JP2022131762A - Active ray-sensitive or radiation-sensitive resin composition, active ray-sensitive or radiation-sensitive membrane, pattern formation method, and electronic device production method - Google Patents

Abstract

To provide an active ray-sensitive or radiation-sensitive resin composition excellent in resolution and etching resistance.SOLUTION: The active ray-sensitive or radiation-sensitive resin composition contains a resin (A) with a repeating unit (P1) represented by general formula (1) and a repeating unit having at least one aromatic ring, where the content of the repeating units (P1) in the total solids is 0.25 mmol/g or more.SELECTED DRAWING: None

Description

TECHNICAL FIELD The present invention relates to an actinic ray- or radiation-sensitive resin composition, an actinic ray- or radiation-sensitive film, a pattern forming method, and an electronic device manufacturing method.

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

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

Various resins are known as resins used in resist compositions. For example, Patent Document 1 describes a resin having a repeating unit that is decomposed by exposure to actinic rays or radiation to generate an acid.

JP 2016-47920 A

However, a study by the present inventors has revealed that the resist composition containing the resin described in Patent Document 1 is inferior in resolution and etching resistance when used for pattern formation.

An object of the present invention is to provide an actinic ray- or radiation-sensitive resin composition excellent in resolution and etching resistance, and an actinic ray- or radiation-sensitive film using the actinic ray- or radiation-sensitive resin composition. , a pattern forming method, and an electronic device manufacturing method.

The present inventors have made intensive studies and found that the above-described object can be achieved with the following configuration.

[1]
A repeating unit (P1) represented by the following general formula (1) that decomposes upon exposure to actinic rays or radiation to generate an acid, and a repeating unit (P1) having at least one aromatic ring different from the repeating unit (P1) containing a resin (A) having a),
An actinic ray-sensitive or radiation-sensitive resin composition, wherein the content of the repeating unit (P1) in the total solid content is 0.25 mmol/g or more.

In general formula (1), R ₁₁ to R ₁₃ each independently represent a hydrogen atom, an organic group or a halogen atom. However, R ₁₂ may combine with L to form a ring. L represents a single bond or a divalent linking group. R ₁₄ represents a substituent. Q ⁺ represents an organic onium ion.
[2]
The actinic ray-sensitive or radiation-sensitive resin composition according to [1], wherein the repeating unit (a) is represented by the following general formula (2).

In general formula (2), R ₂₁ to R ₂₄ each independently represent a hydrogen atom, an organic group or a halogen atom. R ₂₂ may combine with R ₂₄ to form a ring, in which case R ₂₂ represents a single bond or an alkylene group. However, at least one of R ₂₁ to R ₂₄ represents a group having an aromatic ring.
[3]
The actinic ray-sensitive or radiation-sensitive resin composition according to [1] or [2], wherein the repeating unit (a) is represented by the following general formula (3).

In general formula (3), R ₃₁ to R ₃₃ each independently represent a hydrogen atom, an organic group or a halogen atom. However, R ₃₂ may combine with Ar to form a ring, in which case R ₃₂ represents a single bond or an alkylene group. _L3 represents a single bond or a divalent linking group. Ar represents an aromatic ring group.
[4]
The actinic ray-sensitive or radiation-sensitive resin composition according to any one of [1] to [3], wherein the repeating unit (a) is represented by the following general formula (4).

In general formula (4), R ₄₁ to R ₄₃ each independently represent a hydrogen atom, an organic group or a halogen atom. However, _R42 may combine with Ar to form a ring, in which case _R42 represents a single bond or an alkylene group. L4 represents a single bond or a _divalent linking group. Ar represents an aromatic ring group. k represents an integer of 1 to 5;
[5]
The resin (A) has a repeating unit (P2) having a group that is decomposed by the action of an acid to increase its polarity,
The repeating unit (P2) is a repeating unit having at least one group selected from the group consisting of a group that decomposes under the action of an acid to yield a carboxyl group and a group that decomposes under the action of an acid to yield a hydroxyl group. The actinic ray-sensitive or radiation-sensitive resin composition according to any one of [1] to [4].
[6]
The repeating unit (P2) is at least selected from the group consisting of a group that decomposes under the action of an acid to produce a carboxy group bound to an aromatic ring, and a group that decomposes under the action of an acid to produce a hydroxyl group bound to an aromatic ring. The actinic ray-sensitive or radiation-sensitive resin composition according to [5], which is a repeating unit having one group.
[7]
The actinic ray-sensitive or radiation-sensitive resin composition according to [5], wherein the repeating unit (P2) is a repeating unit represented by any one of the following general formulas (5) to (9).

In general formula (5), R ₅₁ to R ₅₃ each independently represent a hydrogen atom, an alkyl group, a cycloalkyl group, a halogen atom, a cyano group, or an alkoxycarbonyl group. _L5 represents a single bond or a divalent linking group. R ₅₄ to R ₅₆ each independently represent a hydrogen atom, an alkyl group, a cycloalkyl group, an aryl group, an aralkyl group or an alkenyl group. Two of R ₅₄ to R ₅₆ may combine with each other to form a ring.
In general formula (6), R ₆₁ to R ₆₄ each independently represent a hydrogen atom or an organic group. However, at least one of R ₆₁ and R ₆₂ represents an organic group. X ₆ represents -CO-, -SO- or -SO ₂ -. Y ₆ represents -O-, -S-, -SO-, -SO ₂ -, or -NR ₄₈ -. _R48 represents a hydrogen atom or an organic group. _L6 represents a single bond or a divalent linking group. R ₆₅ to R ₆₇ each independently represent a hydrogen atom, an alkyl group, a cycloalkyl group, an aryl group, an aralkyl group or an alkenyl group. Two of R ₆₅ to R ₆₇ may combine with each other to form a ring.
In general formula (7), R ₇₁ and R ₇₂ each independently represent a hydrogen atom or an organic group. _R73 and _R74 each independently represent a hydrogen atom, an alkyl group, a cycloalkyl group, an aryl group, an aralkyl group, or an alkenyl group. Two of R ₇₁ to R ₇₄ may combine with each other to form a ring.
In general formula (8), R ₈₁ to R ₈₃ each independently represent a hydrogen atom, an alkyl group, a cycloalkyl group, a halogen atom, a cyano group, or an alkoxycarbonyl group. _L8 represents a single bond or a divalent linking group. Ar ₈ represents an aromatic ring group. R ₈₄ to R ₈₆ each independently represent a hydrogen atom, an alkyl group, a cycloalkyl group, an aryl group, an aralkyl group or an alkenyl group. Two of R ₈₄ to R ₈₆ may combine with each other to form a ring. Ar ₈ may combine with R ₈₂ or R ₈₄ to form a ring.
In general formula (9), R ₉₁ to R ₉₃ each independently represent a hydrogen atom, an alkyl group, a cycloalkyl group, a halogen atom, a cyano group, or an alkoxycarbonyl group. _L9 represents a single bond or a divalent linking group. R ₉₄ to R ₉₆ each independently represent a hydrogen atom, an alkyl group, a cycloalkyl group, an aryl group, an aralkyl group or an alkenyl group. R ₉₅ and R ₉₆ may combine with each other to form a ring.
[8]
The actinic ray-sensitive or radiation-sensitive resin composition according to [7], wherein the repeating unit (P2) is a repeating unit represented by the general formula (5), (8), or (9).
[9]
The actinic ray-sensitive or radiation-sensitive resin composition according to [7] or [8], wherein L ₅ in the general formula (5) is a divalent aromatic linking group.
[10]
The actinic ray-sensitive or radiation-sensitive resin composition according to [7] or [8], wherein L ₉ in the general formula (9) is a divalent aromatic linking group.
[11]
The actinic ray-sensitive or radiation-sensitive resin composition according to any one of [1] to [10], wherein the content of the repeating unit (P1) in the total solid content is 0.50 mmol/g or more. .
[12]
The actinic ray-sensitive or radiation-sensitive resin composition according to any one of [1] to [11], wherein L in the general formula (1) is a phenylene group.
[13]
The actinic ray-sensitive or radiation-sensitive resin composition according to any one of [1] to [11], wherein L in the general formula (1) is a single bond.
[14]
The actinic ray-sensitive or radiation-sensitive resin composition according to any one of [1] to [11], wherein L in the general formula (1) is an alkylene group having 1 to 3 carbon atoms.
[15]
The actinic ray-sensitive or radiation-sensitive resin composition according to any one of [1] to [14], wherein R ₁₄ in the general formula (1) represents an aryl group or a fluorinated alkyl group.
[16]
The actinic ray-sensitive or radiation-sensitive resin composition according to any one of [1] to [15], wherein the resin (A) is a resin whose solubility in an alkaline developer is increased by the action of an acid.
[17]
An actinic ray- or radiation-sensitive film formed using the actinic ray- or radiation-sensitive resin composition according to any one of [1] to [16].
[18]
A resist film forming step of forming a resist film using the actinic ray-sensitive or radiation-sensitive resin composition according to any one of [1] to [16], and an exposing step of exposing the resist film, and a developing step of developing the exposed resist film using an alkaline developer.
[19]
A method for manufacturing an electronic device, including the pattern forming method according to [18].

According to the present invention, an actinic ray- or radiation-sensitive resin composition excellent in resolution and etching resistance, an actinic ray- or radiation-sensitive film and a pattern using the actinic ray- or radiation-sensitive resin composition Methods of forming and manufacturing electronic devices can be provided.

The present invention will be described in detail below.
The description of the constituent elements described below may be made based on representative embodiments of the present invention, but the present invention is not limited to such embodiments.
The term "actinic ray" or "radiation" as used herein refers to, for example, the emission line spectrum of a mercury lamp, far ultraviolet rays represented by excimer lasers, extreme ultraviolet rays (EUV: Extreme Ultraviolet), X-rays, soft X-rays, and electron It means a line (EB: Electron Beam) or the like. As used herein, "light" means actinic rays or radiation. The term "exposure" as used herein means, unless otherwise specified, not only the emission line spectrum of a mercury lamp, far ultraviolet rays represented by excimer lasers, extreme ultraviolet rays, X-rays, and EUV exposure, but also electron beams and ion beams. It also includes drawing with particle beams such as beams.
In the present specification, the term "~" is used to include the numerical values before and after it as lower and upper limits.

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

Regarding the notation of groups (atomic groups) in this specification, the notations that do not describe substitution and unsubstituted include not only groups having no substituents but also groups having substituents. For example, an "alkyl group" includes not only an alkyl group having no substituent (unsubstituted alkyl group) but also an alkyl group having a substituent (substituted alkyl group). Also, the term "organic group" as used herein refers to a group containing at least one carbon atom.
In the present specification, the bonding direction of the divalent groups represented is not limited unless otherwise specified. For example, in the compound represented by the formula "XYZ", when Y is -COO-, Y may be -CO-O- or -O-CO- good too. Further, the above compound may be "X—CO—O—Z" or "X—O—CO—Z."

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

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

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

<Actinic ray-sensitive or radiation-sensitive resin composition>
The actinic ray-sensitive or radiation-sensitive resin composition of the present invention (hereinafter also referred to as "the composition of the present invention") is represented by the following general formula (1), which decomposes upon exposure to actinic rays or radiation to generate an acid. Represented repeating unit (P1) and a resin (A) having a repeating unit (a) having at least one aromatic ring different from the repeating unit (P1), and the repeating unit ( The actinic ray-sensitive or radiation-sensitive resin composition has a P1) content of 0.25 mmol/g or more.

In general formula (1), R ₁₁ to R ₁₃ each independently represent a hydrogen atom, an organic group or a halogen atom. However, R ₁₂ may combine with L to form a ring. L represents a single bond or a divalent linking group. R ₁₄ represents a substituent. Q ⁺ represents an organic onium ion.

The compositions of the invention are typically resist compositions.
The composition of the present invention may be a positive resist composition or a negative resist composition. Moreover, it may be a resist composition for alkali development or a resist composition for organic solvent development. The composition of the present invention is a positive resist composition, preferably a resist composition for alkali development.
The composition of the present invention is preferably a chemically amplified resist composition, more preferably a chemically amplified positive resist composition.

The components contained in the composition of the present invention are described below.

[Resin (A)]
The resin (A) comprises a repeating unit (P1) represented by the above general formula (1) that decomposes upon exposure to actinic rays or radiation to generate an acid, and at least one aromatic ring different from the repeating unit (P1). It is a resin having a repeating unit (a) having

(Repeating unit (P1))
The repeating unit (P1) is a repeating unit (acid-generating repeating unit) that decomposes upon exposure to actinic rays or radiation to generate an acid, and is represented by the general formula (1).

In general formula (1) above, R ₁₁ to R ₁₃ each independently represent a hydrogen atom, an organic group or a halogen atom.
When R ₁₁ to R ₁₃ represent an organic group, the organic group is not particularly limited, but is preferably an alkyl group, a cycloalkyl group, an aryl group, or an alkoxycarbonyl group, more preferably an alkyl group.
Alkyl groups for R ₁₁ to R ₁₃ are, for example, methyl group, ethyl group, propyl group, isopropyl group, n-butyl group, sec-butyl group, hexyl group, 2-ethylhexyl group, octyl group, dodecyl group and the like. An alkyl group having 20 or less carbon atoms is preferable, and an alkyl group having 8 or less carbon atoms is more preferable.
The alkyl groups as R ₁₁ to R ₁₃ may have substituents.

Cycloalkyl groups for R ₁₁ to R ₁₃ may be monocyclic or polycyclic, and may have a substituent.
Cycloalkyl groups for R ₁₁ to R ₁₃ are preferably C 3-8 monocyclic cycloalkyl groups such as cyclopropyl, cyclopentyl and cyclohexyl groups.

The aryl group as R ₁₁ to R ₁₃ may have a substituent, and is preferably a monocyclic or polycyclic aryl group having 6 to 14 carbon atoms, specifically a phenyl group and a tolyl group. , chlorophenyl group, methoxyphenyl group, naphthyl group and the like. Also, the aryl groups may be bonded together to form a polycyclic ring.

The alkyl groups contained in the alkoxycarbonyl groups for R ₁₁ to R ₁₃ are preferably the same as the alkyl groups for R ₁₁ to R ₁₃ above.

A halogen atom for R ₁₁ to R ₁₃ is preferably a fluorine atom, a chlorine atom, a bromine atom, or an iodine atom, more preferably a fluorine atom.

It is particularly preferred that R ₁₁ and R ₁₂ are hydrogen atoms.
It is particularly preferred that R ₁₃ is a hydrogen atom or a methyl group.

R ₁₂ may combine with L to form a ring.

In general formula (1), L represents a single bond or a divalent linking group.
When L represents a divalent linking group, the divalent linking group includes an arylene group, a heteroarylene group, an alkylene group, a cycloalkylene group, an alkenylene group, -O-, -SO ₂ -, -CO-, - N(R ₃₃ )— or a divalent linking group combining a plurality of these is preferred.
_R33 represents a hydrogen atom, an alkyl group, a cycloalkyl group, an alkenyl group, or an aryl group.
Alkyl groups as R ₃₃ include, for example, methyl group, ethyl group, propyl group, isopropyl group, n-butyl group, sec-butyl group, hexyl group, 2-ethylhexyl group, octyl group, dodecyl group and the like. The following alkyl groups are preferable, and alkyl groups having 8 or less carbon atoms are more preferable.
The alkyl group as R ₃₃ may have a substituent.

The arylene group as L may have a substituent, and preferably has 6 to 14 carbon atoms. Especially preferred.

The heteroarylene group for L is a divalent aromatic group (divalent aromatic heterocyclic group) containing a heteroatom as a ring member, and the heteroatom includes an oxygen atom, a sulfur atom, a nitrogen atom, and the like. be done. The heteroarylene group preferably has 4 to 20 carbon atoms, more preferably 5 to 12 carbon atoms. Examples of heteroarylene groups include groups obtained by removing two hydrogen atoms from pyrrole, furan, thiophene, indole, benzofuran, benzothiophene, and the like.
The heteroarylene group for L may have a substituent.

The alkylene group as L may have a substituent, preferably a methylene group, an ethylene group, a propylene group, a butylene group, a hexylene group, an octylene group and the like having 1 to 8 carbon atoms. An alkylene group of number 1 to 3 is particularly preferred.

The cycloalkylene group for L may have a substituent, and preferably has 5 to 12 carbon atoms such as cyclopentylene, cyclohexylene and adamantylene.

The alkenylene group for L may have a substituent, preferably having 2 to 8 carbon atoms, and particularly preferably an alkenylene group having 2 to 4 carbon atoms.

L is a single bond, or an arylene group, a heteroarylene group, a cycloalkylene group, an alkylene group, an alkenylene group, —O—, —CO—, —N(R ₃₃ )—, or a bivalent combination of these Preferably represents a linking group, a single bond, an arylene group, an alkylene group, an alkenylene group, a divalent linking group obtained by combining -CO- and an alkylene group, a divalent linking obtained by combining -COO- and an alkylene group group, a divalent linking group obtained by combining -CONH- and an alkylene group, or a divalent linking group obtained by combining -COO-, a cycloalkylene group and an alkylene group, a single bond, phenylene or an alkylene group having 1 to 3 carbon atoms is particularly preferred.

When the aforementioned R ₁₁ to R ₁₃ and L can further have one or more substituents, the additional substituents are not particularly limited, but for example, the substituents exemplified for R ₁₄ described later, etc. is mentioned.

In general formula (1), R ₁₄ represents a substituent.
The substituent represented by R ₁₄ is not particularly limited, but examples include hydroxyl group, halogen atom (preferably fluorine atom, bromine atom, chlorine atom, or iodine atom), nitro group, cyano group, amide group, sulfonamide group, and alkyl group. (preferably alkyl group having 1 to 8 carbon atoms), cycloalkyl group (preferably cycloalkyl group having 5 to 12 carbon atoms), alkoxy group (preferably alkoxy group having 1 to 8 carbon atoms), alkoxycarbonyl group (preferably is an alkoxycarbonyl group having 2 to 8 carbon atoms), an alkylcarbonyl group (preferably an alkylcarbonyl group having 2 to 8 carbon atoms), an acyl group (preferably an acyl group having 2 to 8 carbon atoms), an acyloxy group (preferably a carbon 2 to 8 acyloxy groups), carboxy groups, aryl groups (preferably aryl groups having 6 to 12 carbon atoms), heteroaryl groups (preferably at least one of an oxygen atom, a nitrogen atom, and a sulfur atom as hetero atoms heteroaryl group containing 3 to 8 carbon atoms) and the like.
Further, the substituent represented by R ₁₄ may be an acid-decomposable group described later.
The substituent represented by R ₁₄ is preferably an alkyl group, an aryl group or a heteroaryl group, more preferably an alkyl group or an aryl group.

_In addition, when the substituent represented by R ₁₄ can further have one or more substituents, the group having a substituent selected from the above-described substituents represented by R ₁₄ as the further substituent is also included in the example. As the further substituent, a halogen atom is preferable, and a fluorine atom is more preferable.
R ₁₄ is preferably an aryl group or a fluorinated alkyl group, more preferably an aryl group having 6 to 12 carbon atoms or a fluorinated alkyl group having 1 to 6 carbon atoms, and further a fluorinated alkyl group having 1 to 6 carbon atoms. preferable.

In general formula (1), Q ⁺ represents an organic onium ion.
More preferably, Q ⁺ is an organic sulfonium ion or an organic iodonium ion.
Q ⁺ is particularly preferably represented by the following general formula (ZIa) or (ZIIa).

In the above general formula (ZIa),
R ₂₀₁ , R ₂₀₂ and R ₂₀₃ each independently represent an organic group.
The number of carbon atoms in the organic groups as R ₂₀₁ , R ₂₀₂ and R ₂₀₃ is generally 1-30, preferably 1-20.
Also, two of R ₂₀₁ to R ₂₀₃ may combine to form a ring structure, and the ring may contain an oxygen atom, a sulfur atom, an ester bond, an amide bond or a carbonyl group. Examples of the group formed by combining two of R ₂₀₁ to R ₂₀₃ include an alkylene group (eg, a butylene group and a pentylene group).

Examples of organic groups for R ₂₀₁ , R ₂₀₂ and R ₂₀₃ include groups corresponding to (ZI-1a), (ZI-2a), (ZI-3a) or (ZI-4a) described later. can.
More preferred organic sulfonium ions represented by general formula (ZIa) include (ZI-1a), (ZI-2a), (ZI-3a), and (ZI-4a) described below.

(ZI-1a) is an arylsulfonium ion in which at least one of R ₂₀₁ to R ₂₀₃ in general formula (ZIa) above is an aryl group.

All of R ₂₀₁ to R ₂₀₃ may be aryl groups, or part of R ₂₀₁ to R ₂₀₃ may be aryl groups and the rest may be alkyl groups or cycloalkyl groups.
(ZI-1a) includes, for example, triarylsulfonium, diarylalkylsulfonium, aryldialkylsulfonium, diarylcycloalkylsulfonium, and aryldicycloalkylsulfonium.

The aryl group in the arylsulfonium is preferably a phenyl group or a naphthyl group, more preferably a phenyl group. The aryl group may be an aryl group having a heterocyclic structure containing an oxygen atom, a nitrogen atom, a sulfur atom, or the like. Heterocyclic structures include structures such as pyrrole, furan, thiophene, indole, benzofuran, and benzothiophene. When the arylsulfonium has two or more aryl groups, the two or more aryl groups may be the same or different.

The alkyl group or cycloalkyl group optionally possessed by the arylsulfonium is preferably a linear or branched alkyl group having 1 to 15 carbon atoms and a cycloalkyl group having 3 to 15 carbon atoms, such as methyl group, ethyl group, propyl group, n-butyl group, sec-butyl group, t-butyl group, cyclopropyl group, cyclobutyl group, cyclohexyl group and the like.

The aryl group, alkyl group, and cycloalkyl group of R ₂₀₁ to R ₂₀₃ are an alkyl group (eg, 1 to 15 carbon atoms), a cycloalkyl group (eg, 3 to 15 carbon atoms), an aryl group (eg, 6 to 14 carbon atoms). , an alkoxy group (eg, having 1 to 15 carbon atoms), a halogen atom, a hydroxyl group, or a phenylthio group as a substituent. Preferred substituents are linear or branched alkyl groups having 1 to 12 carbon atoms, cycloalkyl groups having 3 to 12 carbon atoms, and linear, branched or cyclic alkoxy groups having 1 to 12 carbon atoms, more preferably carbon atoms. It is an alkyl group having 1 to 4 carbon atoms and an alkoxy group having 1 to 4 carbon atoms. Any one of the three R ₂₀₁ to R ₂₀₃ may be substituted with a substituent, or all three may be substituted. Further, when R ₂₀₁ to R ₂₀₃ are aryl groups, the substituent is preferably substituted at the p-position of the aryl group.

Next, (ZI-2a) will be described.
(ZI-2a) is an organic sulfonium ion in which R ₂₀₁ to R ₂₀₃ in general formula (ZIa) each independently represents an organic group having no aromatic ring. Here, the aromatic ring includes heteroatom-containing aromatic rings.
The aromatic ring-free organic groups for R ₂₀₁ to R ₂₀₃ generally have 1 to 30 carbon atoms, preferably 1 to 20 carbon atoms.

R ₂₀₁ to R ₂₀₃ are each independently preferably alkyl group, cycloalkyl group, allyl group or vinyl group, and more preferably linear or branched 2-oxoalkyl group, 2-oxocycloalkyl group or alkoxy A carbonylmethyl group, particularly preferably a straight-chain or branched 2-oxoalkyl group.

The alkyl group and cycloalkyl group represented by R ₂₀₁ to R ₂₀₃ are preferably linear or branched alkyl groups having 1 to 10 carbon atoms (eg, methyl group, ethyl group, propyl group, butyl group, pentyl group), carbon Cycloalkyl groups of number 3 to 10 (cyclopentyl group, cyclohexyl group, norbornyl group) can be mentioned. More preferably, the alkyl group includes a 2-oxoalkyl group and an alkoxycarbonylmethyl group. As the cycloalkyl group, a 2-oxocycloalkyl group can be mentioned more preferably.

The 2-oxoalkyl group may be either linear or branched, and preferably includes groups having >C=O at the 2-position of the above alkyl groups.
The 2-oxocycloalkyl group preferably includes groups having >C=O at the 2-position of the above cycloalkyl group.

The alkoxy group in the alkoxycarbonylmethyl group preferably includes an alkoxy group having 1 to 5 carbon atoms (methoxy group, ethoxy group, propoxy group, butoxy group, pentoxy group).
R ₂₀₁ to R ₂₀₃ may be further substituted with a halogen atom, an alkoxy group (eg, 1-5 carbon atoms), a hydroxyl group, a cyano group, or a nitro group.

(ZI-3a) and (ZI-4a) are organic sulfonium ions represented by the following general formula (ZI-3a) or (ZI-4a), respectively. (ZI-3a) and (ZI-4a) are highly transparent to the ArF exposure wavelength (193 nm).

In general formula (ZI-3a), M represents an alkyl group, a cycloalkyl group, an aryl group or a benzyl group, and when it has a ring structure, the ring structure is an oxygen atom, a sulfur atom, an ester bond, an amide bond, or It may contain carbon-carbon double bonds.
_R1c and _R2c each independently represent a hydrogen atom, an alkyl group, a cycloalkyl group, a halogen atom, a cyano group or an aryl group.
R _x and R _y each independently represent an alkyl group, a cycloalkyl group, a 2-oxoalkyl group, an alkoxycarbonylalkyl group, an allyl group, or a vinyl group.
R _x and R _y may combine to form a ring.
At least two of M, R _1c and R _2c may combine to form a ring, and the ring structure may contain a carbon-carbon double bond.

In the general formula (ZIa-4),
_R13 represents a hydrogen atom, a fluorine atom, a hydroxyl group, an alkyl group, a cycloalkyl group, an alkoxy group, an alkoxycarbonyl group, or a group having a monocyclic or polycyclic cycloalkyl skeleton.
When multiple R ₁₄ are present, they are each independently an alkyl group, a cycloalkyl group, an alkoxy group, an alkoxycarbonyl group, an alkylcarbonyl group, an alkylsulfonyl group, a cycloalkylsulfonyl group, or a monocyclic or polycyclic cycloalkyl skeleton. represents a group having
Each R ₁₅ independently represents an alkyl group, a cycloalkyl group or a naphthyl group. Two R ₁₅ may be bonded together to form a ring.
k represents an integer of 0 to 2;
r represents an integer of 0 to 8;

First, the organic sulfonium ion represented by general formula (ZI-3a) will be described.
M represents an alkyl group, a cycloalkyl group, an aryl group or a benzyl group as described above, and when it has a ring structure, the ring structure is an oxygen atom, a sulfur atom, an ester atom, an amide bond or a carbon-carbon double May contain a bond.

The alkyl group for M may be linear or branched. The alkyl group preferably has 1 to 20 carbon atoms, more preferably 1 to 12 carbon atoms. Examples of such alkyl groups include methyl, ethyl, n-propyl, isopropyl, n-butyl, sec-butyl, tert-butyl, pentyl, hexyl, octyl, 2- Mention may be made of the ethylhexyl group.

The cycloalkyl group for M preferably has 3 to 12 carbon atoms. Examples of such cycloalkyl groups include cyclopropyl, cyclobutyl, cyclopentyl, cyclohexyl, cycloheptyl and cyclodecyl groups.

The aryl group for M preferably has 5 to 15 carbon atoms. Such aryl groups include phenyl and naphthyl groups.

Each group for M may have a cycloalkyl group, an alkoxy group, a halogen atom, a phenylthio group, or the like as a substituent. The cycloalkyl group and aryl group as M may have an alkyl group as a substituent. The number of carbon atoms in these substituents is preferably 15 or less.

When M is a phenyl group, it preferably has at least one alkyl group, cycloalkyl group, alkoxy group, cycloalkoxy group, or phenylthio group as a substituent. In this case, it is more preferable that the total number of carbon atoms in the substituents is 2-15. By adopting such a configuration, the solubility of the acid generator in the solvent is improved, and it becomes possible to further suppress the generation of particles during storage.

Each of R _1c and R _2c represents a hydrogen atom, an alkyl group, a cycloalkyl group, a halogen atom, a cyano group or an aryl group, as described above.
This alkyl group may be linear or branched. The alkyl group preferably has 1 to 12 carbon atoms, more preferably 1 to 5 carbon atoms. Such alkyl groups include, for example, methyl groups, ethyl groups, and straight or branched chain propyl groups.

The cycloalkyl group is, for example, a cycloalkyl group having 3 to 12 carbon atoms, preferably a cyclopropyl group, a cyclobutyl group, a cyclopentyl group, a cyclohexyl group, a cycloheptyl group, a cyclodecyl group and the like.

Halogen atoms include fluorine, chlorine, bromine and iodine atoms.

The aryl group for R _1c and R _2c preferably has 5 to 15 carbon atoms, and examples thereof include phenyl and naphthyl groups.

As described above, at least two of M, _R1c and _R2c may combine with each other to form a ring. This ring is preferably a 3- to 12-membered ring, more preferably a 3- to 10-membered ring, and still more preferably a 3- to 6-membered ring. The ring may contain a carbon-carbon double bond.

When R _1c and R _2c combine to form a ring, the group formed by combining R _1c and R _2c is preferably an alkylene group having 2 to 10 carbon atoms, such as ethylene and propylene. group, butylene group, pentylene group, hexylene group, and the like. Moreover, the ring formed by combining R _1c and R _2c may have a heteroatom such as an oxygen atom in the ring.

Each of R _x and R _y represents an alkyl group, cycloalkyl group, 2-oxoalkyl group, alkoxycarbonylalkyl group, cycloalkoxycarbonylmethyl group, allyl group, or vinyl group, as described above.

As the alkyl group, for example, the same groups as those described above as the alkyl groups for R _1c and R _2c can be mentioned.
The cycloalkyl group preferably has 3 to 12 carbon atoms, and examples thereof include cyclopropyl, cyclobutyl, cyclopentyl, cyclohexyl, cycloheptyl and cyclodecyl groups.

Examples of 2-oxoalkyl groups include groups having >C=O at the 2-position of the above alkyl groups.

The alkoxy group portion of the alkoxycarbonylmethyl group may be linear or branched. The alkoxy group portion preferably has 1 to 10 carbon atoms, more preferably 1 to 5 carbon atoms. Such alkoxy groups include, for example, methoxy groups, ethoxy groups, straight-chain or branched propoxy groups, straight-chain or branched butoxy groups, and straight-chain or branched pentoxy groups.

The cycloalkoxy group portion of the cycloalkoxycarbonylalkyl group preferably has 3 to 8 carbon atoms. Such cycloalkoxy groups include, for example, cyclopentyloxy and cyclohexyloxy groups. The alkyl group in the alkoxycarbonylalkyl group includes, for example, an alkyl group having 1 to 12 carbon atoms, preferably a linear alkyl group having 1 to 5 carbon atoms, such as a methyl group and an ethyl group. be able to.

As described above, R _x and R _y may combine with each other to form a ring. Examples of the group formed by combining R _x and R _y include alkylene groups such as a butylene group and a pentylene group.
The allyl group is not particularly limited, but is preferably an allyl group substituted with an unsubstituted monocyclic or polycyclic cycloalkyl group.
Although the vinyl group is not particularly limited, it is preferably a vinyl group substituted with an unsubstituted monocyclic or polycyclic cycloalkyl group.

Each of R _x and R _y is preferably an alkyl group having 4 or more carbon atoms, more preferably an alkyl group having 6 or more carbon atoms, and even more preferably an alkyl group having 8 or more carbon atoms.

Specific examples of the organic sulfonium ion represented by formula (ZI-3a) are shown below, but the present invention is not limited thereto.

Next, the organic sulfonium ion represented by the general formula (ZI-4a) will be described.
The alkyl groups of R ₁₃ , R ₁₄ and R ₁₅ may be linear or branched. This alkyl group preferably has 1 to 10 carbon atoms. Such alkyl groups include, for example, methyl group, ethyl group, n-propyl group, i-propyl group, n-butyl group, 2-methylpropyl group, 1-methylpropyl group, t-butyl group, n- Examples include pentyl, neopentyl, n-hexyl, n-heptyl, n-octyl, 2-ethylhexyl, n-nonyl and n-decyl groups. Among these, methyl group, ethyl group, n-butyl group and t-butyl group are particularly preferred.

Cycloalkyl groups for R ₁₃ , R ₁₄ and R ₁₅ include, for example, cyclopropyl, cyclobutyl, cyclopentyl, cyclohexyl, cycloheptyl, cyclooctyl, cyclododecanyl, cyclopentenyl, cyclohexenyl and cyclooctadienyl groups. be done. Of these, cyclopropyl, cyclopentyl, cyclohexyl and cyclooctyl groups are particularly preferred.

The alkoxy groups of R ₁₃ and R ₁₄ may be linear or branched. This alkoxy group preferably has 1 to 10 carbon atoms. Examples of such alkoxy groups include methoxy, ethoxy, n-propoxy, i-propoxy, n-butoxy, 2-methylpropoxy, 1-methylpropoxy, t-butoxy, n- pentyloxy, neopentyloxy, n-hexyloxy, n-heptyloxy, n-octyloxy, 2-ethylhexyloxy, n-nonyloxy and n-decyloxy groups. Among these, methoxy group, ethoxy group, n-propoxy group and n-butoxy group are particularly preferred.

The alkoxycarbonyl groups of R ₁₃ and R ₁₄ may be linear or branched. The alkoxycarbonyl group preferably has 2 to 11 carbon atoms. Examples of such alkoxycarbonyl groups include methoxycarbonyl, ethoxycarbonyl, n-propoxycarbonyl, i-propoxycarbonyl, n-butoxycarbonyl, 2-methylpropoxycarbonyl and 1-methylpropoxycarbonyl groups. , t-butoxycarbonyl group, n-pentyloxycarbonyl group, neopentyloxycarbonyl group, n-hexyloxycarbonyl group, n-heptyloxycarbonyl group, n-octyloxycarbonyl group, 2-ethylhexyloxycarbonyl group, n- A nonyloxycarbonyl group and an n-decyloxycarbonyl group can be mentioned. Among these, methoxycarbonyl group, ethoxycarbonyl group and n-butoxycarbonyl group are particularly preferred.

The group having a monocyclic or polycyclic cycloalkyl skeleton represented by R ₁₃ and R ₁₄ preferably has a total carbon number of 7 or more, more preferably 7 or more and 15 or less.

The group having a monocyclic or polycyclic cycloalkyl skeleton includes, for example, a monocyclic or polycyclic cycloalkyloxy group and an alkoxy group having a monocyclic or polycyclic cycloalkyl group. A group having a cycloalkyl skeleton is preferred. These groups may further have a substituent.

Monocyclic cycloalkyloxy groups include, for example, cyclopropyloxy, cyclobutyloxy, cyclopentyloxy, cyclohexyloxy, cycloptyloxy, cyclooctyloxy and cyclododecanyloxy groups. These groups have substituents such as methyl group, ethyl group, propyl group, butyl group, pentyl group, hexyl group, heptyl group, octyl group, dodecyl group, 2-ethylhexyl group, isopropyl group, sec-butyl group, Alkyl groups such as tert-butyl and iso-amyl groups; hydroxyl groups: halogen atoms such as fluorine, chlorine, bromine and iodine atoms; nitro groups; cyano groups; amide groups; sulfonamide groups; alkoxy groups such as methoxycarbonyl and ethoxycarbonyl; acyl groups such as formyl, acetyl and benzoyl; acyloxy such as acetoxy and butyryloxy; group; or a carboxy group.

Polycyclic cycloalkyloxy groups include, for example, norbornyloxy and adamantyloxy groups.

The monocyclic or polycyclic cycloalkyloxy group preferably has 7 or more carbon atoms in total, as described above. That is, it is preferable to employ a structure in which the total number of carbon atoms in the cycloalkyloxy group and the substituent is 7 or more.

Alkoxy groups having monocyclic cycloalkyl groups include methoxy, ethoxy, propoxy, butoxy, pentyloxy, hexyloxy, heptoxy, octyloxy, dodecyloxy, 2-ethylhexyloxy, isopropoxy, sec-butoxy and t-butoxy. , iso-amyloxy, etc., substituted with a monocyclic cycloalkyl group. This monocyclic cycloalkyl group may further have the substituents listed above. Examples thereof include a cyclohexylmethoxy group, a cyclopentylethoxy group, a cyclohexylethoxy group and the like, with a cyclohexylmethoxy group being preferred.

Polycyclic cycloalkyloxy groups include, for example, norbornyloxy and adamantyloxy groups.

The alkoxy group having a monocyclic or polycyclic cycloalkyl group preferably has 7 or more carbon atoms in total, as described above. That is, it is preferable to employ a configuration in which the total number of carbon atoms in the alkoxy group, the monocyclic cycloalkyl group, and the substituent is 7 or more.

Specific examples of the alkyl group of the alkylcarbonyl group for R ¹⁴ are the same as the alkyl groups for R ₁₃ to R ₁₅ described above.

The alkylsulfonyl group for R ₁₄ may be linear or branched.
The alkylsulfonyl group and cycloalkylsulfonyl group for R ₁₄ preferably have 1 to 10 carbon atoms. Examples of such alkylsulfonyl groups and cycloalkylsulfonyl groups include methanesulfonyl, ethanesulfonyl, n-propanesulfonyl, n-butanesulfonyl, tert-butanesulfonyl, n-pentanesulfonyl, and neopentane. sulfonyl group, n-hexanesulfonyl group, n-heptanesulfonyl group, n-octanesulfonyl group, 2-ethylhexanesulfonyl group, n-nonanesulfonyl group, n-decanesulfonyl group, cyclopentanesulfonyl group and cyclohexanesulfonyl group; be done. Among these, methanesulfonyl group, ethanesulfonyl group, n-propanesulfonyl group, n-butanesulfonyl group, cyclopentanesulfonyl group and cyclohexanesulfonyl group are particularly preferred.

Each of the above groups may further have a substituent. Examples of this substituent include halogen atoms such as fluorine atoms, hydroxy groups, carboxy groups, cyano groups, nitro groups, alkoxy groups, cycloalkoxy groups, alkoxyalkyl groups, cycloalkoxyalkyl groups, alkoxycarbonyl groups, and cycloalkoxycarbonyl groups. groups, alkoxycarbonyloxy groups and cycloalkoxycarbonyloxy groups. Among these, a hydroxy group, an alkoxy group, an alkoxycarbonyl group and a halogen atom are more preferable. A fluorine atom is particularly preferable as the halogen atom.

An alkoxy group may be linear or branched. The alkoxy group includes, for example, a methoxy group, an ethoxy group, an n-propoxy group, an i-propoxy group, an n-butoxy group, a 2-methylpropoxy group, a 1-methylpropoxy group and a t-butoxy group. 1 to 20 are included.
Examples of cycloalkoxy groups include those having 4 to 20 carbon atoms such as cyclopentyloxy and cyclohexyloxy groups.

An alkoxyalkyl group may be linear or branched. Examples of the alkoxyalkyl group include those having 2 to 21 carbon atoms such as methoxymethyl group, ethoxymethyl group, 1-methoxyethyl group, 2-methoxyethyl group, 1-ethoxyethyl group and 2-ethoxyethyl group. is mentioned.

Cycloalkoxyalkyl groups include, for example, cyclopentyloxymethyl and cyclopentyloxymethylethoxy groups.

An alkoxycarbonyl group may be linear or branched. Examples of the alkoxycarbonyl group include methoxycarbonyl group, ethoxycarbonyl group, n-propoxycarbonyl group, i-propoxycarbonyl group, n-butoxycarbonyl group, 2-methylpropoxycarbonyl group, 1-methylpropoxycarbonyl group and t Examples include those having 2 to 21 carbon atoms such as -butoxycarbonyl group.
Examples of cycloalkoxycarbonyl groups include those having 4 to 21 carbon atoms such as cyclopentyloxycarbonyl and cyclohexyloxycarbonyl groups.

An alkoxycarbonyloxy group may be linear or branched. Examples of the alkoxycarbonyloxy group include carbon atoms such as methoxycarbonyloxy, ethoxycarbonyloxy, n-propoxycarbonyloxy, i-propoxycarbonyloxy, n-butoxycarbonyloxy and t-butoxycarbonyloxy groups. Those having a number of 2 to 21 can be mentioned.
The cycloalkoxycarbonyloxy group includes those having 4 to 21 carbon atoms such as cyclopentyloxycarbonyloxy group and cyclohexyloxycarbonyloxy group.

The ring structure that can be formed by bonding two R ₁₅ together includes, for example, a 5- or 6-membered ring, particularly preferably a 5-membered ring (ie, tetrahydro thiophene ring).

This ring structure may further have a substituent. Examples of such substituents include hydroxy, carboxy, cyano, nitro, alkoxy, alkoxyalkyl, alkoxycarbonyl, and alkoxycarbonyloxy groups.

R ₁₅ is particularly preferably a methyl group, an ethyl group, a 1-naphthyl group, or a divalent group in which two R ₁₅ are bonded together to form a tetrahydrothiophene ring structure together with a sulfur atom.

The above k is preferably 0 or 1, more preferably 1.
The above r is preferably 0-2.

Preferred specific examples of the organic sulfonium ion represented by formula (Z1-4a) are shown below, but the present invention is not limited thereto.

In general formula (ZIIa) above, R ₂₀₄ to R ₂₀₅ each independently represent an aryl group, an alkyl group or a cycloalkyl group.
Specific examples and preferred aspects of the aryl group, alkyl group and cycloalkyl group for R ₂₀₄ to R ₂₀₇ are described as the aryl group, alkyl group and cycloalkyl group for R ₂₀₁ to R ₂₀₃ in (ZI-1a) above. is the same as the aryl group described above.

The aryl group, alkyl group and cycloalkyl group of R ₂₀₄ to R ₂₀₇ may have a substituent. Examples of this substituent also include those that the aryl group, alkyl group and cycloalkyl group of R ₂₀₁ to R ₂₀₃ in (ZI-1a) described above may have.

When the composition containing the resin (A) is used in the resist composition for ArF exposure, at least part of the repeating units (P1) preferably do not contain aromatic rings other than naphthalene rings. When the composition containing the resin (A) is used in the resist composition for EB or EUV exposure, at least part of the repeating units (P1) preferably contain an aromatic ring from the viewpoint of secondary electron generation efficiency.

The type of the repeating unit (P1) that the resin (A) has may be only one type, or may be two or more types.

The content of the repeating unit (P1) in the total solid content of the composition of the present invention is 0.25 mmol/g or more. The composition of the present invention can exhibit excellent resolution by setting the content of the repeating unit (P1) in the total solid content to 0.25 mmol/g or more.
The content of the repeating unit (P1) in the total solid content of the composition of the present invention is preferably 0.30 mmol/g or more, more preferably 0.40 mmol/g or more, and 0.50 mmol. /g or more, and particularly preferably 0.60 mmol/g or more.
In addition, the content of the repeating unit (P1) in the total solid content of the composition of the present invention is preferably 1.00 mmol/g or less, more preferably 0.90 mmol/g or less, and 0 It is more preferably 0.80 mmol/g or less.
The total solid content of the composition of the present invention is the total components of the composition of the present invention excluding the solvent.
The content of the repeating unit (P1) in the total solid content of the composition of the present invention is the repeating unit (P1) in the resin (A) determined by ¹ H-NMR (nuclear magnetic resonance) and ¹³ C-NMR. content ratio, nitrogen, and sulfur elemental measurements.

The content of the repeating unit (P1) in the resin (A) is preferably in the range of 5 to 80 mol%, more preferably in the range of 6 to 60 mol%, based on the total repeating units of the resin (A), More preferably, it is in the range of 7 to 40 mol %.

(Repeating unit (a) having at least one aromatic ring)
Resin (A) further has a repeating unit (a) having at least one aromatic ring.
The repeating unit (a) is a repeating unit different from the repeating unit (P1) described above. That is, the repeating unit (a) is not a repeating unit represented by the general formula (1).
The composition of the present invention can exhibit excellent etching resistance by having a repeating unit (a) having at least one aromatic ring as a repeating unit different from the repeating unit (P1) described above.

The structure of the repeating unit (a) is not particularly limited.
It is preferable that the repeating unit (a) is represented by the following general formula (2).

In general formula (2), R ₂₁ to R ₂₄ each independently represent a hydrogen atom, an organic group or a halogen atom. R ₂₂ may combine with R ₂₄ to form a ring, in which case R ₂₂ represents a single bond or an alkylene group. However, at least one of R ₂₁ to R ₂₄ represents a group having an aromatic ring.

When R ₂₁ to R ₂₃ represent an organic group, the organic group is not particularly limited, but is preferably an alkyl group, a cycloalkyl group, an aryl group, a heteroaryl group, or an alkoxycarbonyl group, and is preferably an alkyl group. more preferred.
Alkyl groups for R ₂₁ to R ₂₃ are, for example, methyl group, ethyl group, propyl group, isopropyl group, n-butyl group, sec-butyl group, hexyl group, 2-ethylhexyl group, octyl group, dodecyl group and the like. An alkyl group having 20 or less carbon atoms is preferable, and an alkyl group having 8 or less carbon atoms is more preferable.
The alkyl groups as R ₂₁ to R ₂₃ may have substituents.

Cycloalkyl groups for R ₂₁ to R ₂₃ may be monocyclic or polycyclic, and may have a substituent.
Cycloalkyl groups for R ₂₁ to R ₂₃ are preferably C 3-8 monocyclic cycloalkyl groups such as cyclopropyl, cyclopentyl and cyclohexyl groups.

The aryl group as R ₂₁ to R ₂₃ may have a substituent, and is preferably a monocyclic or polycyclic aryl group having 6 to 14 carbon atoms, specifically a phenyl group, hydroxyphenyl group, tolyl group, chlorophenyl group, methoxyphenyl group, naphthyl group, hydroxynaphthyl group and the like. Also, the aryl groups may be bonded together to form a polycyclic ring.

The heteroaryl group for R ₂₁ to R ₂₃ may have a substituent, preferably a heteroaryl having 3 to 8 carbon atoms containing at least one of an oxygen atom, a nitrogen atom and a sulfur atom as a heteroatom and the like.

The alkyl groups contained in the alkoxycarbonyl groups for R ₂₁ to R ₂₃ are preferably the same as the alkyl groups for R ₂₁ to R ₂₃ above.

A halogen atom for R ₂₁ to R ₂₃ is preferably a fluorine atom, a chlorine atom, a bromine atom or an iodine atom, more preferably a fluorine atom.

It is particularly preferred that R ₂₁ and R ₂₂ are hydrogen atoms.
It is particularly preferred that R ₂₃ is a hydrogen atom or a methyl group.

In general formula (2), _R24 represents a hydrogen atom, an organic group or a halogen atom.
When R ₂₄ represents an organic group, the organic group is not particularly limited, but is preferably an alkyl group, a cycloalkyl group, an aryl group, or an alkoxycarbonyl group, more preferably an aryl group.
Specific examples and preferred ranges of the alkyl group, cycloalkyl group, aryl group and alkoxycarbonyl group for R ₂₄ are the alkyl groups, cycloalkyl groups, aryl groups and alkoxycarbonyl groups for R ₂₁ to R ₂₃ described above, respectively. is the same as

Specific examples and preferred ranges of the halogen atom as R ₂₄ are the same as the halogen atoms as R ₂₁ to R ₂₃ described above.

When R ₂₁ to R ₂₄ can further have one or more substituents, the further substituents are not particularly limited, but examples include hydroxyl groups, halogen atoms (preferably fluorine atoms, bromine atoms, chlorine atoms, or iodine atom), nitro group, cyano group, amide group, sulfonamide group, alkyl group (preferably alkyl group having 1 to 8 carbon atoms), cycloalkyl group (preferably cycloalkyl group having 5 to 12 carbon atoms), alkoxy group (preferably alkoxy group having 1 to 8 carbon atoms), alkoxycarbonyl group (preferably alkoxycarbonyl group having 2 to 8 carbon atoms), alkylcarbonyl group (preferably alkylcarbonyl group having 2 to 8 carbon atoms), acyl group (preferably acyl group having 2 to 8 carbon atoms), acyloxy group (preferably acyloxy group having 2 to 8 carbon atoms), carboxy group, aryl group (preferably aryl group having 6 to 12 carbon atoms), heteroaryl group ( Preferred heteroatoms include a heteroaryl group having 3 to 8 carbon atoms containing at least one of an oxygen atom, a nitrogen atom and a sulfur atom.

However, at least one of R ₂₁ to R ₂₄ represents a group having an aromatic ring.

At least two of R ₂₁ to R ₂₄ may combine with each other to form a ring.

The repeating unit (a) is more preferably represented by the following general formula (3).

In general formula (3), R ₃₁ to R ₃₃ each independently represent a hydrogen atom, an organic group or a halogen atom. However, R ₃₂ may combine with Ar to form a ring, in which case R ₃₂ represents a single bond or an alkylene group. _L3 represents a single bond or a divalent linking group. Ar represents an aromatic ring group.

Specific examples and preferred ranges of R ₃₁ to R ₃₃ are the same as R ₂₁ to R ₂₃ in formula (2) above.

_L3 represents a single bond or a divalent linking group.
When L ₃ represents a divalent linking group, the divalent linking group includes an alkylene group, a cycloalkylene group, an alkenylene group, —O—, —SO ₂ —, —CO—, —N(R ₃₄ )— Alternatively, a divalent linking group obtained by combining a plurality of these is preferred.
_R34 represents a hydrogen atom, an alkyl group, a cycloalkyl group, an alkenyl group, or an aryl group.
The alkyl group as R ₃₄ is, for example, a methyl group, ethyl group, propyl group, isopropyl group, n-butyl group, sec-butyl group, hexyl group, 2-ethylhexyl group, octyl group, dodecyl group, etc. The following alkyl groups are preferable, and alkyl groups having 8 or less carbon atoms are more preferable.
The alkyl group as R ₃₄ may have a substituent.

The alkylene group as L ₃ may have a substituent, preferably those having 1 to 8 carbon atoms such as methylene group, ethylene group, propylene group, butylene group, hexylene group and octylene group, An alkylene group having 1 to 3 carbon atoms is particularly preferred.

The cycloalkylene group for L ₃ may have a substituent, and preferably has 5 to 12 carbon atoms such as a cyclopentylene group, a cyclohexylene group and an adamantylene group.

The alkenylene group for L ₃ may have a substituent, preferably having 2 to 8 carbon atoms, and particularly preferably an alkenylene group having 2 to 4 carbon atoms.

It is particularly preferred that L3 is a single bond or _-COO- .

Ar represents an aromatic ring group. The aromatic ring group represented by Ar may have a substituent.
The aromatic ring group represented by Ar is preferably an aryl group or a heteroaryl group, preferably an aryl group.
The aryl group as Ar may have a substituent, and is preferably a monocyclic or polycyclic aryl group having 6 to 14 carbon atoms, and specifically includes a phenyl group, a naphthyl group, and the like. , is preferably a phenyl group. Also, the aryl groups may be bonded together to form a polycyclic ring. The aryl group preferably has a hydroxyl group as a substituent.
The heteroaryl group for Ar may have a substituent, and is thiophene ring, furan ring, pyrrole ring, benzothiophene ring, benzofuran ring, benzopyrrole ring, triazine ring, imidazole ring, benzimidazole ring, triazole ring. , a thiadiazole ring, and an aromatic ring group containing a hetero ring such as a thiazole ring.

When the above R ₃₁ to R ₃₃ , L ₃ and Ar can further have one or more substituents, the further substituents are not particularly limited, for example, the above R ₂₁ to R ₂₄ have Examples of further substituents which may be present include the substituents exemplified above.

The repeating unit (a) is more preferably represented by the following general formula (4).

In general formula (4), R ₄₁ to R ₄₃ each independently represent a hydrogen atom, an organic group or a halogen atom. However, _R42 may combine with Ar to form a ring, in which case _R42 represents a single bond or an alkylene group. L represents a single bond or a divalent linking group. Ar represents an aromatic ring group. k represents an integer of 1 to 5;

Specific examples and preferred ranges of R ₄₁ to R ₄₃ are the same as R ₂₁ to R ₂₃ in formula (2) above.
Specific examples and preferred ranges of L ₄ are the same as those of L ₃ in general formula (3) above.
Specific examples and preferred ranges of Ar are the same as those of Ar in general formula (3) above.

k represents an integer of 1 to 5, preferably an integer of 1 to 3, more preferably 1 or 2;

When the above R ₄₁ to R ₄₃ , L ₄ and Ar can further have one or more substituents, the further substituents are not particularly limited, for example, the above R ₂₁ to R ₂₄ have Examples of further substituents which may be present include the substituents exemplified above.

Specific examples of the repeating unit (a) are shown below, but the present invention is not limited thereto. In the following specific examples, a represents an integer of 1-3.

The type of the repeating unit (a) contained in the resin (A) may be one type, or two or more types.

The content of the repeating unit (a) in the resin (A) is preferably in the range of 10 to 95 mol%, more preferably in the range of 20 to 90 mol%, based on the total repeating units of the resin (A), More preferably, it is in the range of 30 to 90 mol %.

(Repeating unit (P2))
The resin (A) preferably has a repeating unit (P2) having a group that is decomposed by the action of an acid to increase polarity (also referred to as an "acid-decomposable group").
The resin (A) may have a repeating unit (P2) as a repeating unit different from the repeating unit (P1), although the repeating unit (P1) may have an acid-decomposable group. preferable.
Further, the repeating unit (P2) may be a repeating unit applicable to the repeating unit (a), or may be a repeating unit different from the repeating unit (a).

The resin (A) is preferably a resin whose solubility in a developer is changed by the action of acid.
The resin whose solubility in the developer changes under the action of acid may be a resin whose solubility in the developer increases under the action of acid or a resin whose solubility in the developer decreases under the action of acid.
Resin (A) is preferably a resin whose solubility in an alkaline developer is increased by the action of an acid.
When the resin (A) is a resin whose solubility in a developer changes under the action of an acid, in the pattern forming method of the present invention, typically when an alkaline developer is employed as the developer, a positive type A pattern is preferably formed, and when an organic developer is used as the developer, a negative pattern is preferably formed.
In the pattern forming method of the present invention, the resist composition containing the resin (A) preferably forms a negative pattern, typically when an alkaline developer is employed as the developer. Even when a system developer is used, a negative pattern is preferably formed.

The acid-decomposable group preferably has a structure in which a polar group is protected by a group that decomposes and leaves by the action of an acid (leaving group).
Polar groups include, for example, carboxyl group, phenolic hydroxyl group, fluorinated alcohol group, sulfonic acid group, sulfonamide group, sulfonylimide group, (alkylsulfonyl)(alkylcarbonyl)methylene group, (alkylsulfonyl)(alkylcarbonyl) imido group, bis(alkylcarbonyl)methylene group, bis(alkylcarbonyl)imide group, bis(alkylsulfonyl)methylene group, bis(alkylsulfonyl)imide group, tris(alkylcarbonyl)methylene group, and tris(alkylsulfonyl) Examples include acidic groups such as methylene groups (typically, groups that dissociate in a 2.38% by mass aqueous solution of tetramethylammonium hydroxide), alcoholic hydroxyl groups, and the like.

The alcoholic hydroxyl group is a hydroxyl group bonded to a hydrocarbon group, and refers to a hydroxyl group other than a hydroxyl group directly bonded to an aromatic ring (phenolic hydroxyl group). It excludes aliphatic alcohols substituted with functional groups (eg, hexafluoroisopropanol groups, etc.). The alcoholic hydroxyl group is preferably a hydroxyl group with a pKa (acid dissociation constant) of 12 or more and 20 or less.

The polar group is preferably a carboxy group, a phenolic hydroxyl group, a fluorinated alcohol group (preferably a hexafluoroisopropanol group), or a sulfonic acid group, more preferably a carboxy group or a phenolic hydroxyl group. That is, the acid-decomposable group is preferably a group that is decomposed by the action of an acid to form a carboxyl group or a group that is decomposed by the action of an acid to form a phenolic hydroxyl group.
The repeating unit (P2) is preferably a repeating unit having at least one group selected from the group consisting of a group that decomposes under the action of an acid to yield a carboxyl group and a group that decomposes under the action of an acid to yield a hydroxyl group. preferable.

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

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

In formula (Y3), R ₃₆ to R ₃₈ each independently represent a hydrogen atom or a monovalent organic group. R ₃₇ and R ₃₈ may combine with each other to form a ring. Monovalent organic groups include alkyl groups, cycloalkyl groups, aryl groups, aralkyl groups, alkenyl groups, and the like. It is also preferred that R ₃₆ is a hydrogen atom.
The alkyl group, cycloalkyl group, aryl group, and aralkyl group may contain a heteroatom such as an oxygen atom and/or a group having a heteroatom such as a carbonyl group. For example, in the alkyl group, cycloalkyl group, aryl group, and aralkyl group, one or more methylene groups are replaced with a heteroatom such as an oxygen atom and/or a group having a heteroatom such as a carbonyl group. good too.
In addition, R ₃₈ may combine with another substituent of the main chain of the repeating unit to form a ring. The group formed by bonding R ₃₈ and another substituent of the main chain of the repeating unit to each other is preferably an alkylene group such as a methylene group.

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

Here, L ₁ and L ₂ each independently represent a hydrogen atom, an alkyl group, a cycloalkyl group, an aryl group, or a group combining these (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 optionally containing a heteroatom, a cycloalkyl group optionally containing a heteroatom, an aryl group optionally containing a heteroatom, an amino group, an ammonium group, a mercapto group, a cyano group, an aldehyde group, or a group in which these are combined (for example, a group in which an alkyl group and a cycloalkyl group are combined).
Alkyl and cycloalkyl groups may, for example, have one of the methylene groups replaced by a heteroatom such as an oxygen atom or a heteroatom-bearing group such as a carbonyl group.
One of L ₁ and L ₂ is preferably a hydrogen atom, and the other is preferably an alkyl group, a cycloalkyl group, an aryl group, or a combination of an alkylene group and an aryl group.
At _least two of Q, M, and L1 may combine to form a ring (preferably a 5- or 6-membered ring).
From the viewpoint of pattern refinement, L2 is preferably a _secondary or tertiary alkyl group, more preferably a tertiary alkyl group. Secondary alkyl groups include isopropyl, cyclohexyl and norbornyl groups, and tertiary alkyl groups include tert-butyl and adamantane groups. In these embodiments, the Tg (glass transition temperature) and the activation energy are increased, so that the film strength can be ensured and fogging can be suppressed.

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

From the viewpoint of excellent acid decomposability of the repeating unit, when a non-aromatic ring is directly bonded to a polar group (or a residue thereof) in a leaving group that protects a polar group, in the non-aromatic ring, It is also preferable that the ring member atoms adjacent to the ring member atoms directly bonded to the polar group (or residue thereof) do not have halogen atoms such as fluorine atoms as substituents.

The leaving group that leaves by the action of an acid also includes a 2-cyclopentenyl group having a substituent (such as an alkyl group) such as a 3-methyl-2-cyclopentenyl group, and a 1,1,4 , 4-tetramethylcyclohexyl group having a substituent (such as an alkyl group) may also be used.

The repeating unit (P2) is a group that is decomposed by the action of an acid to give a carboxy group bonded to an aromatic ring (particularly preferably a benzene ring), and a group that is decomposed by the action of an acid to an aromatic ring (particularly preferably a benzene ring). More preferably, the repeating unit has at least one group selected from the group consisting of groups that form a bonded hydroxyl group.

The repeating unit (P2) is preferably a repeating unit represented by any one of the following general formulas (5) to (9).

In general formula (5), R ₅₁ to R ₅₃ each independently represent a hydrogen atom, an alkyl group, a cycloalkyl group, a halogen atom, a cyano group, or an alkoxycarbonyl group. _L5 represents a single bond or a divalent linking group. R ₅₄ to R ₅₆ each independently represent a hydrogen atom, an alkyl group, a cycloalkyl group, an aryl group, an aralkyl group or an alkenyl group. Two of R ₅₄ to R ₅₆ may combine with each other to form a ring.
In general formula (6), R ₆₁ to R ₆₄ each independently represent a hydrogen atom or an organic group. However, at least one of R ₆₁ and R ₆₂ represents an organic group. X ₆ represents -CO-, -SO- or -SO ₂ -. Y ₆ represents -O-, -S-, -SO-, -SO ₂ -, or -NR ₄₈ -. _R48 represents a hydrogen atom or an organic group. _L6 represents a single bond or a divalent linking group. R ₆₅ to R ₆₇ each independently represent a hydrogen atom, an alkyl group, a cycloalkyl group, an aryl group, an aralkyl group or an alkenyl group. Two of R ₆₅ to R ₆₇ may combine with each other to form a ring.
In general formula (7), R ₇₁ and R ₇₂ each independently represent a hydrogen atom or an organic group. _R73 and _R74 each independently represent a hydrogen atom, an alkyl group, a cycloalkyl group, an aryl group, an aralkyl group, or an alkenyl group. Two of R ₇₁ to R ₇₄ may combine with each other to form a ring.
In general formula (8), R ₈₁ to R ₈₃ each independently represent a hydrogen atom, an alkyl group, a cycloalkyl group, a halogen atom, a cyano group, or an alkoxycarbonyl group. _L8 represents a single bond or a divalent linking group. Ar ₈ represents an aromatic ring group. R ₈₄ to R ₈₆ each independently represent a hydrogen atom, an alkyl group, a cycloalkyl group, an aryl group, an aralkyl group or an alkenyl group. Two of R ₈₄ to R ₈₆ may combine with each other to form a ring. Ar ₈ may combine with R ₈₂ or R ₈₄ to form a ring.
In general formula (9), R ₉₁ to R ₉₃ each independently represent a hydrogen atom, an alkyl group, a cycloalkyl group, a halogen atom, a cyano group, or an alkoxycarbonyl group. _L9 represents a single bond or a divalent linking group. R ₉₄ to R ₉₆ each independently represent a hydrogen atom, an alkyl group, a cycloalkyl group, an aryl group, an aralkyl group or an alkenyl group. R ₉₅ and R ₉₆ may combine with each other to form a ring.

The repeating unit represented by formula (5) is described below.

The alkyl groups represented by R ₅₁ to R ₅₃ may be linear or branched. Although the number of carbon atoms in the alkyl group is not particularly limited, it is preferably 1-5, more preferably 1-3.
Cycloalkyl groups represented by R ₅₁ to R ₅₃ include monocyclic cycloalkyl groups such as cyclopentyl group and cyclohexyl group, norbornyl group, tetracyclodecanyl group, tetracyclododecanyl group, and adamantyl group. is preferred.
Halogen atoms represented by R ₅₁ to R ₅₃ include a fluorine atom, a chlorine atom, a bromine atom and an iodine atom, preferably a fluorine atom or an iodine atom.
The alkyl group contained in the alkoxycarbonyl groups represented by R ₅₁ to R ₅₃ may be linear or branched. Although the number of carbon atoms in the alkyl group contained in the alkoxycarbonyl group is not particularly limited, it is preferably 1-5, more preferably 1-3.

Divalent linking groups represented by L ₅ include -CO-, -O-, -S-, -SO-, -SO ₂ -, divalent aliphatic linking groups, and divalent aromatic linking groups. , and a linking group in which a plurality of these are linked. Examples of divalent aliphatic linking groups include alkylene groups, cycloalkylene groups, and alkenylene groups. The divalent aliphatic linking group may have a heteroatom (eg, oxygen atom, nitrogen atom, sulfur atom, etc.) and may have a substituent. The divalent aromatic linking group includes an arylene group, a heteroarylene group, and the like. The divalent aromatic linking group may have a substituent.

When L ₅ contains an arylene group, the arylene group may have a substituent, preferably having 6 to 14 carbon atoms, specifically a phenylene group, a tolylene group, a naphthylene group, a biphenylene group, and the like. and a phenylene group is particularly preferred.

When L ₅ contains a heteroarylene group, the heteroarylene group is a divalent aromatic group (divalent aromatic heterocyclic group) containing a heteroatom as a ring member, and the heteroatom includes an oxygen atom, sulfur atoms, nitrogen atoms, and the like. The heteroarylene group preferably has 4 to 20 carbon atoms, more preferably 5 to 12 carbon atoms. Examples of heteroarylene groups include groups obtained by removing two hydrogen atoms from pyrrole, furan, thiophene, indole, benzofuran, benzothiophene, and the like. The heteroarylene group may have a substituent.

When L ₅ contains an alkylene group, the alkylene group may have a substituent, preferably a C 1-8 group such as a methylene group, ethylene group, propylene group, butylene group, hexylene group, octylene group, etc. and particularly preferably an alkylene group having 1 to 3 carbon atoms.

When L ₅ contains a cycloalkylene group, the cycloalkylene group may have a substituent and preferably has 5 to 12 carbon atoms such as a cyclopentylene group, a cyclohexylene group and an adamantylene group.

When L ₅ contains an alkenylene group, the alkenylene group may have a substituent, preferably one having 2 to 8 carbon atoms, and particularly preferably an alkenylene group having 2 to 4 carbon atoms. .

_L5 is preferably a divalent aromatic linking group, more preferably an arylene group.

The alkyl groups represented by R ₅₄ to R ₅₆ may be linear or branched. Although the number of carbon atoms in the alkyl group is not particularly limited, it is preferably 1-5, more preferably 1-3. In the alkyl groups represented by R ₅₄ to R ₅₆ , methylene groups may be substituted with -CO- and/or -O-.
Cycloalkyl groups represented by R ₅₄ to R ₅₆ include monocyclic cycloalkyl groups such as cyclopentyl group and cyclohexyl group, norbornyl group, tetracyclodecanyl group, tetracyclododecanyl group, and adamantyl group. is preferred.
A phenyl group is preferable as the aryl group represented by R ₅₄ to R ₅₆ .
As the aralkyl group represented by R ₅₄ to R ₅₆ , one hydrogen atom in the alkyl group represented by R ₅₄ to R ₅₆ is replaced by an aryl group having 6 to 10 carbon atoms (preferably a phenyl group). Substituted groups are preferred, and examples thereof include benzyl groups and the like.
A vinyl group is preferred as the alkenyl group represented by R ₅₄ to R ₅₆ .
The ring formed by combining two of R ₅₄ to R ₅₆ is preferably a cycloalkyl group. The cycloalkyl group formed by combining two of R ₅₄ to R ₅₆ includes a monocyclic cycloalkyl group such as a cyclopentyl group or a cyclohexyl group, a norbornyl group, a tetracyclodecanyl group, and a tetracyclododecanyl group. or a polycyclic cycloalkyl group such as an adamantyl group, and more preferably a monocyclic cycloalkyl group having 5 to 6 carbon atoms.
The cycloalkyl group formed by combining two of R ₅₄ to R ₅₆ is, for example, a group in which one of the methylene groups constituting the ring has a heteroatom such as an oxygen atom, a heteroatom such as a carbonyl group, or vinylidene group may be substituted. In these cycloalkyl groups, one or more ethylene groups constituting the cycloalkane ring may be replaced with a vinylene group.

Each of the above groups in the general formula (5) may have a substituent, and examples of the substituent include the following substituent T.

(substituent T)
The substituent T includes halogen atoms such as a fluorine atom, a chlorine atom, a bromine atom and an iodine atom; alkoxy groups such as a methoxy group, an ethoxy group and a tert-butoxy group; an aryloxy group such as a phenoxy group and a 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; acetyl group, benzoyl group, isobutyryl group, acryloyl group, methacryloyl group and methoxalyl group, etc. an acyl group; an alkylsulfanyl group such as a methylsulfanyl group and a tert-butylsulfanyl group; an arylsulfanyl group such as a phenylsulfanyl group and a p-tolylsulfanyl group; aryl group (e.g., 6 to 20 carbon atoms); heteroaryl group; hydroxyl group; carboxy group; formyl group; sulfo group; silyl groups; amino groups; monoalkylamino groups; dialkylamino groups; arylamino groups, nitro groups; formyl groups;

The repeating unit represented by formula (6) is described below.

The organic groups represented by R ₆₁ to R ₆₄ are preferably alkyl groups, cycloalkyl groups, aryl groups, aralkyl groups or alkenyl groups.
Examples of the alkyl group, cycloalkyl group, aryl group, aralkyl group and alkenyl group represented by R ₆₁ to R ₆₄ include the alkyl group represented by R ₅₄ to R ₅₆ in the above general formula (5), cyclo Examples include groups similar to alkyl groups, aryl groups, aralkyl groups, and alkenyl groups.

X ₆ is preferably -CO-.
The organic group represented by R ₄₈ has the same meaning as the organic group represented by R ₆₁ to R ₆₄ described above, and the preferred embodiments are also the same.
_Y6 is preferably -O-.
The divalent linking group represented by L6 is synonymous with the divalent linking group represented by _L5 in the general formula ( ₅ ) described above, and the preferred embodiments are also the same.
Examples of the alkyl group, cycloalkyl group, aryl group, aralkyl group and alkenyl group represented by R ₆₅ to R ₆₇ include the alkyl group represented by R ₅₄ to R ₅₆ in the above general formula (5), cyclo Examples include groups similar to alkyl groups, aryl groups, aralkyl groups, and alkenyl groups.

A cycloalkyl group is preferable as the ring formed by combining two of R ₆₅ to R ₆₇ . The cycloalkyl group formed by combining two of R ₆₅ to R ₆₇ includes a monocyclic cycloalkyl group such as a cyclopentyl group or a cyclohexyl group, a norbornyl group, a tetracyclodecanyl group, and a tetracyclododecanyl group. or a polycyclic cycloalkyl group such as an adamantyl group, and more preferably a monocyclic cycloalkyl group having 5 to 6 carbon atoms.
The cycloalkyl group formed by combining two of R ₆₅ to R ₆₇ is, for example, a group in which one of the methylene groups constituting the ring has a heteroatom such as an oxygen atom, a heteroatom such as a carbonyl group, or vinylidene group may be substituted. In these cycloalkyl groups, one or more ethylene groups constituting the cycloalkane ring may be replaced with a vinylene group.

Each group in the general formula (6) may have a substituent, and examples of the substituent include the substituent T described above.

The repeating unit represented by formula (7) is described below.

The organic groups represented by R ₇₁ and R ₇₂ have the same meanings as the organic groups represented by R ₆₁ to R ₆₄ in general formula (6) described above, and the preferred embodiments are also the same.
Examples of the alkyl group, cycloalkyl group, aryl group, aralkyl group and alkenyl group represented by R ₇₃ and R ₇₄ include the alkyl group represented by R ₅₄ to R ₅₆ in the above general formula (5), cyclo Examples include groups similar to alkyl groups, aryl groups, aralkyl groups, and alkenyl groups.
The alkyl group, cycloalkyl group, aryl group, aralkyl group, and alkenyl group represented by R ₇₃ and R ₇₄ may have a substituent. mentioned.

The ring formed by combining R ₇₃ and R ₇₄ is preferably a cycloalkyl group. The cycloalkyl group formed by combining R ₇₃ and R ₇₄ includes a monocyclic cycloalkyl group such as a cyclopentyl group or a cyclohexyl group, a norbornyl group, a tetracyclodecanyl group, a tetracyclododecanyl group, Alternatively, a polycyclic cycloalkyl group such as an adamantyl group is preferable, and a monocyclic cycloalkyl group having 5 to 6 carbon atoms is more preferable.
In the cycloalkyl group formed by combining R ₇₃ and R ₇₄ , for example, one of the methylene groups constituting the ring is a group having a heteroatom such as an oxygen atom, a heteroatom such as a carbonyl group, or a vinylidene group. may be replaced. In these cycloalkyl groups, one or more ethylene groups constituting the cycloalkane ring may be replaced with a vinylene group.

The repeating unit represented by formula (8) is described below.

R ₈₁ to R ₈₃ and L ₈ have the same definitions as R ₅₁ to R ₅₃ and L ₅ in general formula (5), and the preferred embodiments are also the same.
The aromatic ring group represented by Ar ₈ is not particularly limited, but includes, for example, a phenylene group and a naphthylene group, preferably a phenylene group.
Examples of the alkyl group, cycloalkyl group, aryl group, aralkyl group and alkenyl group represented by R ₈₄ to R ₈₆ include the alkyl group represented by R ₅₄ to R ₅₆ in the above general formula (5), cyclo Examples include groups similar to alkyl groups, aryl groups, aralkyl groups, and alkenyl groups.
The alkyl group, cycloalkyl group, aryl group, aralkyl group, and alkenyl group represented by R ₈₄ to R ₈₆ may have a substituent. mentioned.

Two of R ₈₄ to R ₈₆ may combine with each other to form a ring, or Ar ₈ may combine with R ₈₂ or R ₈₄ to form a ring. The ring formed in these cases is preferably a monocyclic or polycyclic alicyclic ring, more preferably a monocyclic alicyclic ring having 4 to 8 carbon atoms.
The alicyclic ring formed by bonding two of R ₈₄ to R ₈₆ is, for example, a group in which one of the methylene groups constituting the ring has a heteroatom such as an oxygen atom, a heteroatom such as a carbonyl group, or a vinylidene group may be substituted. Moreover, one or more of the ethylene groups constituting these alicyclic rings may be replaced with a vinylene group.

The repeating unit represented by formula (9) is described below.

R ₉₁ to R ₉₃ and L ₉ have the same definitions as R ₅₁ to R ₅₃ and L ₅ in general formula (5), and the preferred embodiments are also the same.
_L9 is preferably a divalent aromatic linking group, more preferably an arylene group.
Examples of the alkyl group, cycloalkyl group, aryl group, aralkyl group and alkenyl group represented by R ₉₄ to R ₉₆ include the alkyl group represented by R ₅₄ to R ₅₆ in the above general formula (5), cyclo Examples include groups similar to alkyl groups, aryl groups, aralkyl groups, and alkenyl groups.
The alkyl group, cycloalkyl group, aryl group, aralkyl group, and alkenyl group represented by R ₉₄ to R ₉₆ may have a substituent. mentioned.
The ring formed by combining R ₉₅ and R ₉₆ is preferably a monocyclic or polycyclic alicyclic ring, more preferably a monocyclic alicyclic ring having 4 to 8 carbon atoms.
In the alicyclic ring formed by combining R ₉₅ and R ₉₆ , for example, one of the methylene groups constituting the ring is replaced with a heteroatom such as an oxygen atom, a heteroatom-containing group such as a carbonyl group, or a vinylidene group. may be Moreover, one or more of the ethylene groups constituting these alicyclic rings may be replaced with a vinylene group.

The repeating unit (P2) may or may not contain a halogen atom, but preferably does not contain a halogen atom.

The repeating unit (P2) is more preferably a repeating unit represented by the general formula (5), (8), or (9).

When the resin (A) has repeating units (P2), the number of repeating units (P2) may be one, or two or more.
The content of the repeating unit (P2) in the resin (A) is preferably 5 mol% or more, more preferably 10 mol% or more, more preferably 15 mol% of the total repeating units in the resin (A). % or more is more preferable. In addition, the content of the repeating unit (P2) in the resin (A) is preferably 95 mol% or less, more preferably 90 mol% or less, relative to all repeating units in the resin (A). 85 mol % or less is particularly preferred.

Specific examples of the repeating unit (P2) are shown below, but are not limited thereto. In the following structural formulas, Xa ₁ represents any one of H, CH ₃ , CF ₃ and CH ₂ OH, and Rxa and Rxb each independently represents a linear or branched alkyl group having 1 to 5 carbon atoms. show.

(Repeating unit having lactone group or sultone group)
Resin (A) may further have a repeating unit having a lactone group or a sultone group.
As the lactone group or sultone group, any group having a lactone structure or sultone structure can be used, but a group having a 5- to 7-membered ring lactone structure or a 5- to 7-membered ring sultone structure is preferred. A 5- to 7-membered lactone structure in which another ring structure is condensed to form a bicyclo structure or a spiro structure, or a 5- to 7-membered sultone structure in a bicyclo structure or a spiro structure is more preferably condensed with another ring structure to form A group having a lactone structure represented by any of the following general formulas (LC1-1) to (LC1-21), or a sultone represented by any of the following general formulas (SL1-1) to (SL1-3) It is more preferable to have a repeating unit having a group having a structure. Also, a group having a lactone structure or a sultone structure may be directly bonded to the main chain. Preferred structures include general formula (LC1-1), general formula (LC1-4), general formula (LC1-5), general formula (LC1-6), general formula (LC1-13), and general formula ( Groups represented by LC1-14) are preferred.

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

Examples of repeating units having a group having a lactone structure or sultone structure include repeating units represented by the following general formula (AII).

In general formula (AII), Rb ₀ represents a hydrogen atom, a halogen atom, or an alkyl group having 1 to 4 carbon atoms.
Preferred substituents that the alkyl group of Rb ₀ may have include a hydroxyl group and a halogen atom.
Halogen atoms for Rb ₀ include fluorine, chlorine, bromine and iodine atoms. Rb ₀ is preferably a hydrogen atom or a methyl group.
Ab is a single bond, an alkylene group, a divalent linking group having a monocyclic or polycyclic alicyclic hydrocarbon structure, an ether group, an ester group, a carbonyl group, a carboxyl group, or a combination of these divalent groups represents Among them, a single bond or a linking group represented by -Ab ₁ -CO ₂ - is preferred. Ab ₁ is a linear or branched alkylene group or a monocyclic or polycyclic cycloalkylene group, preferably a methylene group, ethylene group, cyclohexylene group, adamantylene group or norbornylene group.
V represents a group having a lactone structure or a sultone structure.
Groups having a lactone structure or sultone structure for V include groups represented by any of general formulas (LC1-1) to (LC1-21) and general formulas (SL1-1) to (SL1-3). preferable.

A repeating unit having a group having a lactone structure or a sultone structure usually has optical isomers, and any optical isomers may be used. Moreover, one kind of optical isomer may be used alone, or a plurality of optical isomers may be mixed and used. When one kind of optical isomer is mainly used, its optical purity (ee) is preferably 90 or more, more preferably 95 or more.

Specific examples of the repeating unit having a group having a lactone structure or sultone structure are shown below, but the present invention is not limited thereto. In addition, in formula, Rx represents H, _CH3 , _CH2OH , or _CF3 .

The resin (A) may or may not have a repeating unit having a lactone group or a sultone group. , preferably 1 to 60 mol %, more preferably 5 to 50 mol %, still more preferably 10 to 40 mol %, based on all repeating units in the resin (A).

(Other repeating units)
In addition to the repeating units described above, the resin (A) has various repeating units for the purpose of adjusting, for example, dry etching resistance, suitability for standard developer, substrate adhesion, resist profile, resolution, heat resistance, sensitivity, and the like. may be
Other repeating units other than those described above can be referred to in paragraphs [0097] to [0100] and [0102] to [0133] of International Publication No. WO 2018/193954, the contents of which are incorporated herein. .

Resin (A) can be synthesized according to a conventional method (for example, radical polymerization).
The weight average molecular weight of resin (A) is not particularly limited, but is preferably 1,000 to 200,000, more preferably 2,000 to 30,000, even more preferably 3,000 to 20,000.
The dispersity (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. , 1.0 to 2.0.

Although the Ohnishi parameter of the resin (A) is not particularly limited, it is preferably 4.1 or less, more preferably 3.5 or less, and even more preferably 3.0 or less. The Ohnishi parameter is a value expressed by the formula "total number of atoms/(number of carbon atoms-number of acid elements)". The Ohnishi parameter of the resin (A) is obtained by counting the number of atoms from the structural formula of each repeating unit contained in the resin (A) to obtain the Ohnishi parameter of each repeating unit, and adding that value to the content ratio of each repeating unit ( It can be obtained by adding the values multiplied by the molar ratio).
The Ohnishi parameter P _A of the resin (A) having n kinds of repeating units is obtained by the following formula (1) using the Ohnishi parameter P _Ui of each repeating unit and the content ratio (mol%) X _Ui of each repeating unit. be done. i represents an integer from 1 to n.

In addition, the Ohnishi parameter of the total solid content in the composition of the present invention is not particularly limited, but is preferably 4.1 or less, more preferably 3.5 or less, and 3.0 or less is more preferred. The Ohnishi parameter for the total solid content in the composition of the present invention is obtained by counting the number of each atom from the structural formula of the total solid content (all components other than the solvent) contained in the composition of the present invention. and adding the values obtained by multiplying the value by the content ratio (molar ratio) of each component.
The _Ohnishi parameter T of the total solid content in the resist composition having m _kinds of components (solid components) is obtained by the following formula ( 2). i represents an integer from 1 to m.

The content of the resin (A) in the composition of the present invention is not particularly limited, but it is preferably 50.00 to 99.99% by mass with respect to the total solid content of the composition of the present invention, and 60.00 More preferably, it is up to 99.90% by mass.
The term "total solid content" means all the components except the solvent in the composition of the present invention, and components other than the solvent are regarded as the solid content even if they are liquid components.
The resin (A) contained in the composition of the present invention may be of one type, or may be of two or more types.

[Acid diffusion control agent]
The composition of the present invention preferably contains an acid diffusion controller (hereinafter also referred to as "acid diffusion controller (Q)").

The acid diffusion control agent (Q) can act as a quencher that traps the acid generated from the photoacid generator or the like during exposure and suppresses the reaction of the acid-decomposable resin in the unexposed area due to excess generated acid. can.
The acid diffusion control agent (Q) includes, for example, a basic compound (DA), a basic compound (DB) whose basicity is reduced or lost by irradiation with actinic rays or radiation, and an acid generated from an acid generator. An onium salt (DC) that is a relatively weak acid, a compound (DD) that has a nitrogen atom and a group that can be eliminated by the action of an acid, or an onium salt compound (DE) that has a nitrogen atom in the cation portion is used. can do.
Known acid diffusion control agents can be used as appropriate in the composition of the present invention. 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, US Patent Application Publication No. 2016/0237190A1. Known compounds disclosed in paragraphs [0403] to [0423] of the specification and paragraphs [0259] to [0328] of US Patent Application Publication No. 2016/0274458A1 can be suitably used as acid diffusion control agents. .

As the basic compound (DA), compounds having structures represented by the following general formulas (A) to (E) are preferred.

In 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 represents a group (6 to 20 carbon atoms). R ²⁰¹ and R ²⁰² may combine 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 represent an alkyl group having 1 to 20 carbon atoms.

The alkyl groups in general formulas (A) and (E) may be substituted or unsubstituted.
Regarding the above alkyl group, the substituted alkyl group is preferably an aminoalkyl group having 1 to 20 carbon atoms, a hydroxyalkyl group having 1 to 20 carbon atoms, or a cyanoalkyl group having 1 to 20 carbon atoms.
The alkyl groups in general formulas (A) and (E) are more preferably unsubstituted.

The basic compound (DA) is preferably thiazole, benzothiazole, oxazole, benzoxazole, guanidine, aminopyrrolidine, pyrazole, pyrazoline, piperazine, aminomorpholine, aminoalkylmorpholine, piperidine, or compounds having these structures. A compound having a thiazole structure, a benzothiazole structure, an oxazole structure, a benzoxazole structure, an imidazole structure, a diazabicyclo structure, an onium hydroxide structure, an onium carboxylate structure, a trialkylamine structure, an aniline structure or a pyridine structure, 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) whose basicity is reduced or lost by irradiation with actinic rays or radiation (hereinafter also referred to as "compound (DB)") has a proton acceptor functional group, and actinic rays or It is a compound whose proton acceptor property is reduced or lost, or whose proton acceptor property is changed to acidic by being decomposed by irradiation with radiation.

The proton-accepting functional group is a functional group having electrons or a group capable of electrostatically interacting with protons, for example, a functional group having a macrocyclic structure such as cyclic polyether, or a π-conjugated means a functional group having a nitrogen atom with a lone pair of electrons that does not contribute to A nitrogen atom having a lone pair of electrons that does not contribute to π-conjugation is, for example, a nitrogen atom having a partial structure represented by the following formula.

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

The compound (DB) is decomposed by exposure to actinic rays or radiation to reduce or eliminate its proton acceptor property, or to generate a compound whose proton acceptor property is changed to an acidic one. Here, the reduction or disappearance of proton acceptor property, or the change from proton acceptor property to acidity is a change in proton acceptor property due to the addition of protons to the proton acceptor functional group. means that when a proton adduct is produced from a compound (DB) having a proton-accepting functional group and a proton, the equilibrium constant in the chemical equilibrium decreases.
Proton acceptor properties can be confirmed by measuring pH.

The acid dissociation constant pKa of the compound generated by decomposition of the compound (DB) by irradiation with actinic rays or radiation preferably satisfies pKa<−1, more preferably satisfies −13<pKa<−1, and − More preferably, 13<pKa<-3 is satisfied.

In the composition of the present invention, an onium salt (DC) (hereinafter also referred to as "compound (DC)"), which is a relatively weak acid relative to the acid generated from the acid generator, is used as the acid diffusion controller (Q). can also be used. Examples of the acid generated from the acid generator include the acid generated from the repeating unit (P1) of the resin (A) described above and the photoacid generator described later. When the compound (DC) is mixed with the resin (A) that also functions as an acid generator or a photoacid generator described later, the repeating unit (P1 ) or the acid generated from the photoacid generator collides with an onium salt having an unreacted weak acid anion, the weak acid is released by salt exchange to yield an onium salt having a strong acid anion. In this process, the strong acid is exchanged for a weak acid with a lower catalytic activity, so that the acid is apparently deactivated and acid diffusion can be controlled.

As the compound (DC), compounds represented by the following general formulas (d1-1) to (d1-3) are preferred.

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

Preferred examples of the sulfonium cation or iodonium cation represented by M ⁺ include the sulfonium cation represented by the above general formula (ZIa) and the iodonium cation represented by the above general formula (ZIIa).

The compound (DC) is a compound (hereinafter also referred to as "compound (DCA)") having a cation site and an anion site in the same molecule and in which the cation site and the anion site are linked by a covalent bond. may
As the compound (DCA), compounds represented by any one of the following general formulas (C-1) to (C-3) are preferable.

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 a single bond that links the cation site and the anion site.
—X ^— represents an anionic moiety selected from —COO ⁻ , —SO ₃ ⁻ , —SO ₂ ⁻ , and —N ⁻ —R ₄ . R ₄ has 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 combine with each other to form a ring structure. In general formula (C-3), two of R ₁ to R ₃ together represent one divalent substituent, which may be bonded to the N atom via a double bond.

Examples of substituents having 1 or more carbon atoms for R ₁ to R ₃ include an alkyl group, a cycloalkyl group, an aryl group, an alkyloxycarbonyl group, a cycloalkyloxycarbonyl group, an aryloxycarbonyl group, an alkylaminocarbonyl group, and a cycloalkylamino A carbonyl group, an arylaminocarbonyl group, and the like can be mentioned. An alkyl group, a cycloalkyl group, or an aryl group is preferred.

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 of these A group formed by combining more than one species and the like 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 of these.

A compound (DD) having a nitrogen atom and a group that leaves by the action of an acid (hereinafter also referred to as "compound (DD)") is an amine having a group that leaves on the nitrogen atom by the action of an acid. Derivatives are preferred.
The group that leaves by the action of an acid is preferably an acetal group, a carbonate group, a carbamate group, a tertiary ester group, a tertiary hydroxyl group, or a hemiaminal ether group, more preferably a carbamate group or a hemiaminal ether group. .
The molecular weight of the compound (DD) is preferably 100-1000, more preferably 100-700, even more preferably 100-500.
Compound (DD) may have a carbamate group with a protecting group on the nitrogen atom. A protecting group constituting a carbamate group is represented by the following general formula (d-1).

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), an aralkyl group ( preferably 1 to 10 carbon atoms) or an alkoxyalkyl group (preferably 1 to 10 carbon atoms). Rb's may combine with each other to form a ring.
The alkyl group, cycloalkyl group, aryl group, and aralkyl group represented by Rb are each independently a hydroxyl group, a cyano group, an amino group, a pyrrolidino group, a piperidino group, a morpholino group, a functional group such as an oxo group, an alkoxy group, or It may be substituted with a halogen atom. The same applies to the alkoxyalkyl group represented by Rb.

Rb is preferably a linear or branched alkyl group, cycloalkyl group or aryl group, more preferably a linear or branched alkyl group or cycloalkyl group.
Examples of the ring formed by connecting two Rb's to each other include alicyclic hydrocarbons, aromatic hydrocarbons, heterocyclic hydrocarbons and derivatives thereof.
Specific structures of the group represented by formula (d-1) include, but are not limited to, structures disclosed in paragraph [0466] of US Patent Publication No. US2012/0135348A1.

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

In general formula (6),
l represents an integer of 0 to 2, m represents an integer of 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 linked together to form a heterocyclic ring together with the nitrogen atom in the formula. This heterocyclic ring may contain a heteroatom other than the nitrogen atom in the formula.
Rb has the same definition as Rb in formula (d-1) above, and preferred examples are also the same.
In the general formula (6), the alkyl group, cycloalkyl group, aryl group, and aralkyl group as Ra are each independently substituted with an alkyl group, cycloalkyl group, aryl group, and aralkyl group as Rb. It may be substituted with the same groups as the groups described above as good groups.

Specific examples of the alkyl group, cycloalkyl group, aryl group, and aralkyl group (these groups may be substituted with the above groups) for Ra include the same groups as the specific examples described above for Rb. be done.
Specific examples of particularly preferred compounds (DD) in the present invention include, but are not limited to, 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 moiety (hereinafter also referred to as "compound (DE)") is preferably a compound having a basic site containing a nitrogen atom in the cation moiety. The basic moiety is preferably an amino group, more preferably an aliphatic amino group. More preferably all of the atoms adjacent to the nitrogen atom in the basic moiety are hydrogen atoms or carbon atoms. Moreover, from the viewpoint of improving basicity, it is preferable that an electron-withdrawing functional group (a carbonyl group, a sulfonyl group, a cyano group, a halogen atom, etc.) is not directly connected to the nitrogen atom.
Preferred specific examples of the compound (DE) include, but are not limited to, compounds disclosed in paragraph [0203] of US Patent Application Publication No. 2015/0309408A1.

In the present invention, the acid diffusion control agent is preferably a basic compound (DA), and among them, a compound having a structure represented by the general formula (C) is preferable, and the following general formula (DAC1), A compound represented by (DAC2) or (DAC3) is more preferable.

In general formulas (DAC1), (DAC2) and (DAC3), Ar ^D1 to Ar ^D3 each independently represent an aromatic group.
Ar ^D1 to Ar ^D3 preferably represent an aryl group, more preferably a phenyl group.
The aromatic group represented by Ar ^D1 to Ar ^D3 may have a substituent, and examples of the substituent include an alkyl group, an alkoxy group and an ester group, with a methoxy group being particularly preferred.

Preferred examples of the acid diffusion controller (Q) are shown below, but the present invention is not limited to these.

The acid diffusion controller (Q) may be used alone or in combination of two or more.
The composition of the present invention may or may not contain an acid diffusion control agent (Q). It is preferably 0.001 to 20% by mass, more preferably 0.01 to 10% by mass, based on the total solid content.

[solvent]
The composition of the invention preferably contains a solvent.
Examples of solvents include, but are not limited to, alkylene glycol monoalkyl ether carboxylates, alkylene glycol monoalkyl ethers, lactic acid alkyl esters, alkyl alkoxypropionates, cyclic lactones (preferably having 4 to 10 carbon atoms), and rings. and organic solvents such as monoketone compounds (preferably having 4 to 10 carbon atoms), alkylene carbonates, alkyl alkoxyacetates, and alkyl pyruvates.
Regarding the solvent, the description in paragraphs [0187] to [0197] of International Publication No. 2019/058890 can be referred to, and the contents thereof are incorporated herein.

As the organic solvent, a mixed solvent in which a solvent having a hydroxyl group in its structure and a solvent having no hydroxyl group are mixed may be used.
As the solvent having a hydroxyl group and the solvent not having a hydroxyl group, the compounds described above can be appropriately selected. As the solvent containing a hydroxyl group, alkylene glycol monoalkyl ether, alkyl lactate, etc. are preferable, and propylene glycol monomethyl ether (PGME ), propylene glycol monoethyl ether (PGEE), or methyl 2-hydroxyisobutyrate are more preferred. As the solvent having no hydroxyl group, alkylene glycol monoalkyl ether acetate, alkylalkoxypropionate, monoketone compound which may have a ring, cyclic lactone, or alkyl acetate are preferable. Glycol monomethyl ether acetate (PGMEA), ethyl ethoxy propionate, 2-heptanone, γ-butyrolactone, cyclohexanone, cyclopentanone or butyl acetate are more preferred, propylene glycol monomethyl ether acetate, γ-butyrolactone, ethyl ethoxy propionate, Cyclohexanone, cyclopentanone or 2-heptanone are more preferred. Propylene carbonate is also preferred as the solvent having no hydroxyl group.
The mixing ratio (mass ratio) of the solvent having a hydroxyl group and the solvent having no hydroxyl group is preferably 1/99 to 99/1, more preferably 10/90 to 90/10, and 20/ More preferably 80 to 60/40. A mixed solvent containing 50% by mass or more of a solvent having no hydroxyl group is preferable from the viewpoint of coating uniformity.
The solvent preferably contains propylene glycol monomethyl ether acetate, and may be a single solvent of propylene glycol monomethyl ether acetate or a mixed solvent of two or more kinds containing propylene glycol monomethyl ether acetate.

Although the content of the solvent in the composition of the present invention is not particularly limited, it is preferable to use the solvent so that the solid content concentration of the composition of the present invention is 1.0 to 10% by mass. The solid content concentration of the composition of the present invention is preferably 2.0 to 5.7% by mass, more preferably 2.0 to 5.3% by mass.
The solid content concentration is the mass percentage of the sum of the masses of other components excluding the solvent with respect to the total mass of the composition of the present invention.

[Compound that generates acid upon exposure to actinic rays or radiation]
The composition of the present invention may contain, as a component different from the resin (A) described above, a compound that generates an acid upon exposure to actinic rays or radiation (also referred to as a “photoacid generator”).
A photoacid generator is a compound that generates an acid upon exposure to actinic rays or radiation.
As the photoacid generator, a compound that generates an organic acid upon exposure to actinic rays or radiation is preferred. Examples include sulfonium salt compounds, iodonium salt compounds, diazonium salt compounds, phosphonium salt compounds, imidosulfonate compounds, oximesulfonate compounds, diazodisulfone compounds, disulfone compounds, and o-nitrobenzylsulfonate compounds.

As the photoacid generator, a known compound that generates an acid upon exposure to actinic rays or radiation can be appropriately selected and used either singly or as a mixture thereof. For example, paragraphs [0125] to [0319] of US Patent Application Publication No. 2016/0070167A1, paragraphs [0086] to [0094] of US Patent Application Publication No. 2015/0004544A1, US Patent Application Publication No. 2016/0237190A1 Known compounds disclosed in paragraphs [0323] to [0402] of the specification and paragraphs [0328] to [0350] of Japanese Patent No. 5548473 can be preferably used.

The photoacid generator may be in the form of a low-molecular-weight compound, or may be in the form of being incorporated into a part of the polymer. Moreover, the form of a low-molecular-weight compound and the form incorporated into a part of a polymer may be used in combination.
The photoacid generator is preferably in the form of a low molecular weight compound.
When the photoacid generator is in the form of a low-molecular-weight compound, the molecular weight is preferably 3,000 or less, more preferably 2,000 or less, and even more preferably 1,000 or less.
A photo-acid generator may be used individually by 1 type, and may use 2 or more types together.

The composition of the present invention may or may not contain the photoacid generator, but when it does contain the photoacid generator, the content of the photoacid generator is the total solid content of the composition of the present invention. Based on, it is preferably 0.1 to 25% by mass, more preferably 0.5 to 20% by mass, even more preferably 1 to 15% by mass, 1 to 10% by mass is particularly preferred.

[Surfactant]
The composition of the invention may contain a surfactant. By containing a surfactant, when an exposure light source with a wavelength of 250 nm or less, particularly 220 nm or less is used, it is possible to form a pattern with good adhesion and less development defects with good sensitivity and resolution. Become.
As the surfactant, it is particularly preferable to use a fluorine-based and/or silicon-based surfactant.
Examples of fluorine-based and/or silicon-based surfactants include surfactants described in [0276] of US Patent Application Publication No. 2008/0248425. In addition, F-top EF301 or EF303 (manufactured by Shin-Akita Kasei Co., Ltd.); Florard FC430, 431 or 4430 (manufactured by Sumitomo 3M Co., Ltd.); Megafac F171, F173, F176, F189, F113, F110, F177, F120 or R08 (manufactured by DIC Corporation); Surflon S-382, SC101, 102, 103, 104, 105 or 106 (manufactured by Asahi Glass Co., Ltd.); Troisol S-366 (manufactured by Troy Chemical Co., Ltd.); GF-300 or GF-150 (manufactured by Toagosei Chemical Co., Ltd.), Surflon S-393 (manufactured by Seimi Chemical Co., Ltd.); PF636, PF656, PF6320 or PF6520 (manufactured by OMNOVA); or FTX-204G, 208G, 218G, 230G, 204D, 208D, 212D, 218D or 222D (manufactured by Neos). may Polysiloxane polymer KP-341 (manufactured by Shin-Etsu Chemical Co., Ltd.) can also be used as a silicon-based surfactant.

In addition to the known surfactants shown above, fluoroaliphatic compounds produced by the telomerization method (also called the telomer method) or the oligomerization method (also called the oligomer method) are used as the surfactant. may be synthesized. Specifically, a polymer having a fluoroaliphatic group derived from this fluoroaliphatic compound may be used as a surfactant. This fluoroaliphatic compound can be synthesized, for example, by the method described in JP-A-2002-90991.
Surfactants other than fluorine-based and/or silicone-based surfactants described in [0280] of US Patent Application Publication No. 2008/0248425 may also be used.

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

When the composition of the present invention contains a surfactant, its content is preferably 0.00001 to 2% by mass, more preferably 0.0001 to 2% by mass, based on the total solid content of the composition of the present invention. 2% by mass, more preferably 0.0005 to 1% by mass.

[Other additives]
In addition to the components described above, the composition of the present invention contains a carboxylic acid, an onium carboxylate, a dissolution inhibiting compound having a molecular weight of 3000 or less described in Proceeding of SPIE, 2724, 355 (1996), a dye, and a plasticizer. , a photosensitizer, a light absorber, an antioxidant, and the like can be appropriately contained.

Carboxylic acid, in particular, can also be preferably used to improve performance. Preferred carboxylic acids are aromatic carboxylic acids such as benzoic acid and naphthoic acid.

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, based on the total solid content of the composition. It is preferably 0.01 to 3% by mass.

From the viewpoint of improving resolution, the composition of the present invention is preferably used at a film thickness of 10 to 250 nm, more preferably at a film thickness of 20 to 200 nm, and even more preferably at a film thickness of 30 to 100 nm. preferably used. Such a film thickness can be obtained by setting the solid content concentration in the composition to an appropriate range to give an appropriate viscosity, thereby improving the coatability and the film formability.

[Use]
The composition of the present invention is an actinic ray- or radiation-sensitive resin composition that reacts with irradiation of actinic rays or radiation to change its properties. More specifically, the composition of the present invention can be used in semiconductor manufacturing processes such as IC (Integrated Circuit), circuit board manufacturing such as liquid crystals or thermal heads, manufacturing of imprint mold structures, other photofabrication processes, or The present invention relates to an actinic ray- or radiation-sensitive resin composition used for producing a lithographic printing plate or 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 forming process, a rewiring forming process, MEMS (Micro Electro Mechanical Systems), and the like.
The present invention also relates to an actinic ray-sensitive or radiation-sensitive resin composition for photomask production.

[Actinic ray-sensitive or radiation-sensitive film]
The present invention also relates to an actinic ray- or radiation-sensitive film (preferably a resist film) formed from the composition of the present invention as 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 this film is preferably 0.02 to 0.1 μm. As a method of coating on the substrate, a suitable coating method such as spin coating, roll coating, flow coating, dip coating, spray coating, doctor coating, etc. is used, and spin coating is preferred, and the number of revolutions is 1000 to 3000 rpm (rotations per minute) is preferred. The coated 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.
_The material constituting the substrate to be processed and its outermost layer can be, for example, a silicon wafer in the case of a semiconductor wafer. WSi, BPSG (Boron Phosphorus Silicon Glass), SOG (Spin on Glass), organic antireflection film, and the like.

Before forming the resist film, an antireflection film may be applied on the substrate in advance.
As the antireflection film, both an inorganic film type such as titanium, titanium dioxide, titanium nitride, chromium oxide, carbon and amorphous silicon, and an organic film type consisting of a light absorbing agent and a polymer material can be used. In addition, as the organic antireflection film, commercially available organic antireflection films such as DUV30 series and DUV-40 series manufactured by Brewer Science, AR-2, AR-3 and AR-5 manufactured by Shipley can be used. can.

[Pattern formation method]
The present invention includes a resist film forming step of forming a resist film using the composition of the present invention, an exposure step of exposing the resist film, and a developing step of developing the exposed resist film using a developer, It also relates to a patterning method comprising
In the present invention, the exposure is preferably carried out using an electron beam, an ArF excimer laser or extreme ultraviolet rays, more preferably using an electron beam or extreme ultraviolet rays.

In the manufacture of precision integrated circuit elements, etc., the exposure (pattern forming step) on the resist film is preferably performed by irradiating the resist film with an ArF excimer laser, an electron beam, or extreme ultraviolet (EUV) in a pattern. The exposure amount is about 1 to 100 mJ/cm ² , preferably about 20 to 60 mJ/cm 2 in the case of ArF excimer laser, and about 0.1 to ^{20 μC/cm 2 ,} preferably 3 to 10 μC/cm in the case of electron beam. ² , and in the case of extreme ultraviolet rays, about 0.1 to 20 mJ/cm ² , preferably about 3 to 15 mJ/cm ² .
Then, post-exposure heating 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, still more preferably at 80 to 120°C for 1 to 10 minutes. (Post-exposure baking) is performed, followed by development, rinsing, and drying to form a pattern. Here, post-exposure heating is appropriately adjusted depending on the acid decomposability of the repeating unit having an acid decomposable group in the resin (A). When the 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.
Although the developer is appropriately selected, it is preferable to use an alkaline developer (typically an alkaline aqueous solution) or a developer containing an organic solvent (also referred to as an organic developer). When the developer is an alkaline aqueous solution, a 0.1 to 5% by mass, preferably 2 to 3% by mass alkaline aqueous solution of tetramethylammonium hydroxide (TMAH), tetrabutylammonium hydroxide (TBAH), etc. Development is carried out for 0.1 to 3 minutes, preferably 0.5 to 2 minutes, by a conventional method such as dip method, puddle method or spray method. Suitable amounts of alcohols and/or surfactants may be added to the alkaline developer. Thus, in the formation of a negative pattern, the unexposed portion of the film dissolves and the exposed portion is difficult to dissolve in the developer, and in the formation of a positive pattern, the exposed portion of the film is dissolved, and the unexposed portion of the film is difficult to dissolve in the developer, so that the desired pattern is formed on the substrate.

When the pattern forming method of the present invention includes a step of developing using an alkaline developer, examples of the alkaline developer include sodium hydroxide, potassium hydroxide, sodium carbonate, sodium silicate, sodium metasilicate, and aqueous ammonia. Inorganic alkalis such as ethylamine, primary amines such as n-propylamine, secondary amines such as diethylamine and di-n-butylamine, tertiary amines such as triethylamine and methyldiethylamine, dimethylethanolamine, triethanol alcohol amines such as amines, tetramethylammonium hydroxide, tetraethylammonium hydroxide, tetrapropylammonium hydroxide, tetrabutylammonium hydroxide, tetrapentylammonium hydroxide, tetrahexylammonium hydroxide, tetraoctylammonium hydroxide, ethyl Tetraalkylammonium hydroxide such as trimethylammonium hydroxide, butyltrimethylammonium hydroxide, methyltriamylammonium hydroxide, dibutyldipentylammonium hydroxide, trimethylphenylammonium hydroxide, trimethylbenzylammonium hydroxide, triethylbenzylammonium hydroxide, dimethyl Alkaline aqueous solutions of quaternary ammonium salts such as bis(2-hydroxytethyl)ammonium hydroxide and cyclic amines such as pyrrole and pyreridine can be used.
Furthermore, appropriate amounts of alcohols and surfactants may be added to the alkaline aqueous solution.
The alkali concentration of the alkali developer is usually 0.1 to 20 mass %.
The pH of the alkaline developer is usually 10.0-15.0.
In particular, a 2.38% by weight aqueous solution of tetramethylammonium hydroxide is desirable.

Pure water may be used as the rinse solution in the rinse treatment performed after alkali development, and an appropriate amount of surfactant may be added.
Further, after the development processing or the rinsing processing, a processing for removing the developer or the rinsing liquid adhering to the pattern with a supercritical fluid can be performed.

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

In the present invention, an ester solvent is a solvent having an ester group in the molecule, a ketone solvent is a solvent having a ketone group in the molecule, and an alcohol solvent is an alcoholic solvent in the molecule. It means a solvent having a hydroxyl group, an amide solvent means a solvent having an amide group in its molecule, and an ether solvent means a solvent having an ether bond in its molecule. Some of these solvents have multiple types of the above-mentioned functional groups in one molecule, and in such cases, the solvent species containing the functional groups possessed by the solvent is also applicable. For example, diethylene glycol monomethyl ether applies to both alcohol solvents and ether solvents in the above classification. A hydrocarbon solvent is a hydrocarbon solvent having no substituents.
In particular, a developer containing at least one solvent selected from ketone solvents, ester solvents, alcohol solvents and ether solvents is preferred.

The developer has 7 or more carbon atoms (preferably 7 to 14, more preferably 7 to 12, even more preferably 7 to 10) and 2 or less heteroatoms in order to suppress the swelling of the resist film. It is preferable to use an ester solvent of
The heteroatom of the ester solvent is an atom other than a carbon atom and a hydrogen atom, and examples thereof include an oxygen atom, a nitrogen atom, a sulfur atom and the like. The number of heteroatoms is preferably 2 or less.
Preferable examples of ester solvents having 7 or more carbon atoms and 2 or less heteroatoms include amyl acetate, isoamyl acetate, 2-methylbutyl acetate, 1-methylbutyl acetate, hexyl acetate, pentyl propionate, hexyl propionate, Examples include heptyl propionate, butyl butanoate, and isobutyl isobutanoate, and it is particularly preferred to use isoamyl acetate or isobutyl isobutanoate.

The developer is a mixed solvent of the ester solvent and the hydrocarbon solvent, or the ketone solvent and the carbonized solvent, instead of the ester solvent having 7 or more carbon atoms and 2 or less heteroatoms. A mixed solvent of hydrogen solvent may be used. Even in this case, it is effective in suppressing the swelling of the resist film.
When an ester solvent and a hydrocarbon solvent are used in combination, isoamyl acetate is preferably used as the ester solvent. As the hydrocarbon solvent, it is preferable to use a saturated hydrocarbon solvent (eg, octane, nonane, decane, dodecane, undecane, hexadecane, etc.) from the viewpoint of adjusting the solubility of the resist film.
Ketone solvents include, for example, 1-octanone, 2-octanone, 1-nonanone, 2-nonanone, acetone, 2-heptanone (methyl amyl ketone), 4-heptanone, 1-hexanone, 2-hexanone, diisobutyl ketone, 2,5-dimethyl-4-hexanone, diisobutyl ketone, cyclohexanone, methylcyclohexanone, phenylacetone, methyl ethyl ketone, methyl isobutyl ketone, acetylacetone, acetonyl acetone, ionone, diacetonyl alcohol, acetylcarbinol, acetophenone, methylnaphthyl ketone, Isophorone, propylene carbonate and the like can be mentioned, and it is particularly preferable to use diisobutyl ketone and 2,5-dimethyl-4-hexanone.
Examples of ester solvents include methyl acetate, butyl acetate, ethyl acetate, isopropyl acetate, pentyl acetate, isoamyl acetate, amyl acetate, propylene glycol monomethyl ether acetate, ethylene glycol monoethyl ether acetate, diethylene glycol monobutyl ether acetate, and diethylene glycol monoethyl. ether acetate, ethyl-3-ethoxypropionate, 3-methoxybutyl acetate, 3-methyl-3-methoxybutyl acetate, methyl formate, ethyl formate, butyl formate, propyl formate, ethyl lactate, butyl lactate, propyl lactate, butyric acid Butyl, methyl 2-hydroxyisobutyrate and the like can be mentioned.
Examples of alcohol solvents include methyl alcohol, ethyl alcohol, n-propyl alcohol, isopropyl alcohol, n-butyl alcohol, sec-butyl alcohol, 4-methyl-2-pentanol, tert-butyl alcohol, isobutyl alcohol, n - Alcohols such as hexyl alcohol, n-heptyl alcohol, n-octyl alcohol, n-decanol, glycol solvents such as ethylene glycol, diethylene glycol, triethylene glycol, ethylene glycol monomethyl ether, propylene glycol monomethyl ether, ethylene glycol mono Glycol ether solvents such as ethyl ether, propylene glycol monoethyl ether, diethylene glycol monomethyl ether, triethylene glycol monoethyl ether, and methoxymethylbutanol can be used.
Examples of ether-based solvents include the above glycol ether-based solvents, as well as anisole, dioxane, tetrahydrofuran, and the like.
Examples of amide solvents include N-methyl-2-pyrrolidone, N,N-dimethylacetamide, N,N-dimethylformamide, hexamethylphosphoric triamide, 1,3-dimethyl-2-imidazolidinone, and the like. Available.
Examples of hydrocarbon solvents include aromatic hydrocarbon solvents such as toluene and xylene, and aliphatic hydrocarbon solvents such as pentane, hexane, octane, decane, and undecane.
The aliphatic hydrocarbon-based solvent, which is a hydrocarbon-based solvent, may be a mixture of compounds having the same number of carbon atoms but different structures. For example, when decane is used as the aliphatic hydrocarbon solvent, aliphatic hydrocarbon solvents such as 2-methylnonane, 2,2-dimethyloctane, 4-ethyloctane, and isooctane, which are compounds with the same number of carbon atoms but different structures, may be included in
Further, the compounds having the same number of carbon atoms but different structures may be contained alone, or may be contained in a plurality of types as described above.
A plurality of the above solvents may be mixed, or a solvent other than the above or water may be mixed and used. However, in order to fully exhibit the effects of the present invention, the water content of the developer as a whole is preferably less than 10% by mass, and more preferably substantially free of water.
The concentration of the organic solvent (in the case of multiple mixtures, the total) in the organic developer is preferably 50% by mass or more, more preferably 50 to 100% by mass, still more preferably 85 to 100% by mass, still more preferably 90 to 100% by weight, particularly preferably 95 to 100% by weight. Most preferably, it consists essentially of an organic solvent. In addition, the case where it consists substantially only of the organic solvent includes the case where a small amount of surfactant, antioxidant, stabilizer, antifoaming agent, etc. are contained.
In particular, the organic developer is preferably a developer containing at least one organic solvent selected from the group consisting of ketone solvents, ester solvents, alcohol solvents, amide solvents and ether solvents. .

The vapor pressure of the organic developer at 20° C. is preferably 5 kPa or less, more preferably 3 kPa or less, and particularly preferably 2 kPa or less. By setting the vapor pressure of the organic developer to 5 kPa or less, evaporation of the developer on the substrate or in the developing cup is suppressed, temperature uniformity within the wafer surface is improved, and as a result, dimension uniformity is achieved within the wafer surface. sex improves.
Specific examples having a vapor pressure of 5 kPa or less include 1-octanone, 2-octanone, 1-nonanone, 2-nonanone, 2-heptanone (methyl amyl ketone), 4-heptanone, 2-hexanone, diisobutyl ketone, Ketone solvents such as cyclohexanone, methylcyclohexanone, phenylacetone, methyl isobutyl ketone, butyl acetate, pentyl acetate, isoamyl acetate, amyl acetate, propylene glycol monomethyl ether acetate, ethylene glycol monoethyl ether acetate, diethylene glycol monobutyl ether acetate, diethylene glycol monoethyl Ester-based solvents such as ether acetate, ethyl-3-ethoxypropionate, 3-methoxybutyl acetate, 3-methyl-3-methoxybutyl acetate, butyl formate, propyl formate, ethyl lactate, butyl lactate, propyl lactate, n- Alcohol solvents such as propyl alcohol, isopropyl alcohol, n-butyl alcohol, sec-butyl alcohol, tert-butyl alcohol, isobutyl alcohol, n-hexyl alcohol, n-heptyl alcohol, n-octyl alcohol, n-decanol, ethylene glycol , diethylene glycol, triethylene glycol and other glycol-based solvents, ethylene glycol monomethyl ether, propylene glycol monomethyl ether, ethylene glycol monoethyl ether, propylene glycol monoethyl ether, diethylene glycol monomethyl ether, triethylene glycol monoethyl ether, methoxymethylbutanol, etc. , ether solvents such as tetrahydrofuran, amide solvents such as N-methyl-2-pyrrolidone, N,N-dimethylacetamide, and N,N-dimethylformamide, aromatic hydrocarbon solvents such as toluene and xylene. , octane, and decane.
Specific examples having a vapor pressure of 2 kPa or less, which is a particularly preferred range, include 1-octanone, 2-octanone, 1-nonanone, 2-nonanone, 2-heptanone, 4-heptanone, 2-hexanone, diisobutyl ketone, Ketone solvents such as cyclohexanone, methylcyclohexanone, phenylacetone, butyl acetate, amyl acetate, propylene glycol monomethyl ether acetate, ethylene glycol monoethyl ether acetate, diethylene glycol monobutyl ether acetate, diethylene glycol monoethyl ether acetate, ethyl-3-ethoxypropio acid, 3-methoxybutyl acetate, 3-methyl-3-methoxybutyl acetate, ethyl lactate, butyl lactate, propyl lactate ester solvents, n-butyl alcohol, sec-butyl alcohol, tert-butyl alcohol, isobutyl alcohol, Alcohol solvents such as n-hexyl alcohol, n-heptyl alcohol, n-octyl alcohol and n-decanol, glycol solvents such as ethylene glycol, diethylene glycol and triethylene glycol, ethylene glycol monomethyl ether, propylene glycol monomethyl ether, ethylene Glycol ether solvents such as glycol monoethyl ether, propylene glycol monoethyl ether, diethylene glycol monomethyl ether, triethylene glycol monoethyl ether, methoxymethylbutanol, N-methyl-2-pyrrolidone, N,N-dimethylacetamide, N,N - Amide solvents such as dimethylformamide, aromatic hydrocarbon solvents such as xylene, and aliphatic hydrocarbon solvents such as octane, decane and undecane.

The organic developer may contain a basic compound. Specific examples and preferred examples of the basic compound that can be contained in the developer used in the present invention are the same as those in the above-mentioned basic compound that can be contained in the actinic ray- or radiation-sensitive composition.

An appropriate amount of surfactant can be added to the organic developer as needed.
Although the surfactant is not particularly limited, for example, ionic or nonionic fluorine-based and/or silicon-based surfactants can be used. Examples of these fluorine and/or silicon surfactants include JP-A-62-36663, JP-A-61-226746, JP-A-61-226745, JP-A-62-170950, JP-A-63-34540, JP-A-7-230165, JP-A-8-62834, JP-A-9-54432, JP-A-9-5988, US Pat. No. 5,405,720, the same 5360692, 5529881, 5296330, 5436098, 5576143, 5294511 and 5824451. , preferably non-ionic surfactants. Although the nonionic surfactant is not particularly limited, it is more preferable to use a fluorine-based surfactant or a silicon-based surfactant.
The amount of surfactant used is preferably 0.0001 to 2% by mass, more preferably 0.0001 to 1% by mass, and particularly preferably 0.0001 to 0.1% by mass, relative to the total amount of the developer. .

Examples of the development method include a method of immersing the substrate in a bath filled with a developer for a certain period of time (dip method), and a method of developing by standing still for a certain period of time while the developer is heaped up on the surface of the substrate by surface tension (puddle method). method), a method of spraying the developer onto the substrate surface (spray method), and a method of continuously discharging the developer while scanning the developer discharge nozzle at a constant speed onto the substrate rotating at a constant speed (dynamic dispensing method). etc. can be applied.
When the above-described various developing methods include a step of discharging the developer from the developing nozzle of the developing device toward the resist film, the discharge pressure of the discharged developer (flow velocity per unit area of the discharged developer) is It is preferably 2 mL/sec/mm ² or less, more preferably 1.5 mL/sec/mm ² or less, and even more preferably 1 mL/sec/mm ² or less. Although there is no particular lower limit for the flow rate, it is preferably 0.2 mL/sec/mm ² or more in consideration of throughput.
By setting the ejection pressure of the ejected developer within the above range, pattern defects caused by resist residues after development can be significantly reduced.
Although the details of this mechanism are not clear, it is probable that by setting the ejection pressure within the above range, the pressure exerted by the developing solution on the resist film is reduced, and the resist film/pattern may be inadvertently scraped or collapsed. This is thought to be due to suppression.
The developer discharge pressure (mL/sec/mm ² ) is the value at the outlet of the developing nozzle in the developing device.

Examples of methods for adjusting the discharge pressure of the developer include a method of adjusting the discharge pressure with a pump or the like, and a method of changing the pressure by adjusting the pressure supplied from a pressure tank.

Further, after the step of developing using a developer containing an organic solvent, a step of stopping development while replacing with another solvent may be performed.

A step of washing with a rinse solution may be included after the step of developing with a developer containing an organic solvent. It is not necessary to include the step of washing with

The rinse solution used in the rinse step after the step of developing with a developer containing an organic solvent is not particularly limited as long as it does not dissolve the resist pattern, and a common solution containing an organic solvent can be used. . As the rinse liquid, a rinse liquid containing at least one organic solvent selected from the group consisting of hydrocarbon solvents, ketone solvents, ester solvents, alcohol solvents, amide solvents and ether solvents is used. is preferred.
Specific examples of the hydrocarbon-based solvent, ketone-based solvent, ester-based solvent, alcohol-based solvent, amide-based solvent, and ether-based solvent are the same as those described for the developer containing an organic solvent. Particularly preferred are butyl acetate and methyl isobutyl carbinol.
After the step of developing with a developer containing an organic solvent, a rinse solution containing at least one organic solvent selected from the group consisting of ester solvents, alcohol solvents, and hydrocarbon solvents is more preferably applied. It is preferable to carry out the step of washing with a rinsing solution containing an alcoholic solvent or a hydrocarbon solvent.

As the organic solvent contained in the rinse liquid, it is preferable to use a hydrocarbon-based solvent among the organic solvents, and it is more preferable to use an aliphatic hydrocarbon-based solvent. Aliphatic hydrocarbon solvents having 5 or more carbon atoms (for example, pentane, hexane, octane, decane, undecane, dodecane, hexadecane, etc.), aliphatic hydrocarbon solvents having 8 or more carbon atoms are preferable, and aliphatic hydrocarbon solvents having 10 or more carbon atoms are more preferable.
Although the upper limit of the number of carbon atoms in the aliphatic hydrocarbon-based solvent is not particularly limited, it may be, for example, 16 or less, preferably 14 or less, and more preferably 12 or less.
Among the above fatty hydrocarbon solvents, decane, undecane and dodecane are particularly preferred, and undecane is most preferred.
By using a hydrocarbon-based solvent (especially an aliphatic hydrocarbon-based solvent) as the organic solvent contained in the rinsing solution in this way, the developer that slightly soaked into the resist film after development is washed away, further suppressing swelling. The effect of suppressing pattern collapse is further exhibited.

A plurality of the above components may be mixed, or may be used by mixing with an organic solvent other than the above.

The water content in the rinse liquid is preferably 10% by mass or less, more preferably 5% by mass or less, and particularly preferably 3% by mass or less. Good developing properties can be obtained by setting the water content to 10% by mass or less.

The vapor pressure of the rinsing solution used after the step of developing with the developer containing an organic solvent is preferably 0.05 kPa or more and 5 kPa or less, more preferably 0.1 kPa or more and 5 kPa or less, at 20°C. 12 kPa or more and 3 kPa or less are most preferable. By setting the vapor pressure of the rinsing liquid to 0.05 kPa or more and 5 kPa or less, the temperature uniformity within the wafer surface is improved, swelling caused by the permeation of the rinsing liquid is suppressed, and the dimensional uniformity within the wafer surface is improved. improves.

An appropriate amount of surfactant may be added to the rinse solution before use.

In the rinsing step, the wafer that has been developed with the developer containing the organic solvent is washed with the rinse liquid containing the organic solvent. The method of cleaning treatment is not particularly limited, but for example, a method of continuously discharging the rinse solution onto the substrate rotating at a constant speed (rotation coating method), or a method of immersing the substrate in a tank filled with the rinse solution for a certain period of time. A method (dip method), a method of spraying a rinse solution onto the substrate surface (spray method), etc. can be applied. It is preferable to rotate to remove the rinse liquid from the substrate. It is also preferable to include a heating step (PostBake) after the rinsing step. The developer and rinse liquid remaining between the patterns and inside the patterns are removed by baking. The heating step after the rinsing step is usually carried out at 40 to 160° C., preferably 70 to 95° C., for usually 10 seconds to 3 minutes, preferably 30 seconds to 90 seconds.

If there is no step of washing with a rinsing solution, for example, the development processing methods described in paragraphs [0014] to [0086] of JP-A-2015-216403 can be employed.

Moreover, the pattern forming method of the present invention may have a developing step using an organic developer and a developing step using an alkaline developer. A portion with a weak exposure intensity is removed by development using an organic developer, and a portion with a high exposure intensity is also removed by performing development with an alkaline developer. By the multiple development process in which development is performed multiple times in this way, pattern formation can be performed without dissolving only the intermediate exposure intensity region, so that a finer pattern than usual can be formed (paragraph of Japanese Patent Laid-Open No. 2008-292975). mechanism similar to [0077]).

Various materials used in the composition of the present invention and the pattern forming method of the present invention (e.g., developer, rinse, composition for forming an antireflection film, composition for forming a top coat, etc.) contain metals, halogen It is preferable not to contain impurities such as metal salts containing, acids, alkalis, components containing sulfur atoms or phosphorus atoms. Here, examples of impurities containing metal atoms include Na, K, Ca, Fe, Cu, Mn, Mg, Al, Cr, Ni, Zn, Ag, Sn, Pb, Li, and salts thereof. can.
The content of impurities contained in these materials is preferably 1 ppm or less, more preferably 1 ppb (parts per billion) or less, still more preferably 100 ppt (parts per trillion) or less, particularly preferably 10 ppt or less, and substantially free. (below the detection limit of the measuring device) is most preferable.
As a method for removing impurities such as metals from various materials, for example, filtration using a filter can be mentioned. The pore size of the filter is preferably 10 nm or less, more preferably 5 nm or less, and even more preferably 3 nm or less. Filters made of polytetrafluoroethylene, polyethylene, or nylon are preferable as the material of the filter. The filter may be a composite material combining these materials and ion exchange media. A filter that has been pre-washed with an organic solvent may be used. In the filter filtration step, multiple types of filters may be connected in series or in parallel for use. When multiple types of filters are used, filters with different pore sizes and/or materials may be used in combination. Further, various materials may be filtered multiple times, and the process of filtering multiple times may be a circulation filtration process.
In addition, as a method for reducing impurities such as metals contained in various materials, there are methods such as selecting raw materials with a low metal content as raw materials constituting various materials, performing filter filtration on raw materials constituting various materials, and For example, distillation may be performed under conditions in which contamination is suppressed as much as possible by, for example, lining the inside with Teflon (registered trademark). Preferred conditions for filtering the raw materials constituting various materials are the same as those described above.
In addition to filter filtration, an adsorbent may be used to remove impurities, or a combination of filter filtration and an adsorbent may be used. As the adsorbent, known adsorbents can be used. For example, inorganic adsorbents such as silica gel and zeolite, and organic adsorbents such as activated carbon can be used.
In addition, as a method for reducing impurities such as metals contained in the organic treatment liquid of the present invention, a raw material having a low metal content is selected as a raw material constituting various materials. Examples include a method of performing filtration, and a method of performing distillation under conditions in which contamination is suppressed as much as possible by lining the inside of the apparatus with Teflon (registered trademark). Preferred conditions for filtering the raw materials constituting various materials are the same as those described above.
In addition to filter filtration, impurities may be removed by an adsorbent, or a combination of filter filtration and adsorbent may be used. As the adsorbent, known adsorbents can be used. For example, inorganic adsorbents such as silica gel and zeolite, and organic adsorbents such as activated carbon can be used.

The organic treatment liquid of the present invention may be added with a conductive compound in order to prevent electrostatic charging and failure of chemical piping and various parts (filters, O-rings, tubes, etc.) due to subsequent electrostatic discharge. good. Examples of conductive compounds include, but are not limited to, methanol. The amount of addition is not particularly limited, but is preferably 10% by mass or less, more preferably 5% by mass or less, from the viewpoint of maintaining preferable developing properties. As for chemical liquid pipes, SUS (stainless steel), antistatic treated polyethylene, polypropylene, or various pipes coated with fluororesin (polytetrafluoroethylene, perfluoroalkoxy resin, etc.) can be used. can. As for filters and O-rings, antistatic treated polyethylene, polypropylene, or fluororesin (polytetrafluoroethylene, perfluoroalkoxy resin, etc.) can also be used.

In general, the developing solution and the rinsing solution are stored in a waste solution tank through pipes after use. At that time, if a hydrocarbon solvent is used as the rinse liquid, the resist dissolved in the developer will precipitate and adhere to the back of the wafer or the side of the pipe. There is a way to pass As for the method of passing through the piping, there is a method of washing the back and sides of the substrate with a solvent that dissolves the resist after washing with the rinse solution, and a method of passing the solvent that dissolves the resist through the piping without contacting the resist. There is a method of flushing.
The solvent to be passed through the piping is not particularly limited as long as it can dissolve the resist, and examples thereof include the above-described organic solvents such as propylene glycol monomethyl ether acetate (PGMEA), propylene glycol monoethyl ether acetate, propylene glycol monopropyl. Ether Acetate, Propylene Glycol Monobutyl Ether Acetate, Propylene Glycol Monomethyl Ether Propionate, Propylene Glycol Monoethyl Ether Propionate, Ethylene Glycol Monomethyl Ether Acetate, Ethylene Glycol Monoethyl Ether Acetate, Propylene Glycol Monomethyl Ether (PGME), Propylene Glycol Mono Ethyl ether, propylene glycol monopropyl ether, propylene glycol monobutyl ether, ethylene glycol monomethyl ether, ethylene glycol monoethyl ether, 2-heptanone, ethyl lactate, 1-propanol, acetone, and the like can be used. Among them, PGMEA, PGME, and cyclohexanone can be preferably used.

[Method for manufacturing electronic device]
The present invention also relates to a method of manufacturing an electronic device, including the pattern forming method described above. The electronic device manufactured by the method for manufacturing an electronic device of the present invention is suitably mounted in electrical and electronic equipment (for example, home appliances, OA (Office Automation) related equipment, media related equipment, optical equipment, communication equipment, etc.). be done.

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

Synthesis Examples of Resin (A) Synthesis examples of resin (A) are shown below, but are not limited thereto.

Synthesis of compound (1-c)

Compound (1-a) (10.0 g, 29.67 mmol), triphenylsulfonium bromide (compound (1-b)) (10.6 g, 31.1 mmol), 150 g of methylene chloride, and 100 g of pure water were charged at room temperature. Stirred for 3 hours. After the organic phase was washed with pure water, the solvent was distilled off under reduced pressure and azeotroped with isopropyl ether. The obtained crude product was recrystallized with ethyl acetate/isopropyl ether, and after vacuum drying, compound (1-c) (8.56 g, 14.8 mmol) was obtained. Compound identification was performed by ESI-MS (electrospray ionization mass spectrometry).
MS-ESI (positive) m/z = 263.1 [M] ⁺
MS-ESI (negative) m/z = 314.0 [M] ⁺

Synthesis of compound (2-c)

Org. Lett. Compound (2-a) was synthesized according to the method described in 2010, 12, 2.
Compound (2-a) (12.7 g, 100 mmol), trifluoromethanesulfonamide (14.9 g, 100 mmol), potassium carbonate (27.6 g, 200 mmol), and 200 ml of acetonitrile were charged and refluxed to boiling point for 3 hours under nitrogen atmosphere. reacted with Acetonitrile was distilled off from the reaction mixture, the mixture was concentrated, 400 ml of acetone was added, and the mixture was stirred. Insoluble matter was filtered off, and the acetone solution was concentrated to obtain 25 g of crude crystals of compound (2-b). Tris(3-methoxyphenyl)sulfonium bromide (43.3 g, 100 mmol), 300 g of methylene chloride and 150 g of pure water were charged and stirred at room temperature for 3 hours. After the organic phase was washed with pure water, the solvent was distilled off under reduced pressure and azeotroped with isopropyl ether. The obtained crude product was recrystallized with ethyl acetate/isopropyl ether, and after vacuum drying, compound (2-c) (24.8 g, 41.9 mmol) was obtained. Compound identification was performed by ESI-MS.
MS-ESI (positive) m/z = 353.1 [M] ⁺
MS-ESI (negative) m/z = 238.0 [M] ⁺

Synthesis of resin (A-11)

(M-1), (M-2), (1-c) are used as monomers, and each monomer is (M-1): (M-2): (1-c) = 50: 40: 10 moles A mixed solvent of diacetone alcohol: methanol = 4: 3 (mass ratio) was added so that the monomer concentration became a solution of 30% by mass, and dimethyl 2,2'-azobis ( 2-methylpropionate) was added to prepare a monomer solution. A 0.1 mass-fold volume of diacetone alcohol was heated to 75° C. in a nitrogen atmosphere, and the monomer solution was added dropwise over 2 hours, followed by further reaction at 75° C. for 2 hours. The resulting resin solution was dropped into a mixed solvent of ethyl acetate:n-heptane=1:9 (mass ratio) to precipitate the resin, which was collected by filtration. The recovered resin was dissolved in diacetone alcohol and added dropwise to water to reprecipitate the resin, followed by filtration, recovery, and vacuum drying to obtain Resin (A-11) with a yield of 46%.

Synthesis of resin (A-12)

Using (M-3), (M-4), (M-5), and (2-c) as monomers, each monomer is (M-3): (M-4): (M-5): ( 2-c) = 40: 40: 7: 13 molar ratio, and a mixed solvent of diacetone alcohol: methanol = 4: 3 (mass ratio) so that the monomer concentration becomes a solution of 30% by mass. 12 mol % of dimethyl 2,2′-azobis(2-methylpropionate) was added as an initiator to prepare a monomer solution. A 0.1 mass-fold volume of diacetone alcohol was heated to 75° C. in a nitrogen atmosphere, and the monomer solution was added dropwise over 2 hours, followed by further reaction at 75° C. for 2 hours. The resulting resin solution was dropped into a mixed solvent of ethyl acetate:n-heptane=1:9 (mass ratio) to precipitate the resin, which was collected by filtration. The recovered resin was dissolved in diacetone alcohol and added dropwise to water to reprecipitate the resin, followed by filtration, recovery, and vacuum drying to obtain Resin (A-12) with a yield of 50%.

Other resins used in Examples were synthesized in the same manner as described above.

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

〔resin〕
The structure of the repeating units of the resins (A-1) to (A-36) and (AX-1) to (AX-5) used, the content of each repeating unit (content ratio (mol%)), and the weight average molecular weight (Mw), and dispersity (Mw/Mn).
The weight average molecular weight (Mw) and the degree of dispersion (Mw/Mn) of the resin were measured by GPC (carrier: tetrahydrofuran (THF)) (in terms of polystyrene). Also, the ratio of each repeating unit was measured by ¹³ C-NMR (nuclear magnetic resonance).
Me represents a methyl group, Et represents an ethyl group, and Bu represents an n-butyl group.

[Photoacid generator]
The structure of the photoacid generator (B-1) used is shown below.

[Acid diffusion control agent]
The structures of the acid diffusion controllers (C-1 to C-14) used are shown below.

[Surfactant]
W-1 to W-4 below were used as surfactants.
W-1: Megafac R08 (manufactured by Dainippon Ink and Chemicals Co., Ltd.; fluorine and silicon type)
W-2: Polysiloxane polymer KP-341 (manufactured by Shin-Etsu Chemical Co., Ltd.; silicon-based)
W-3: Troyl S-366 (manufactured by Troy Chemical Co., Ltd.; fluorine-based)
W-4: PF6320 (manufactured by OMNOVA; fluorine-based)

〔solvent〕
The solvents used are shown below.
S-1: diacetoxyacetone (DAA)
S-2: Propylene glycol monomethyl ether acetate (PGMEA)
S-3: Propylene glycol monomethyl ether (PGME)
S-4: ethyl lactate (EL)
S-5: Ethyl 3-ethoxypropionate (EEP)
S-6: 2-heptanone (MAK)
S-7: methyl 3-methoxypropionate (MMP)
S-8: 3-methoxybutyl acetate S-9: γ-butyrolactone

[Preparation of resist composition]
Components shown in Tables 1 and 2 below were dissolved in solvents shown in Tables 3 and 4 below to prepare solutions, which were filtered through a polyethylene filter having a pore size of 0.02 μm to prepare resist compositions. . Tables 1 and 2 below show the content of acid-generating repeating units in the resins used and the Ohnishi parameter of the total solid content of the resist composition. The solid content concentration of each resist composition is as shown in Tables 3 and 4 below. The content of each component excluding the solvent is the ratio (% by mass) to the total solid content of the resist composition. When a surfactant was used, the type of surfactant used is shown in Tables 1 and 2 below. The amount (content) of the surfactant used was 0.01% by mass with respect to the total solid content of the resist composition.

[Coating of resist composition]
The resist composition is coated on a 6-inch Si wafer that has been previously treated with hexamethyldisilazane (HMDS) using a Tokyo Electron spin coater Mark 8, and dried on a hot plate at 130° C. for 300 seconds to form a film. A resist film with a thickness of 100 nm was obtained.
Similar results can be obtained by replacing the Si wafer with a chromium substrate.

[EB exposure and development]
The wafer coated with the resist film obtained above was subjected to pattern irradiation using an electron beam lithography system (HL750 manufactured by Hitachi, Ltd., acceleration voltage 50 keV). At this time, drawing was performed so as to form a line and space of 1:1. After electron beam lithography, after heating at 100° C. for 60 seconds on a hot plate, a 2.38% by mass tetramethylammonium hydroxide aqueous solution was paddled to develop for 30 seconds, rinsed with pure water, and spun at 4000 rpm. After rotating the wafer at the number of revolutions for 30 seconds, it was heated at 95° C. for 60 seconds to obtain a 1:1 line-and-space resist pattern with a line width of 50 nm.

[evaluation]
The obtained pattern was evaluated for resolution and etching resistance by the following methods.

The sensitivity (Eop) was defined as the irradiation energy for resolving a 1:1 line-and-space pattern with a line width of 50 nm.

<Resolution>
The limit resolving power (minimum line width at which lines and spaces (line:space=1:1) are separated and resolved) at the exposure dose showing the above sensitivity (Eop) was defined as resolution (nm).
The resolution evaluation result is preferably less than 30 nm.

<Etching resistance>
A resist film having a line width of 100 nm (line: space = 1: 1) was formed with an irradiation dose (electron beam irradiation dose) exhibiting the above sensitivity, and a resist film was exposed to Ar/C ₄ F ₆ /O ₂ gas with HITACHI U-621. Dry etching was performed for 60 seconds using (a mixed gas with a volume ratio of 100/4/2). After that, the residual film ratio was measured and used as an index of etching resistance, and evaluated according to the following criteria.
Remaining film ratio (%) = 100 x (thickness of resist film after etching)/(thickness of resist film before etching)
AA: Remaining film rate 97.5% or more A: Remaining film rate 95.0% or more and less than 97.5% B: Remaining film rate 92.5% or more and less than 95.0% C: Remaining film rate 90.0% or more Less than 92.5% D: Less than 90.0% residual film rate

The evaluation results are shown in Table 5.

From the evaluation results in Table 5, it was found that the resist compositions of Examples 1a to 37a were excellent in resolution and etching resistance when used for pattern formation.
The resist compositions of Comparative Examples 1a to 3a were inferior in resolution and etching resistance to those of Examples. This is because the content of the acid-generating repeating unit in the resin used is not more than 0.25 mmol/g, and the repeating unit (a) having at least one aromatic ring different from the acid-generating repeating unit is included. This is thought to be due to the fact that there is no
The resist composition of Comparative Example 4a was inferior in resolution to those of Examples. This is because the resin used does not have an acid-generating repeating unit and a low-molecular-weight photo-acid generator is used, but the content of the photo-acid generator is small, so the resolution is not improved. It is thought that this is because
In the resist composition of Comparative Example 5a, the content of the low-molecular-weight photoacid generator was increased compared to Comparative Example 4a, but this deteriorated the film quality of the resist film and lowered the resolution and etching resistance. It is considered that
In Comparative Example 6a, a resin having an acid-generating repeating unit content of 0.25 mmol/g or more was used. Therefore, it is considered that the resolution was inferior to that of the examples.

Claims (19)

A repeating unit (P1) represented by the following general formula (1) that decomposes upon exposure to actinic rays or radiation to generate an acid, and a repeating unit (P1) having at least one aromatic ring different from the repeating unit (P1) containing a resin (A) having a),
An actinic ray-sensitive or radiation-sensitive resin composition, wherein the content of the repeating unit (P1) in the total solid content is 0.25 mmol/g or more.

In general formula (1), R ₁₁ to R ₁₃ each independently represent a hydrogen atom, an organic group or a halogen atom. However, R ₁₂ may combine with L to form a ring. L represents a single bond or a divalent linking group. R ₁₄ represents a substituent. Q ⁺ represents an organic onium ion. 2. The actinic ray-sensitive or radiation-sensitive resin composition according to claim 1, wherein the repeating unit (a) is represented by the following general formula (2).

In general formula (2), R ₂₁ to R ₂₄ each independently represent a hydrogen atom, an organic group or a halogen atom. R ₂₂ may combine with R ₂₄ to form a ring, in which case R ₂₂ represents a single bond or an alkylene group. However, at least one of R ₂₁ to R ₂₄ represents a group having an aromatic ring. 3. The actinic ray-sensitive or radiation-sensitive resin composition according to claim 1, wherein the repeating unit (a) is represented by the following general formula (3).

In general formula (3), R ₃₁ to R ₃₃ each independently represent a hydrogen atom, an organic group or a halogen atom. However, R ₃₂ may combine with Ar to form a ring, in which case R ₃₂ represents a single bond or an alkylene group. _L3 represents a single bond or a divalent linking group. Ar represents an aromatic ring group. The actinic ray-sensitive or radiation-sensitive resin composition according to any one of claims 1 to 3, wherein the repeating unit (a) is represented by the following general formula (4).

In general formula (4), R ₄₁ to R ₄₃ each independently represent a hydrogen atom, an organic group or a halogen atom. However, _R42 may combine with Ar to form a ring, in which case _R42 represents a single bond or an alkylene group. L4 represents a single bond or a _divalent linking group. Ar represents an aromatic ring group. k represents an integer of 1 to 5; The resin (A) has a repeating unit (P2) having a group that is decomposed by the action of an acid to increase its polarity,
The repeating unit (P2) is a repeating unit having at least one group selected from the group consisting of a group that decomposes under the action of an acid to yield a carboxyl group and a group that decomposes under the action of an acid to yield a hydroxyl group. The actinic ray-sensitive or radiation-sensitive resin composition according to any one of claims 1 to 4. The repeating unit (P2) is at least selected from the group consisting of a group that decomposes under the action of an acid to produce a carboxy group bound to an aromatic ring, and a group that decomposes under the action of an acid to produce a hydroxyl group bound to an aromatic ring. 6. The actinic ray-sensitive or radiation-sensitive resin composition according to claim 5, which is a repeating unit having one group. 6. The actinic ray-sensitive or radiation-sensitive resin composition according to claim 5, wherein the repeating unit (P2) is a repeating unit represented by any one of the following general formulas (5) to (9).

In general formula (5), R ₅₁ to R ₅₃ each independently represent a hydrogen atom, an alkyl group, a cycloalkyl group, a halogen atom, a cyano group, or an alkoxycarbonyl group. _L5 represents a single bond or a divalent linking group. R ₅₄ to R ₅₆ each independently represent a hydrogen atom, an alkyl group, a cycloalkyl group, an aryl group, an aralkyl group or an alkenyl group. Two of R ₅₄ to R ₅₆ may combine with each other to form a ring.
In general formula (6), R ₆₁ to R ₆₄ each independently represent a hydrogen atom or an organic group. However, at least one of R ₆₁ and R ₆₂ represents an organic group. X ₆ represents -CO-, -SO- or -SO ₂ -. Y ₆ represents -O-, -S-, -SO-, -SO ₂ -, or -NR ₄₈ -. _R48 represents a hydrogen atom or an organic group. _L6 represents a single bond or a divalent linking group. R ₆₅ to R ₆₇ each independently represent a hydrogen atom, an alkyl group, a cycloalkyl group, an aryl group, an aralkyl group or an alkenyl group. Two of R ₆₅ to R ₆₇ may combine with each other to form a ring.
In general formula (7), R ₇₁ and R ₇₂ each independently represent a hydrogen atom or an organic group. _R73 and _R74 each independently represent a hydrogen atom, an alkyl group, a cycloalkyl group, an aryl group, an aralkyl group, or an alkenyl group. Two of R ₇₁ to R ₇₄ may combine with each other to form a ring.
In general formula (8), R ₈₁ to R ₈₃ each independently represent a hydrogen atom, an alkyl group, a cycloalkyl group, a halogen atom, a cyano group, or an alkoxycarbonyl group. _L8 represents a single bond or a divalent linking group. Ar ₈ represents an aromatic ring group. R ₈₄ to R ₈₆ each independently represent a hydrogen atom, an alkyl group, a cycloalkyl group, an aryl group, an aralkyl group or an alkenyl group. Two of R ₈₄ to R ₈₆ may combine with each other to form a ring. Ar ₈ may combine with R ₈₂ or R ₈₄ to form a ring.
In general formula (9), R ₉₁ to R ₉₃ each independently represent a hydrogen atom, an alkyl group, a cycloalkyl group, a halogen atom, a cyano group, or an alkoxycarbonyl group. _L9 represents a single bond or a divalent linking group. R ₉₄ to R ₉₆ each independently represent a hydrogen atom, an alkyl group, a cycloalkyl group, an aryl group, an aralkyl group or an alkenyl group. R ₉₅ and R ₉₆ may combine with each other to form a ring. 8. The actinic ray-sensitive or radiation-sensitive resin composition according to claim 7, wherein said repeating unit (P2) is a repeating unit represented by said general formula (5), (8) or (9). The actinic ray-sensitive or radiation-sensitive resin composition according to claim 7 or 8, wherein L5 in the general formula ( ₅ ) is a divalent aromatic linking group. The actinic ray-sensitive or radiation-sensitive resin composition according to claim 7 or 8, wherein L9 in the general formula ( ₉ ) is a divalent aromatic linking group. The actinic ray-sensitive or radiation-sensitive resin composition according to any one of claims 1 to 10, wherein the content of the repeating unit (P1) in the total solid content is 0.50 mmol/g or more. The actinic ray-sensitive or radiation-sensitive resin composition according to any one of claims 1 to 11, wherein L in the general formula (1) is a phenylene group. The actinic ray-sensitive or radiation-sensitive resin composition according to any one of claims 1 to 11, wherein L in the general formula (1) is a single bond. The actinic ray-sensitive or radiation-sensitive resin composition according to any one of claims 1 to 11, wherein L in the general formula (1) is an alkylene group having 1 to 3 carbon atoms. The actinic ray-sensitive or radiation-sensitive resin composition according to any one of claims 1 to 14, wherein R ₁₄ in the general formula (1) represents an aryl group or a fluorinated alkyl group. 16. The actinic ray-sensitive or radiation-sensitive resin composition according to any one of claims 1 to 15, wherein the resin (A) is a resin whose solubility in an alkaline developer is increased by the action of an acid. An actinic ray- or radiation-sensitive film formed using the actinic ray- or radiation-sensitive resin composition according to any one of claims 1 to 16. A resist film forming step of forming a resist film using the actinic ray-sensitive or radiation-sensitive resin composition according to any one of claims 1 to 16, an exposure step of exposing the resist film, and an exposed and a developing step of developing the resist film using an alkaline developer. A method for manufacturing an electronic device, comprising the patterning method according to claim 18 .