alkylene group or arylene group, Rf is a hydrocarbon group containing a fluorine atom, M ⁺ is each independently an ammonium cation, It is a sulfonium cation or an iodonium cation.

Preferred examples of the sulfonium cation or iodonium cation represented as M ⁺ include the sulfonium cation exemplified by general formula (ZI) and the iodonium cation exemplified by general formula (ZII).

Onium salt (DC), which is a relatively weak acid relative to a photoacid generator, is a compound (hereinafter referred to as "compound") that has a cationic moiety and an anionic moiety in the same molecule, and in which the cationic moiety and anionic moiety are connected by a covalent bond. (DCA)".) may also be used.

As the compound (DCA), a compound represented by any of the following general formulas (C-1) to (C-3) is preferable.

[Formula 56]

In general formulas (C-1) to (C-3),

R ₁ , R ₂ , and R ₃ each independently represent a substituent having 1 or more carbon atoms.

L ₁ represents a divalent linking group or single bond connecting the cation site and the anion site.

-X ^- represents an anion moiety selected from -COO ^- , -SO ₃ ^- , -SO ₂ ^- , and -N ^- -R ₄ . R ₄ is, at the connection site with the adjacent N atom, a carbonyl group (-C(=O)-), a sulfonyl group (-S(=O) ₂ -), and a sulfinyl group (-S(=O)- ) represents a monovalent substituent having at least one of

R ₁ , R ₂ , R ₃ , R ₄ , and L ₁ may be combined with each other to form a ring structure. Moreover, in general formula (C-3), two of R ₁ to R ₃ together represent one divalent substituent, and may be bonded to the N atom by a double bond.

Substituents having 1 or more carbon atoms for R ₁ to R ₃ include alkyl group, cycloalkyl group, aryl group, alkyloxycarbonyl group, cycloalkyloxycarbonyl group, aryloxycarbonyl group, alkylaminocarbonyl group, cycloalkylaminocarbonyl group, and Arylaminocarbonyl group, etc. can be mentioned. Preferably, it is an alkyl group, cycloalkyl group, or aryl group.

L ₁ as a divalent linking group is a linear or branched alkylene group, a cycloalkylene group, an arylene group, a carbonyl group, an ether bond, an ester bond, an amide bond, a urethane bond, a urea bond, and two or more types thereof. Groups formed by combination, etc. can be mentioned. L ₁ is preferably an alkylene group, an arylene group, an ether bond, an ester bond, or a group formed by combining two or more types thereof.

The low-molecular-weight compound (DD) (hereinafter also referred to as “compound (DD)”), which has a nitrogen atom and a group that is released by the action of an acid, is an amine derivative that has a group that is released by the action of an acid on the nitrogen atom. It is desirable.

As the group that is released by the action of an acid, an acetal group, a carbonate group, a carbamate group, a tertiary ester group, a tertiary hydroxyl group, or a hemiaminal ether group is preferable, and a carbamate group or a hemiaminal ether group is preferable. It is more desirable.

The molecular weight of the compound (DD) is preferably 100 to 1000, more preferably 100 to 700, and still more preferably 100 to 500.

Compound (DD) may have a carbamate group having a protecting group on the nitrogen atom. The protecting group constituting the carbamate group is represented by the following general formula (d-1).

[Formula 57]

In general formula (d-1),

Rb each independently represents a hydrogen atom, an alkyl group (preferably having 1 to 10 carbon atoms), a cycloalkyl group (preferably having 3 to 30 carbon atoms), an aryl group (preferably having 3 to 30 carbon atoms), or an aralkyl group (preferably having 3 to 30 carbon atoms). represents an alkoxyalkyl group (preferably having 1 to 10 carbon atoms) or an alkoxyalkyl group (preferably having 1 to 10 carbon atoms). Rb may be bonded to each other to form a ring.

The alkyl group, cycloalkyl group, aryl group, and aralkyl group represented by Rb are each independently a functional group such as hydroxyl group, cyano group, amino group, pyrrolidino group, piperidino group, morpholino group, and oxo group, and an alkoxy group. , or may be substituted with a halogen atom. The same applies to the alkoxyalkyl group represented by Rb.

As Rb, a linear or branched alkyl group, cycloalkyl group, or aryl group is preferable, and a linear or branched alkyl group or cycloalkyl group is more preferable.

Examples of the ring formed by linking two Rb to each other include alicyclic hydrocarbons, aromatic hydrocarbons, heterocyclic hydrocarbons, and derivatives thereof.

Specific structures of the group represented by general formula (d-1) include, but are not limited to, the structure disclosed in paragraph [0466] of US Patent Publication US2012/0135348A1.

Compound (DD) preferably has a structure represented by the following general formula (6).

[Formula 58]

In general formula (6),

l represents an integer from 0 to 2, m represents an integer from 1 to 3, and satisfies l+m=3.

Ra represents a hydrogen atom, an alkyl group, a cycloalkyl group, an aryl group, or an aralkyl group. When l is 2, the two Ra's may be the same or different, and the two Ra's may be connected to each other to form a heterocycle with the nitrogen atom in the formula. This heterocycle may contain heteroatoms other than the nitrogen atom in the formula.

Rb has the same meaning as Rb in the general formula (d-1), and preferred examples are the same.

In the general formula (6), the alkyl group, cycloalkyl group, aryl group, and aralkyl group as Ra are each independently the same as the above-mentioned groups, which may be substituted with the alkyl group, cycloalkyl group, aryl group, and aralkyl group as Rb. It may be substituted with a group.

Specific examples of the alkyl group, cycloalkyl group, aryl group, and aralkyl group (these groups may be substituted with the above groups) of Ra include the same groups as the specific examples described above for Rb.

Specific examples of the particularly preferred compound (DD) in the present invention include, but are not limited to, the compounds disclosed in paragraph [0475] of US Patent Application Publication No. 2012/0135348A1.

The onium salt compound (DE) having a nitrogen atom in the cation portion (hereinafter also referred to as “compound (DE)”) is preferably a compound having a basic site containing a nitrogen atom in the cation portion. The basic moiety is preferably an amino group, and more preferably an aliphatic amino group. It is more preferable that all atoms adjacent to the nitrogen atom in the basic site are hydrogen atoms or carbon atoms. Also, from the viewpoint of improving basicity, it is preferable that no electron-withdrawing functional group (carbonyl group, sulfonyl group, cyano group, halogen atom, etc.) is directly connected to the nitrogen atom.

Preferred specific examples of the compound (DE) include, but are not limited to, the compounds disclosed in paragraph [0203] of US Patent Application Publication No. 2015/0309408A1.

As a specific example of the acid diffusion control agent, reference may be made to the descriptions in paragraphs [0204] to [0206] of International Publication No. 2018/193954, and these contents are incorporated herein by reference. However, the acid diffusion control agent that can be used in the present invention is not limited to these.

Acid diffusion control agents may be used individually, or two or more types may be used in combination.

When the composition of the present invention further contains other acid diffusion control agents in addition to the compound represented by general formula (DA1), the content of the other acid diffusion control agent in the composition of the present invention (if more than one type is present, Total) is preferably 0.001 to 20% by mass, and more preferably 0.01 to 15% by mass, based on the total solid content of the composition of the present invention.

[solvent]

The composition of the present invention preferably contains a solvent.

In the composition of the present invention, a known resist solvent can be appropriately used as a solvent.

Examples of solvents include alkylene glycol monoalkyl ether carboxylate, alkylene glycol monoalkyl ether, alkyl lactic acid ester, alkoxypropionic acid, cyclic lactone (preferably having 4 to 10 carbon atoms), and ring-containing solvents. Organic solvents such as monoketone compounds (preferably having 4 to 10 carbon atoms), alkylene carbonates, alkyl alkoxyacetates, and alkyl pyruvates can be mentioned.

Regarding the solvent, reference may be made to the description in paragraphs [0187] to [0197] of International Publication No. 2019/058890, and these contents are incorporated in this specification.

The solid content concentration of the actinic ray-sensitive or radiation-sensitive resin composition of the present invention is usually 1.0 to 30 mass%, preferably 1.5 to 10 mass%. By keeping the solid content concentration within the above range, the resist solution can be uniformly applied onto the substrate.

Solid content concentration is the mass percentage of the mass of other components excluding the solvent relative to the total mass of the actinic ray-sensitive or radiation-sensitive resin composition.

[Surfactants]

The composition of the present invention may further contain a surfactant. By containing a surfactant, it becomes possible to form a pattern with good sensitivity and resolution and fewer adhesion and development defects when an exposure light source with a wavelength of 250 nm or less, especially 220 nm or less, is used.

As the surfactant, it is particularly preferable to use a fluorine-based and/or silicon-based surfactant.

Regarding the surfactant, reference may be made to the description in paragraphs [0183] to [0184] of International Publication No. 2019/058890, and these contents are incorporated in this specification.

When the composition of the present invention contains a surfactant, the content thereof is preferably greater than 0 to 2% by mass, more preferably 0.0001 to 2% by mass, more preferably based on the total solid content of the composition. It is 0.0005 to 1 mass%.

[Other additives]

In addition to the components described above, the composition of the present invention contains carboxylic acids, carboxylic acid onium salts, dissolution-blocking compounds with a molecular weight of 3000 or less described in Proceeding of SPIE, 2724, 355 (1996), etc., dyes, plasticizers, photosensitizers, light absorbers, and oxidizing agents. Preventive agents, etc. may be appropriately contained.

In particular, carboxylic acids may be suitably used to improve performance. As the carboxylic acid, aromatic carboxylic acids such as benzoic acid and naphthoic acid are preferable.

When the composition of the present invention contains a carboxylic acid, the content of the carboxylic acid is preferably 0.01 to 10% by mass, more preferably 0.01 to 5% by mass, and still more preferably 0.01 to 3% by mass, based on the total solid content of the composition. am.

[Usage]

The composition of the present invention relates to an actinic ray-sensitive or radiation-sensitive resin composition whose properties change in response to irradiation of actinic rays or radiation. More specifically, the composition of the present invention can be used in semiconductor manufacturing processes such as ICs (Integrated Circuits), manufacturing of circuit boards such as liquid crystal or thermal heads, manufacturing of mold structures for imprinting, other photofabrication processes, or flat printing plates, Or, it relates to an actinic ray-sensitive or radiation-sensitive resin composition used in the production of an acid-curable composition. The pattern formed in the present invention can be used in an etching process, an ion implantation process, a bump electrode formation process, a rewiring formation process, and MEMS (Micro Electro Mechanical Systems).

[Active ray-sensitive or radiation-sensitive film]

The present invention also relates to an actinic ray-sensitive or radiation-sensitive film (preferably a resist film) formed by the actinic ray-sensitive or radiation-sensitive composition of the present invention described above. Such a film is formed, for example, by applying the composition of the present invention onto a support such as a substrate. The thickness of the actinic ray-sensitive or radiation-sensitive film is not particularly limited, but is preferably 0.02 to 0.1 μm. As a method of coating on the substrate, it is applied on the substrate by an appropriate coating method such as spin coat, roll coat, flow coat, dip coat, spray coat, and doctor coat. Spin coating is preferred, and the number of rotations is 1000 to 1000. 3000 rpm (rotations per minute) is preferred. The coating film is prebaked at 60 to 150°C for 1 to 20 minutes, preferably at 80 to 120°C for 1 to 10 minutes to form a thin film.

Regarding the top coat that may be provided on the substrate and the actinic ray-sensitive or radiation-sensitive film, the descriptions in paragraphs [0342] to [0358] of International Publication No. 2017/056832 can be referred to, and these contents are included in the specification of this application. It is used in

[Pattern formation method]

The present invention,

A resist film forming step of forming a resist film using the actinic ray-sensitive or radiation-sensitive resin composition of the present invention;

An exposure process of exposing a resist film,

It also relates to a pattern forming method including a development process of developing the exposed resist film using a developer.

In the present invention, the exposure is preferably performed using an electron beam (EB), an ArF excimer laser, or extreme ultraviolet rays (EUV), and is more preferably performed using an electron beam or extreme ultraviolet rays.

In the manufacture of precision integrated circuit elements, etc., exposure (pattern formation process) on a resist film is preferably performed by first irradiating the resist film of the present invention with an ArF excimer laser, an electron beam, or extreme ultraviolet ray (EUV) in a pattern. . The exposure amount is about 1 to 100 mJ/cm ² in the case of ArF excimer laser, preferably about 20 to 60 mJ/cm ² , and in the case of electron beam, about 0.1 to 20 μC/cm ² , preferably about 3 to 10 μC/cm ² , In the case of extreme ultraviolet rays, exposure is performed to about 0.1 to 20 mJ/cm ² , preferably about 3 to 15 mJ/cm ² .

Next, exposure on a hot plate, preferably at 60 to 150°C for 5 seconds to 20 minutes, more preferably at 80 to 120°C for 15 seconds to 10 minutes, more preferably at 80 to 120°C for 1 to 10 minutes. After heating (post-exposure bake), a pattern is formed by developing, rinsing, and drying. Here, the heating after exposure is appropriately adjusted depending on the acid decomposability of the repeating unit having an acid decomposable group in the resin (A). When acid decomposability is low, it is also preferable that the post-exposure heating temperature is 110°C or higher and the heating time is 45 seconds or longer.

The developer is appropriately selected, but it is preferable to use an alkaline developer (typically an aqueous alkaline solution) or a developer containing an organic solvent (also referred to as an organic developer). When the developing solution is an aqueous alkaline solution, it is an aqueous alkaline solution of 0.1 to 5% by mass, preferably 2 to 3% by mass, such as tetramethylammonium hydroxide (TMAH) or tetrabutylammonium hydroxide (TBAH). Develop for 3 minutes, preferably 0.5 to 2 minutes, by conventional methods such as the dip method, puddle method, or spray method.

You may add an appropriate amount of alcohol and/or surfactant to the alkaline developer. In this way, in the formation of a negative pattern, the film in the unexposed part is dissolved, and the exposed part is difficult to dissolve in the developer, and in the formation of a positive pattern, the film in the exposed part is dissolved, and the unexposed part is dissolved. Since the film is difficult to dissolve in the developer, the desired pattern is formed on the substrate.

The alkali concentration of the alkaline developer is usually 0.1 to 20 mass%.

The pH of the alkaline developer is usually 10.0 to 15.0.

In particular, a 2.38% by mass aqueous solution of tetramethylammonium hydroxide is preferable.

As a rinse liquid in the rinse treatment performed after alkali development, pure water may be used, and an appropriate amount of surfactant may be added.

In addition, after development or rinsing, a process to remove the developing or rinsing solution adhering to the pattern using a supercritical fluid can be performed.

When the pattern forming method of the present invention has a developing step using a developer containing an organic solvent, the developing solution (hereinafter also referred to as an organic developer) in the step includes a ketone solvent, an ester solvent, and an alcohol. Polar solvents such as solvent-based solvents, amide-based solvents, and ether-based solvents and hydrocarbon-based solvents can be used.

The concentration of the organic solvent (total in the case of multiple mixtures) in the organic developer is preferably 50% by mass or more, more preferably 50 to 100% by mass, further preferably 85 to 100% by mass, even more preferably. Typically, it is 90 to 100 mass%, particularly preferably 95 to 100 mass%.

Most preferably, it is substantially composed only of organic solvents. In addition, the case where it consists substantially only of an organic solvent includes the case where it contains a trace amount of surfactant, antioxidant, stabilizer, anti-foaming agent, etc.

In particular, the organic developer is preferably a developer containing at least one type of organic solvent selected from the group consisting of ketone-based solvents, ester-based solvents, alcohol-based solvents, amide-based solvents, and ether-based solvents.

Regarding the pattern formation method, the descriptions in paragraphs [0359] to [0383] of International Publication No. 2017/056832 can be referred to, and these contents are incorporated in this specification.

Actinic ray-sensitive or radiation-sensitive composition in the present invention, and various materials used in the pattern forming method of the present invention (e.g., resist solvent, developer, rinse solution, composition for forming an antireflection film, top coat forming composition, etc.) preferably does not contain impurities such as metals, metal salts containing halogens, acids, alkalis, and components containing sulfur atoms or phosphorus atoms. Here, impurities containing metal atoms include Na, K, Ca, Fe, Cu, Mn, Mg, Al, Cr, Ni, Zn, Ag, Sn, Pb, Li, and salts thereof. .

The content of impurities contained in these materials is preferably 1 ppm (parts per million) or less, more preferably 1 ppb (parts per billion) or less, more preferably 100 ppt (parts per trillion) or less, and particularly preferably 10 ppt or less. It is most desirable that it is substantially free (below the detection limit of the measuring device).

Regarding methods of removing impurities such as metals from various materials, the descriptions in paragraphs [0384] to [0402] of International Publication No. 2017/056832 can be referred to, and these contents are incorporated in this specification.

[Method for manufacturing electronic devices]

Additionally, the present invention also relates to a method of manufacturing an electronic device, including the pattern formation method described above. The electronic device manufactured by the electronic device manufacturing method of the present invention is suitable for electrical and electronic devices (e.g., home appliances, OA (Office Automation) related devices, media related devices, optical devices, and communication devices, etc.) It is mounted.

Example

The present invention will be described in more detail below based on examples. Materials, usage amounts, ratios, processing details, processing procedures, etc. shown in the following examples can be appropriately changed without departing from the spirit of the present invention. Accordingly, the scope of the present invention should not be construed as limited by the examples shown below.

<Resin (A)>

The structure of the repeating unit of the used resin (A), its content (molar ratio), weight average molecular weight (Mw), and dispersion degree (Pd=Mw/Mn) are shown below.

[Formula 59]

[Formula 60]

[Formula 61]

<Synthesis Example 1: Synthesis of Resin (A-1)>

Cyclohexanone (57 g) was heated to 85°C under a nitrogen stream. While stirring this solution, a monomer (50.5 g) represented by the following formula (M-1), a monomer (37.1 g) represented by the following formula (M-2), cyclohexanone (106 g), and 2,2'- A mixed solution of dimethyl azobisisobutyrate (V-601, manufactured by Fujifilm Wako Pure Chemical Industries, Ltd.) (8.6 g) was added dropwise over 3 hours to obtain a reaction solution. After completion of the dropwise addition, the reaction solution was stirred at 85°C for an additional 3 hours. After the obtained reaction liquid was left to cool, it was reprecipitated with 4100 g of ethyl acetate/heptane (mass ratio 1:9), filtered, and the obtained solid was vacuum dried to obtain Resin (A-1) (86 g).

[Formula 62]

Other resins were synthesized in the same manner.

<Mine generator (B)>

The structure of the photoacid generator (B) used is shown below.

[Formula 63]

<Acid diffusion control agent>

The structure of the acid diffusion control agent used is shown below.

[Formula 64]

[Formula 65]

The pKa of the conjugate acids of acid diffusion controllers (D-1) to (D-10), (DX-1) and (DX-2) is shown in Table 1 below.

[Table 1]

<Synthesis Example 2: Synthesis of Compound (D-1)>

After dissolving 5 g of 2,3,5-triiodobenzoic acid in 20 g of tetrahydrofuran (THF), 1.6 g of carbonyldiimidazole was added and stirred at room temperature for 30 minutes. After that, 2.3 g of 1,1,3,3-tetramethylguanidine was added, and the mixture was stirred at 40°C for 1 hour. After cooling the reaction liquid to room temperature, 100 g of water and 100 g of ethyl acetate were added for separation, and the organic phase was washed three times with 100 g of water. The obtained organic phase was concentrated to obtain compound (D-1) as 3.1 g light yellow crystals.

[Formula 66]

Figure 1 shows an NMR (nuclear magnetic resonance) chart (solvent: biacetone) of compound (D-1) obtained in Synthesis Example 2.

<Surfactant>

As the surfactant, the following was used.

W-1: Megapak F176 (Dainippon Ink, manufactured by Kagaku Kogyo Co., Ltd.; fluorine-based)

W-2: Megapak R08 (Dainippon Ink, manufactured by Kagaku Kogyo Co., Ltd.; fluorine and silicone-based)

W-3: Polysiloxane polymer KP-341 (manufactured by Shin-Etsu Chemical Co., Ltd.; silicone type)

W-4: Troizol S-366 (manufactured by Troy Chemical Co., Ltd.)

W-5: KH-20 (manufactured by Asahi Glass Co., Ltd.)

W-6: PolyFox PF-6320 (manufactured by OMNOVA Solutions Inc.; fluorine-based)

<Solvent>

As the solvent, the following was used.

SL-1: Propylene glycol monomethyl ether acetate (PGMEA)

SL-2: Propylene glycol monomethyl ether propionate

SL-3: 2-heptanone

SL-4: Ethyl lactate

SL-5: Propylene glycol monomethyl ether (PGME)

SL-6: Cyclohexanone

SL-7: γ-Beautyrolactone

SL-8: propylene carbonate

[Preparation and application of coating solution of resist composition]

The components shown in Table 2 below were dissolved in the solvent shown in Table 2 below to prepare a solution with a solid content concentration of 2.7% by mass, which was filtered through a polyethylene filter having a pore size of 0.02 μm to produce resist compositions R-1 to R-. 14, RX-1 and RX-2 were obtained.

In addition, in Table 2 below, when two or more types of each component were used, each type and usage amount were indicated by dividing them with "/". For example, in Example 11, "(A-1)/(A-3)" indicates that two types of resin (A), (A-1) and (A-3), were used, and "5/ 5" indicates that 5g each of (A-1) and (A-3) were used.

The obtained resist composition was applied onto a 6-inch Si (silicon) wafer previously treated with hexamethyldisilazane (HMDS) using a spin coater Mark8 manufactured by Tokyo Electron, dried on a hot plate at 130°C for 300 seconds, and formed into a film. A resist film with a thickness of 100 nm was obtained.

Additionally, even if the Si wafer is changed to a chromium substrate, the same result is obtained.

[Table 2]

[EB exposure and development]

The resist film obtained above was subjected to pattern irradiation using an electron beam drawing device (manufactured by Advantest Co., Ltd.; 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, then rinsed with water for 30 seconds and dried. Afterwards, the wafer was rotated at 4000 rpm for 30 seconds, then baked at 95°C for 60 seconds and dried.

[evaluation]

(1) Evaluation method of roughness performance (LWR performance)

Sensitivity (Eopt) (μC/cm ² ) of the optimal exposure amount when resolving a line and space pattern with a line width of 50 nm (1:1) using a long-length scanning electron microscope (Hitachi Seisakusho S-9380II). I did it.

A line and space pattern with a line width of 50 nm (1:1) resolved at an exposure amount representing the sensitivity (Eopt) was examined using a long-length scanning electron microscope (SEM (Hitachi Seisakusho S-9380II)). When observing from the top of the pattern, the line width was observed at an arbitrary point, and the measurement deviation was evaluated as 3σ (nm). A smaller value indicates better performance.

(2) Evaluation method for exposure latitude (EL)

Sensitivity (Eopt) (μC/cm ² ) of the optimal exposure amount when resolving a line and space pattern with a line width of 50 nm (1:1) using a long-length scanning electron microscope (Hitachi Seisakusho S-9380II). I did it.

Using the obtained sensitivity (Eopt) as a standard, the exposure amount when it reached ±10% (i.e., 45 nm and 55 nm) of the target value of 50 nm was determined. Then, the exposure latitude (EL, unit: %) defined in the following equation was calculated. The larger the EL value, the smaller and better the performance change due to changes in exposure amount (EL performance is excellent).

EL(%)=[〔(Exposure amount at which the line width is 55 nm)-(Exposure amount at which the line width is 45 nm)〕/Eopt]×100

(3) Evaluation method for developing defects

In observing the obtained resist pattern of line and space with a line width of 50 nm (1:1), using 2360 manufactured by KLA Tenko, the pixel size of the defect inspection device was set to 0.16 μm and the threshold value was set to 20, and the random mode was used. By measuring , development defects extracted from the differences caused by the overlap of the comparison image and pixel units were detected. After that, the number of defects per unit area on the wafer (number/cm ² ) was measured using SEMVISION G3 (manufactured by APPLIED MATERIALS). A value less than 0.5 was designated A, a value between 0.5 and less than 0.8 was designated B, and a value greater than 0.8 was designated C.

The evaluation results are shown in the "EB Evaluation" column in Table 3 below.

[Extreme ultraviolet (EUV) exposure and development]

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

[evaluation]

(1) Evaluation method for exposure latitude (EL)

Sensitivity (Eopt) (mJ/cm ² ) of the optimal exposure amount when resolving a line and space pattern with a line width of 50 nm (1:1) using a long-length scanning electron microscope (Hitachi Seisakusho S-9380II). I did it.

Using the obtained sensitivity (Eopt) as a standard, the exposure amount when it reached ±10% (i.e., 45 nm and 55 nm) of the target value of 50 nm was determined. Then, the exposure latitude (EL, unit: %) defined in the following equation was calculated. The larger the EL value, the smaller and better the performance change due to changes in exposure amount (EL performance is excellent).

EL(%)=[〔(Exposure amount at which the line width is 55 nm)-(Exposure amount at which the line width is 45 nm)〕/Eopt]×100

The evaluation results are shown in the "EUV evaluation" column in Table 3 below.

[Table 3]

From the results shown in Table 3, the resist compositions of Examples 1 to 14 contain a resin (A) whose polarity increases by the action of an acid and a compound represented by the general formula (DA1), and have EL performance and LWR performance. It can be seen that this is excellent and can reduce development defects. On the other hand, the resist compositions of Comparative Examples 1 and 2 did not contain the compound represented by general formula (DA1) and were inferior to the resist compositions of the Examples in terms of EL performance, LWR performance, and development defects.

Claims (12)

An actinic ray-sensitive or radiation-sensitive resin composition comprising a resin (A) whose polarity increases by the action of an acid, and a compound represented by the following general formula (DA1).
[Formula 1]

In the general formula (DA1),
X ¹ represents a sulfur atom or NQ ³ .
Q ³ represents a hydrogen atom, an organic group, -OH, or -NH ₂ .
Q ¹ represents a hydrogen atom or a substituent.
X ² represents a linking group Xz or a single bond.
The linking group Xz is a divalent linking group consisting of at least one atom selected from the group consisting of a carbon atom, an oxygen atom, a nitrogen atom, and a sulfur atom. However, the nitrogen atom may be bonded to a hydrogen atom, an alkyl group, an aryl group, or an aromatic heterocyclic group, and the sulfur atom may be bonded to a hydrocarbon group.
Ar ^a1 represents an aromatic group.
Q ² represents a hydrogen atom or an alkyl group.
Q ¹ and Q ² may be combined to form a ring.
At least one selected from the group consisting of Q ¹ and Q ² and Q ³ may combine to form a ring.
k represents an integer from 1 to 5.
m represents an integer from 1 to 3.
n and p each independently represent an integer of 0 to 2.
However, m+n+p=3.
When there are multiple X ¹ , X ² , Q ¹ , Q ² , Q ³ and Ar ^a1 , they may be the same or different.
However, when n represents 0, the following condition (i) or (ii) is satisfied.
Condition (i): X ² represents a single bond, and Ar ^a1 represents an aromatic heterocyclic group.
Condition (ii): X ² represents the linking group Xz. In claim 1,
An actinic ray-sensitive or radiation-sensitive resin composition in which X ² in the general formula (DA1) represents a divalent linking group or a single bond represented by any of the following formulas (X2-1) to (X2-11).
[Formula 2]

In the above formula, Q ⁴ and Q ⁵ each independently represent a hydrogen atom, an alkyl group, an aryl group, or an aromatic heterocyclic group. X ³ and X ⁴ each independently represent a single bond, a hydrocarbon group, an oxygen atom, or NQ ⁶ . Q ⁶ represents a hydrogen atom, an alkyl group, an aryl group, or an aromatic heterocyclic group. X ⁵ represents an oxygen atom, a sulfur atom, or NG ¹ . X ⁶ represents -SG ² or -NG ³ G ⁴ . G ¹ , G ³ and G ⁴ each independently represent a hydrogen atom, an alkyl group, an aryl group, or an aromatic heterocyclic group. G ² represents a hydrocarbon group. *1 represents the bonding position with the nitrogen atom in general formula (DA1), and *2 represents the bonding position with Ar ^a1 in general formula (DA1). In claim 1 or claim 2,
The resin (A) has at least one selected from the group consisting of a repeating unit represented by the following formula (3), a repeating unit represented by the following formula (6), and a repeating unit represented by the following formula (7). Actinic ray-sensitive or radiation-sensitive resin composition.
[Formula 3]

In general formula (3),
R ₅ to R ₇ each independently represent a hydrogen atom, an alkyl group, a cycloalkyl group, a halogen atom, a cyano group, or an alkoxycarbonyl group.
L ₂ represents a divalent linking group.
R ₈ to R ₁₀ each independently represent an alkyl group, cycloalkyl group, aryl group, aralkyl group, or alkenyl group. Two of R ₈ to R ₁₀ may combine with each other to form a ring.
[Formula 4]

In general formula (6),
R ₂₂ to R ₂₄ each independently represent a hydrogen atom, an alkyl group, a cycloalkyl group, a halogen atom, a cyano group, or an alkoxycarbonyl group.
L ₄ represents a single bond or a divalent linking group.
Ar ₁ represents an aromatic group.
R ₂₅ to R ₂₇ each independently represent a hydrogen atom, an alkyl group, a cycloalkyl group, an aryl group, an aralkyl group, or an alkenyl group.
R ₂₆ and R ₂₇ may be combined to form a ring.
R ₂₄ or R ₂₅ may be combined with Ar ₁ .
[Formula 5]

In general formula (7),
R ₂₈ to R ₃₀ each independently represent a hydrogen atom, an alkyl group, a cycloalkyl group, a halogen atom, a cyano group, or an alkoxycarbonyl group.
L ₅ represents a single bond or a divalent linking group.
R ₃₁ and R ₃₂ each independently represent a hydrogen atom, an alkyl group, a cycloalkyl group, an aryl group, an aralkyl group, or an alkenyl group.
R ₃₃ represents an alkyl group, cycloalkyl group, aryl group, aralkyl group, or alkenyl group.
R ₃₂ and R ₃₃ may be combined to form a ring. The method according to any one of claims 1 to 3,
An actinic ray-sensitive or radiation-sensitive resin composition in which the resin (A) has a repeating unit represented by the following general formula (A2).
[Formula 6]

In general formula (A2),
R ₁₀₁ , R ₁₀₂ and R ₁₀₃ each independently represent a hydrogen atom, an alkyl group, a cycloalkyl group, a halogen atom, a cyano group or an alkoxycarbonyl group.
L _A represents a single bond or a divalent linking group.
Ar _A represents an aromatic group.
k represents an integer of 1 to 5.
However, R ₁₀₂ may be bonded to Ar _A , and when R ₁₀₂ and Ar _A are bonded, R ₁₀₂ represents a single bond or an alkylene group. The method according to any one of claims 1 to 4,
An actinic ray-sensitive or radiation-sensitive resin composition in which n in the general formula (DA1) represents 1 or 2. In claim 5,
An actinic ray-sensitive or radiation-sensitive resin composition in which Q ¹ in general formula (DA1) represents a substituent containing a nitrogen atom. The method according to any one of claims 1 to 4,
An actinic ray-sensitive or radiation-sensitive resin composition in which n in the general formula (DA1) represents 0, satisfies the above condition (i), and Ar ^a1 represents an aromatic heterocyclic group containing a nitrogen atom. The method according to any one of claims 1 to 7,
An actinic ray-sensitive or radiation-sensitive resin composition, wherein the conjugate acid of the compound represented by the general formula (DA1) has a pKa of 2 or more. The method according to any one of claims 1 to 8,
An actinic ray-sensitive or radiation-sensitive resin composition, wherein the compound represented by the general formula (DA1) is a nonionic compound. An actinic ray-sensitive or radiation-sensitive film formed using the actinic ray-sensitive or radiation-sensitive resin composition according to any one of claims 1 to 9. A process of forming a resist film using the actinic ray-sensitive or radiation-sensitive resin composition according to any one of claims 1 to 9;
A process of exposing the resist film;
A pattern forming method comprising a step of developing the exposed resist film using a developer. A method of manufacturing an electronic device comprising the pattern forming method according to claim 11.