WO2022215423A1

WO2022215423A1 - Active-light-sensitive or radiation-sensitive resin composition, resist film, pattern formation method, electronic device production method, polymerizable compound, and resin

Info

Publication number: WO2022215423A1
Application number: PCT/JP2022/010353
Authority: WO
Inventors: 洋平石地; 英幸石原; 享平崎田; 翔井本
Original assignee: 富士フイルム株式会社
Priority date: 2021-04-09
Filing date: 2022-03-09
Publication date: 2022-10-13
Also published as: JPWO2022215423A1; TW202307565A

Abstract

Provided is an active-light-sensitive or radiation-sensitive resin composition with which it is possible to form a pattern having exceptional LWR performance and which also has exceptional resolution. Also provided are a resist film, a pattern formation method, and an electronic device production method that involve the active-light-sensitive or radiation-sensitive resin composition. Additionally provided are a polymerizable compound and a resin that are suitably used in the active-light-sensitive or radiation-sensitive resin composition.　The active-light-sensitive or radiation-sensitive resin composition contains a photoacid generator and a resin having repeating units derived from a polymerizable compound having an acid-decomposable group, the polymerizable compound being such that the glass transition temperature of a homopolymer thereof is 220°C or higher, and the molar amount of acid-decomposable groups relative to the mass of the polymerizable compound being 3.40 mmol/g or greater.

Description

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

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

Since the resist for KrF excimer laser (248 nm), a pattern forming method using chemical amplification has been used in order to compensate for the decrease in sensitivity due to light absorption. For example, in a positive chemical amplification method, first, a photoacid generator contained in an exposed area is decomposed by light irradiation to generate an acid. Then, in the post-exposure baking (PEB: Post Exposure Bake) process or the like, the alkali-insoluble groups of the resin contained in the actinic ray-sensitive or radiation-sensitive resin composition are converted into alkali-soluble groups by the catalytic action of the generated acid. The solubility in the developer is changed by, for example, changing the base. Thereafter, development is performed using, for example, a basic aqueous solution. Thereby, the exposed portion is removed to obtain a desired pattern.
For the miniaturization of semiconductor devices, the wavelength of the exposure light source is shortened and the numerical aperture (NA) of the projection lens is increased. Currently, an exposure machine using an ArF excimer laser with a wavelength of 193 nm as a light source has been developed. ing. Moreover, these days, the pattern formation method which uses extreme ultraviolet rays (EUV light: Extreme Ultraviolet) and an electron beam (EB: Electron Beam) as a light source is also being examined.
Under such circumstances, various structures have been proposed as actinic ray-sensitive or radiation-sensitive resin compositions.

For example, Patent Document 1 discloses a resist composition containing a resin containing a structural unit derived from a compound represented by formula (I) and a structural unit having a predetermined structure, and an acid generator. In formula (I), R ¹ and R ² each independently represent a group having an acid-labile group, and W is an optionally substituted C 5-18 alicyclic represents a hydrocarbon group.

JP 2020-154322 A

The present inventors prepared a resist composition with reference to the patent document described in Patent Document 1 and studied it, and found that there is room for further improvement in resolution. In addition, it has been clarified that there is room for further improvement in the LWR (line width roughness) performance of the formed pattern.
Accordingly, an object of the present invention is to provide an actinic ray-sensitive or radiation-sensitive resin composition capable of forming a pattern having excellent LWR performance and having excellent resolution.
Another object of the present invention is to provide a resist film, a pattern forming method, and an electronic device manufacturing method related to the actinic ray-sensitive or radiation-sensitive resin composition.
Another object of the present invention is to provide a polymerizable compound and a resin that are preferably used in the actinic ray-sensitive or radiation-sensitive resin composition.

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

[1] An actinic ray- or radiation-sensitive resin composition containing a resin having repeating units derived from a polymerizable compound having an acid-decomposable group and a photoacid generator,
The polymerizable compound is a polymerizable compound whose homopolymer has a glass transition temperature of 220° C. or higher,
Actinic ray-sensitive or radiation-sensitive resin composition, wherein the molar amount of the acid-decomposable group relative to the mass of the polymerizable compound is 3.40 mmol/g or more.
[2] The actinic ray-sensitive or radiation-sensitive resin composition according to [1], wherein the polymerizable compound contains at least one of an aromatic ring and an aliphatic heterocyclic ring.
[3] The actinic ray-sensitive or radiation-sensitive resin composition according to [1] or [2], wherein the polymerizable compound has a polycyclic structure.
[4] The sensitivity according to [1] or [2], wherein the polymerizable compound is a polymerizable compound having an aliphatic heterocyclic ring of a polycyclic structure, or a polymerizable compound having an aromatic ring. Actinic ray or radiation sensitive resin composition.
[5] The actinic ray-sensitive or radiation-sensitive resin composition according to any one of [1] to [4], wherein the polymerizable compound has at least two acid-decomposable groups.
[6] The actinic ray-sensitive or radiation-sensitive resin composition according to any one of [1] to [5], wherein the polymerizable compound is an acrylic compound or a methacrylic compound.
[7] An actinic ray-sensitive or radiation-sensitive resin composition containing a resin having a repeating unit derived from a polymerizable compound represented by general formula (1) described below and a photoacid generator.
[8] The actinic ray-sensitive or radiation-sensitive resin according to [7], wherein the polymerizable compound represented by the general formula (1) is a polymerizable compound represented by the general formula (3) described later. Composition.
[9] The actinic ray-sensitive or radiation-sensitive resin according to [7], wherein the polymerizable compound represented by the general formula (1) is a polymerizable compound represented by the general formula (4) described later. Composition.
[10] The actinic ray-sensitive or radiation-sensitive resin composition according to any one of [7] to [9], wherein at least two of R ^X1 to R ^X4 represent an acid-decomposable group.
[11] The actinic ray-sensitive or radiation-sensitive resin composition according to any one of [7] to [10], wherein the polymerizable compound is a polymerizable compound represented by general formula (5) described later. .
[12] A resist film formed using the actinic ray-sensitive or radiation-sensitive resin composition according to any one of [1] to [11].
[13] forming a resist film on a substrate using the actinic ray-sensitive or radiation-sensitive resin composition according to any one of [1] to [11];
exposing the resist film;
and developing the exposed resist film using a developer.
[14] A method for manufacturing an electronic device, including the pattern forming method according to [13].
[15] A polymerizable compound represented by general formula (1) described later.
[16] A resin having a repeating unit derived from a polymerizable compound represented by general formula (1) described later.

ADVANTAGE OF THE INVENTION According to this invention, the actinic-ray-sensitive or radiation-sensitive resin composition which can form the pattern which is excellent in LWR performance, and is excellent also in resolution can be provided.
Moreover, according to this invention, the resist film, the pattern formation method, and the manufacturing method of an electronic device regarding the said actinic-ray-sensitive or radiation-sensitive resin composition can be provided.
Moreover, according to the present invention, it is possible to provide a polymerizable compound and a resin that are suitably used in the actinic ray-sensitive or radiation-sensitive resin composition.

¹ H-NMR chart of M-55 synthesized in the Synthesis Example column.

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.
Regarding the notation of groups (atomic groups) in the present specification, as long as it does not contradict the spirit of the present invention, the notation that does not indicate substituted or unsubstituted includes groups having substituents as well as groups not having substituents. do. For example, an "alkyl group" includes not only an alkyl group having no substituent (unsubstituted alkyl group) but also an alkyl group having a substituent (substituted alkyl group). Also, the term "organic group" as used herein refers to a group containing at least one carbon atom.
The substituent is preferably a monovalent substituent unless otherwise specified.
The term "actinic rays" or "radiation" as used herein means, for example, the emission line spectrum of a mercury lamp, far ultraviolet rays represented by excimer lasers, extreme ultraviolet rays (EUV light: Extreme Ultraviolet), X-rays, and electron beams (EB : Electron Beam) and the like. As used herein, "light" means actinic rays or radiation.
Unless otherwise specified, the term "exposure" used herein means not only exposure by the emission line spectrum of a mercury lamp, far ultraviolet rays represented by excimer lasers, extreme ultraviolet rays (EUV light), and X-rays, but also electron beams, Also includes drawing with particle beams such as ion beams.
In the present specification, the term "~" is used to include the numerical values before and after it as lower and upper limits.
The bonding direction of the divalent groups described herein 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, (meth)acrylate refers to acrylate and methacrylate, and (meth)acryl refers to acrylic and methacrylic.
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: differential refraction It is defined as a polystyrene conversion value by a refractive index detector (Refractive Index Detector).

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).

On the other hand, pKa can also be obtained 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.

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

As used herein, halogen atoms include, for example, fluorine, chlorine, bromine, and iodine atoms.

[First embodiment of 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 "resist composition of the first embodiment") is a polymerizable compound having an acid-decomposable group (hereinafter also referred to as "specific monomer A" ) (hereinafter also referred to as “specific acid-decomposable resin A”) and a photoacid generator.
Here, the specific monomer A described above is a polymerizable compound whose homopolymer has a glass transition temperature of 220 ° C. or higher, and the molar amount of the acid-decomposable group with respect to the mass of the polymerizable compound (hereinafter referred to as "protecting group (also referred to as "value") is 3.40 mmol/g or more. In addition, in this specification, the glass transition temperature of the homopolymer of the specific monomer A intends the value measured by the method mentioned later.
The resist composition of the first embodiment can form a pattern with excellent resolution and LWR due to the above configuration.

Although the action mechanism of the resist composition of the first embodiment is not clear, the inventors of the present invention presume as follows.
The specific acid-decomposable resin A contained in the resist composition of the first embodiment has repeating units derived from the specific monomer A. Since the homopolymer of the specific monomer A has a high glass transition temperature, the resist composition of the first embodiment containing the specific acid-decomposable resin A can form a pattern with high film strength. As a result, it is believed that the resist composition of the first embodiment has high resolution (in other words, the critical resolution (nm) is small). Moreover, since the specific monomer A has a high protective group value, the pattern formed by the resist composition of the first embodiment containing the specific acid-decomposable resin A can exhibit excellent dissolution contrast. As a result, it is believed that the pattern formed by the resist composition of the first embodiment has excellent LWR performance. That is, due to the properties of the specific monomer A, it is presumed that the resist composition of the first embodiment has excellent high resolution and that the formed pattern has excellent LWR performance.
Hereinafter, higher resolution of the resist composition and/or better LWR performance of the pattern formed by the resist composition may be referred to as "more excellent effect of the present invention".

The resist composition of the first embodiment will be described in detail below.
The resist composition of the first embodiment 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 resist composition of the first embodiment is typically a chemically amplified resist composition.
First, various components of the resist composition of the first embodiment will be described in detail below.

[Specific acid-decomposable resin A]
The resist composition of the first embodiment contains a resin having repeating units derived from a specific monomer A (specific acid-decomposable resin A).
The specific acid-decomposable resin A is a resin that is decomposed by the action of an acid to increase its polarity.
That is, in the pattern forming method using the resist composition of the first embodiment, typically, when an alkaline developer is employed as the developer, a positive pattern is preferably formed, and the organic developer is used as the developer. When a developer is used, a negative pattern is preferably formed.

<<Specific monomer A>>
First, the specific monomer A will be described below.
The specific monomer A is a polymerizable compound having an acid-decomposable group, the homopolymer of which has a glass transition temperature of 220° C. or higher and a protective group value of 3.40 mmol/g or higher.

An acid-decomposable group means a group that is decomposed by the action of an acid to increase its polarity.
The specific acid-decomposable resin A formed from the specific monomer A having an acid-decomposable group has a repeating unit having an acid-decomposable group (hereinafter also referred to as "acid-decomposable repeating unit"). Due to the presence of this acid-decomposable repeating unit, the specific acid-decomposable resin A exhibits properties such that the action of acid increases the polarity, increases the solubility in alkaline developing solutions, and decreases the solubility in organic solvents.

An acid-decomposable group is usually a group that is decomposed by the action of an acid to form a polar group. The acid-decomposable group preferably has a structure in which a polar group is protected with a leaving group that leaves under the action of an acid. An acid-decomposable group can be decomposed by the action of an acid to produce a polar group.
The polar group is preferably an alkali-soluble group such as a carboxyl group, a phenolic hydroxyl group, a fluorinated alcohol group, a sulfonic acid group, a phosphoric acid group, a sulfonamide group, a sulfonylimide group, (alkylsulfonyl)(alkylcarbonyl)methylene group, (alkylsulfonyl)(alkylcarbonyl)imide group, bis(alkylcarbonyl)methylene group, bis(alkylcarbonyl)imide group, bis(alkylsulfonyl)methylene group, bis(alkylsulfonyl)imide group, tris(alkylcarbonyl) Methylene group, acidic group such as tris(alkylsulfonyl)methylene group, and alcoholic hydroxyl group.
Among them, the polar group is preferably a carboxyl group, a phenolic hydroxyl group, a fluorinated alcohol group (preferably a hexafluoroisopropanol group), or a sulfonic acid group, since the effects of the present invention are more excellent. A group is more preferred, and a carboxyl group is even more preferred.

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, or an alkenyl group (linear or branched). If possible, these groups preferably have a fluorine atom or a group having a fluorine atom as a substituent.
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. more preferred.
Two of Rx ₁ to Rx ₃ may combine with each other to form a ring (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, or t-butyl group. .
The cycloalkyl groups of Rx ₁ to Rx ₃ are monocyclic cycloalkyl groups such as cyclopentyl group or cyclohexyl group, norbornyl group, tetracyclodecanyl group, tetracyclododecanyl group or adamantyl group. Polycyclic cycloalkyl groups are 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.
Aralkyl groups of Rx ₁ to Rx ₃ are preferably aralkyl groups having 7 to 20 carbon atoms.
The alkenyl groups of Rx ₁ to Rx ₃ are preferably vinyl groups.
The ring formed by combining two of Rx ₁ to Rx ₃ is preferably a cycloalkyl group. A cycloalkyl group formed by combining two of Rx ₁ to Rx ₃ is a monocyclic cycloalkyl group such as a cyclopentyl group or a cyclohexyl group, or a norbornyl group, a tetracyclodecanyl group, or 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.
A cycloalkyl group formed by bonding two of Rx ₁ to Rx ₃ together 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 , may be substituted with a vinylidene group. In such a cycloalkyl group, one or more (eg, 1 to 2) 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 also preferred.
Further, in formula (Y1) or formula (Y2), two of Rx ₁ to Rx ₃ combine to form a cycloalkenyl group, and in the cycloalkenyl group, in formula (Y1) or formula (Y2) When a vinylene group is present at a position adjacent to C (carbon atom) specified in "C (Rx ₁ ) (Rx ₂ ) (Rx ₃ )", the remaining one of Rx ₁ to Rx ₃ is a hydrogen atom It's okay.

In formula (Y3), R ₃₆ to R ₃₈ each independently represent a hydrogen atom or an organic group. R ₃₇ and R ₃₈ may combine with each other to form a ring. Examples of organic groups include alkyl groups, cycloalkyl groups, aryl groups, aralkyl groups, and alkenyl groups. It is also preferred that R ₃₆ is a hydrogen atom.
As the alkyl group, cycloalkyl group, aryl group, aralkyl group and alkenyl group represented by R ₃₆ to R ₃₈ in formula (Y3), Rx ₁ to Rx ₃ in formula (Y1) and formula (Y2) The groups described as the alkyl group, cycloalkyl group, aryl group, aralkyl group, and alkenyl group represented by are likewise included.
R ₃₇ and R ₃₈ may combine with each other to form a ring.
Also, R ₃₈ may be bonded to the main chain of the repeating unit in the acid-decomposable repeating unit. R ₃₈ in this case is preferably an alkylene group such as a methylene group.

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

Here, L ₁ and L ₂ each independently represent a hydrogen atom, an alkyl group, a cycloalkyl group, an aryl group, or a group combining these (e.g., a group combining an alkyl group and an aryl group). .
M represents a single bond or a divalent linking group.
Q is an alkyl group optionally containing a heteroatom, a cycloalkyl group optionally containing a heteroatom, an aryl group optionally containing a heteroatom, an amino group, an ammonium group, a mercapto group, a cyano group, an aldehyde group, or a group combining these (for example, a group combining an alkyl group and a cycloalkyl group).
In alkyl groups and cycloalkyl groups, for example, one of the methylene groups may be replaced by a heteroatom such as an oxygen atom or a group containing a heteroatom 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 L ₁ may combine to form a ring (preferably a 5- or 6-membered ring). Q may combine with part of the acid group protected by the group represented by formula (Y3-1) to form a ring. In addition, in the acid-decomposable repeating unit, Q may combine with the main chain of the repeating unit to form a 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 preferably an aryl group.

In the point that the acid decomposability of the acid-decomposable group repeating unit is more excellent, in the leaving group protecting the polar group, when a non-aromatic ring is directly bonded to the polar group (or its residue), the non-aromatic It is also preferred that the ring member atoms adjacent to the ring member atom directly bonded to the above polar group (or residue thereof) in the group ring 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.

A preferred embodiment of the acid-decomposable group is an acid-decomposable group represented by the following general formula (O1) in that the effect of the present invention is more excellent.

In formula (O1), R ¹¹ to R ¹³ each independently represent an alkyl group, a cycloalkyl group, an alkenyl group, or an aryl group. The alkyl group and the alkenyl group may be linear or branched. Moreover, the cycloalkyl group and the aryl group may be either monocyclic or polycyclic.
Two of R ¹¹ to R ¹³ may combine with each other to form a ring, but it is preferred that they do not form a ring from the viewpoint that the effects of the present invention are more excellent.
* represents the binding site.
All of R ¹¹ to R ¹³ are preferably alkyl groups (linear or branched). When all of R ¹¹ to R ¹³ are alkyl groups (linear or branched), at least two of R ¹¹ to R ¹³ are preferably methyl groups.

As the alkyl group for R ¹¹ to R ¹³ , an alkyl group having 1 to 4 carbon atoms is preferable.
The cycloalkyl group for R ¹¹ to R ¹³ includes a monocyclic cycloalkyl group such as a cyclopentyl group or a cyclohexyl group, or a polycyclic group such as a norbornyl group, a tetracyclodecanyl group, a tetracyclododecanyl group, or an adamantyl group. Ring cycloalkyl groups are preferred.
As the aryl group for R ¹¹ to R ¹³ , an aryl group having 6 to 10 carbon atoms is preferable.
A vinyl group is preferred as the alkenyl group for R ¹¹ to R ¹³ .
The cycloalkyl group formed by combining two of R ¹¹ to R ¹³ may be either monocyclic or polycyclic. Single-membered cycloalkyl groups are more preferred. The cycloalkyl group formed by combining two of R ¹¹ to R ¹³ includes, 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, Alternatively, it may be substituted with a vinylidene group. In these cycloalkyl groups, one or more ethylene groups constituting the cycloalkane ring may be replaced with a vinylene group.

In addition, the alkyl group, cycloalkyl group, alkenyl group and aryl group represented by R ¹¹ to R ¹³ may have a substituent. Examples of substituents include alkyl groups (1 to 4 carbon atoms), halogen atoms, hydroxyl groups, alkoxy groups (1 to 4 carbon atoms), carboxyl groups, and alkoxycarbonyl groups (2 to 6 carbon atoms). .

The number of acid-decomposable groups in the specific monomer A is not limited as long as it is 1 or more, but it is preferably 2 or more in terms of the effect of the present invention being more excellent. Although the upper limit is not particularly limited, it is, for example, 8 or less, preferably 6 or less, and more preferably 4 or less.

The specific monomer A is a polymerizable compound whose homopolymer has a glass transition temperature of 220°C or higher. As used herein, the glass transition temperature of the homopolymer of the specific monomer A intends a value measured by the following method.

<<Method for measuring glass transition temperature (Tg (° C.)) of homopolymer of specific monomer A>>
<1> Synthesized with a charging composition of 30% by mass of specific monomer A and 70% by mass of cyclohexyl methacrylate, and having a weight average molecular weight of 60,000 or more (preferably, a weight average molecular weight of 60,000 to 100,000) to obtain a copolymer P1 of
<2> Evaluate the Tg of the obtained copolymer P1 with a differential thermal calorimeter (DSC).
<3> The Tg of the homopolymer of the specific monomer A is calculated using the following formula (1) based on the Fox formula, with the Tg of the homopolymer of cyclohexyl methacrylate set to 98°C.

Formula (1) 1/Tg=w1/Tg1+w2/Tg2
In formula (1), Tg represents the Tg (K) of copolymer P1. Tg1 represents the homopolymer Tg (K) of the specific monomer A. Tg2 represents the homopolymer Tg(K) of cyclohexyl methacrylate. w1 represents the mass fraction of repeating units derived from the specific monomer A with respect to all repeating units in the copolymer P1. w2 represents the mass fraction of repeating units derived from the homopolymer of cyclohexyl methacrylate with respect to all repeating units in copolymer P1. In calculating the homopolymer Tg of the specific monomer A, w1 is set to 0.3 and w2 is set to 0.7.

As a suggestive heat calorimeter, for example, a differential scanning calorimeter "DSC-60 Plus measurement system" manufactured by Shimadzu Corporation can be used.

The glass transition temperature of the homopolymer of the specific monomer A is preferably 220° C. or higher, more preferably 250° C. or higher, and even more preferably 280° C. or higher, from the viewpoint that the effects of the present invention are more excellent. , 300° C. or higher is particularly preferred. Although the upper limit is not particularly limited, it is preferably 400° C. or less.

The protective group value of specific monomer A is 3.40 mmol/g or more. The protective group value represents the molar amount (mmol/g) of the acid-decomposable group relative to the mass of the specific monomer A (polymerizable compound). Although the upper limit is not particularly limited, it is preferably 6.0 mmol/g or less. The protective group value is preferably 3.50 mmol/g or more, and more preferably 3.60 mmol/g or more, from the viewpoint that the effects of the present invention are more excellent.

Although the molecular weight of the specific monomer A is not particularly limited, it is preferably 400 or more, for example. The upper limit is preferably 1,000 or less, more preferably 800 or less, and even more preferably 700 or less.

The specific monomer A has a polymerizable group.
The type of the polymerizable group is not particularly limited, and includes, for example, a radically polymerizable group and a cationic polymerizable group, preferably a radically polymerizable group, and more preferably an ethylenically unsaturated group.
Types of ethylenically unsaturated groups include, for example, a vinyl group, a maleimide group, and CH ₂ ═CR ^T — (R ^T represents a halogen atom (eg, a fluorine atom, a chlorine atom, a bromine atom, and an iodine atom). ), CH ₂ ═CR ^Q —CO—O— (R ^Q is an alkyl group having 1 to 6 carbon atoms optionally substituted with a halogen atom (e.g., fluorine atom, chlorine atom, bromine atom, and iodine atom) , or represents a hydrogen atom, when R ^Q represents a methyl group or a hydrogen atom, CH ₂ =CR ^Q -CO-O- corresponds to a (meth)acryl group, and when R ^Q represents a chlorine atom , CH ₂ ═CR ^Q —CO—O— corresponds to an α-chloroacryl group), etc., and a (meth)acryl group is preferred in that the effects of the present invention are more excellent. That is, the specific monomer A is preferably a (meth)acrylic compound. Among them, the polymerizable group is more preferably a methacryl group because the effects of the present invention are more excellent.
The specific monomer A is preferably a monofunctional monomer.

The specific monomer A preferably contains one or more of an aromatic ring and an aliphatic heterocyclic ring from the viewpoint of setting the glass transition temperature to a predetermined value or higher.
The aromatic ring may be monocyclic or polycyclic, and preferably has 5 to 20 ring member atoms. The aromatic ring group may have one or more (eg, 1 to 5) heteroatoms (oxygen, sulfur, nitrogen, etc.) as ring member atoms.
Examples of aromatic rings include benzene ring, naphthalene ring, tolylene ring, anthracene ring, thiophene ring, furan ring, pyrrole ring, benzothiophene ring, benzofuran ring, benzopyrrole ring, triazine ring, imidazole ring, benzimidazole ring, and triazole. A ring, a thiadiazole ring, a thiazole ring and the like can be mentioned, and a benzene ring is preferred.

The aliphatic heterocycle may be monocyclic or polycyclic, and may be bridged. In addition, the fact that the aliphatic heterocyclic ring has a bridged structure refers to a compound having a bridged structure such as norbornene.
The number of ring member atoms in the aliphatic heterocycle is preferably 5-20. Aliphatic heterocycles contain one or more (eg, 1 to 5) heteroatoms as ring member atoms. In addition, an oxygen atom, a sulfur atom, a nitrogen atom, etc. are mentioned as a heteroatom. In addition, at least one or more of the ring member atoms of the aliphatic heterocycle may be substituted with carbonyl carbon.
As the aliphatic heterocyclic ring, for example, in the following aliphatic hydrocarbon rings (1) to (50), at least one of the ring member atoms is substituted by a hetero atom such as an oxygen atom. is mentioned. In addition, at least one or more of the ring member atoms in the aliphatic hydrocarbon rings (1) to (50) shown below may be substituted with carbonyl carbon.

Among them, the aliphatic heterocycle is preferably a polycyclic aliphatic heterocycle (aliphatic heterocycle having a polycyclic structure) from the viewpoint of setting the glass transition temperature to a predetermined value or higher, especially a bridged type. It is more preferable to have

The specific polymer A may contain only one or more aromatic rings, may contain one or more aliphatic heterocycles, or may contain one or more aromatic rings and one or more aliphatic heterocycles. good too. Moreover, when the specific polymer A contains one or more aromatic rings and one or more aliphatic heterocycles, the aromatic rings and the aliphatic heterocycles may form a polycyclic structure.
In addition, the aromatic ring and the aliphatic heterocyclic ring may further have a substituent.

A preferred embodiment of the specific polymer A is a polymerizable compound having an aliphatic heterocycle with a polycyclic structure or a polymerizable compound having an aromatic ring.

Specific examples of the specific polymer A include compounds represented by the following general formula (A1).
General formula (A1): Y-L-Z-(R) _p
In the formula, Y represents a polymerizable group. L represents a single bond or a divalent linking group. Z represents a (p+1)-valent cyclic structural moiety containing one or more selected from an aromatic ring and an aliphatic heterocycle. R represents an acid-decomposable group. p represents an integer of 1 or more.

Examples of the polymerizable group represented by Y include the polymerizable groups described above. A maleimide group or a (meth)acryl group is preferable, a maleimide group or a methacryl group is more preferable, and a methacryl group is even more preferable, from the viewpoint that the effects of the present invention are more excellent.
Examples of the divalent linking group represented by L include -CO-, -NR ^d -, -O-, -S-, -SO-, -SO ₂ -, an alkylene group, a cycloalkylene group, and an alkenylene group. , a divalent aliphatic heterocyclic group, a divalent aromatic heterocyclic group, a divalent aromatic hydrocarbon ring group, and a divalent linking group combining a plurality of these groups. The alkylene group, cycloalkylene group, alkenylene group, divalent aliphatic heterocyclic group, divalent aromatic heterocyclic group, and divalent aromatic hydrocarbon ring group described above further have a substituent. may be R ^d in —NR ^d — above represents a hydrogen atom or an organic group. The organic group is preferably an alkyl group (eg, 1 to 6 carbon atoms).

The alkylene group may be linear or branched. Also, the number of carbon atoms is preferably 1 to 6.
The cycloalkylene group preferably has 3 to 15 carbon atoms.
The alkenylene group preferably has 2 to 6 carbon atoms.
The divalent aliphatic heterocyclic group is preferably a ring having 5 to 10 ring member atoms and having a heteroatom selected from the group consisting of a nitrogen atom, an oxygen atom, and a sulfur atom as a ring member atom. . Examples of divalent aliphatic heterocyclic groups include groups represented by the following formulas. In the formula, each Rg independently represents a hydrogen atom or a substituent (preferably a hydroxyl group or the like as the substituent), and * represents a bonding position.

The divalent aromatic heterocyclic group is preferably a ring having 5 to 10 ring-member atoms having a heteroatom selected from the group consisting of a nitrogen atom, an oxygen atom, and a sulfur atom as a ring-member atom. .
Examples of the divalent aromatic hydrocarbon ring group include rings having 6 to 10 ring members.

Incidentally, if the divalent linking group represented by L contains a divalent aliphatic heterocyclic group, a divalent aromatic heterocyclic group, or a divalent aromatic hydrocarbon ring group, a divalent aliphatic A heterocyclic group, a divalent aromatic heterocyclic group, or a divalent aromatic hydrocarbon ring group is also preferably arranged at a position adjacent to Z specified in general formula (A1). In other words, the position adjacent to Z specified in general formula (A1) is a divalent aliphatic heterocyclic group, a divalent aromatic heterocyclic group, or a divalent aromatic hydrocarbon ring group. is also preferred.

The divalent linking group represented by L includes, among others, —CO—, —NR ^d —, —O—, —S—, —SO—, —SO ₂ —, an alkylene group, and a divalent aliphatic A heterocyclic group, a divalent aromatic hydrocarbon ring group, and a divalent linking group combining a plurality of these groups are preferred.
Examples of the above-mentioned "a divalent linking group combining a plurality of these" include -alkylene group -O-alkylene group -phenylene group- and the like.

Z represents a cyclic structural moiety containing one or more selected from aromatic rings and aliphatic heterocycles.
The aromatic ring and the aliphatic aromatic ring are as described above.
A cyclic structural site is a p+1-valent group composed of a ring that may have a substituent.
The above ring may be monocyclic or polycyclic, and includes aromatic rings, aliphatic heterocycles, and polycyclic rings formed by an aromatic ring and an aliphatic heterocycle.
Moreover, the cyclic structural part may have a substituent. The term "substituent" as used herein means any substituent other than the group represented by YL- and R in general formula (A1). Examples of substituents include, but are not limited to, hydroxyl groups, phenyl groups, cyano groups, halogen atoms, alkyl groups, cycloalkyl groups, alkoxy groups, and carboxy groups. In addition, these substituents may further have a substituent.

Specific examples of the ring constituting the cyclic structural moiety represented by Z include, in addition to the rings exemplified above as specific examples of the aromatic ring and the above aliphatic aromatic ring, the following rings. be done. In addition, the rings exemplified in the upper part as specific examples of the aromatic ring and the above aliphatic aromatic ring, and the rings shown below are represented by Z by removing p + 1 hydrogen atoms possessed by the ring member atoms. Forms a cyclic structure. That is, for example, in the case of formula (AT1-2) described later, at least p+1 of Rg, Rg ¹ , and Rg ¹ represents a hydrogen atom, and the cyclic structural moiety represented by Z is obtained by removing this hydrogen atom. to form In the case of formula (AT1-1), which will be described later, a hydrogen atom that can be bonded to the carbon atoms of two benzene rings specified in the formula (where n3 is not 4, the benzene ring has a hydrogen atom. ) and Rg ¹ and Rg ² representing hydrogen atoms (in other words, Rg ¹ and Rg ² representing hydrogen atoms) are removed from p + 1 hydrogen atoms to form a cyclic structure represented by Z form a part. In the case of formula (AT1-3) described later, a hydrogen atom that can be bonded to a carbon atom of one benzene ring specified in the formula (where n3 is not 4, the benzene ring has a hydrogen atom. ) and Rg, Rg ¹ , and Rg ² representing hydrogen atoms (in other words, Rg, Rg ¹ , and Rg ² representing hydrogen atoms) are removed from p+1 hydrogen atoms. forms a cyclic structural moiety represented by Z.
Specific examples of the ring constituting the cyclic structural moiety represented by Z are not limited to these.

Monocyclic or polycyclic 5- to 7-membered lactone rings; for example, those represented by the following formulas (LC1-1) to (LC1-21). Examples of the substituent (Rb ₂ ) include a hydroxyl group, a phenyl group, a cyano group, a halogen atom, an alkyl group, a cycloalkyl group, an alkoxy group, and a carboxy group. n2 represents, for example, an integer of 0 to 4 (preferably an integer of 0 to 2). When n2 is 2, multiple Rb ₂ may be different, and multiple Rb ₂ may combine to form a ring. In addition, one or more methylene groups (eg, 1 to 2) not adjacent to -COO- or -O- among the ring member atoms of the lactone ring below are replaced with a hetero atom such as -O- or -S- may

A monocyclic or polycyclic 5- to 7-membered sultone ring; for example, those represented by the following formulas (SL1-1) to (SL1-3). The substituents (Rb ₂ ) and n2 can be explained in the same manner as the substituents (Rb ₂ ) and n2 in the lactone structure.
Further, one or more methylene groups (eg, 1 to 2) not adjacent to -COO- or -O- among the ring member atoms of the sultone ring are replaced with heteroatoms such as -O- or -S- good too.

Other examples: Examples other than the lactone ring and sultone ring described above include the following formulas (AT1-1) to (AT1-3). Rf represents a substituent, and examples thereof include those similar to the substituent (Rb ₂ ) in the lactone structure. n3 represents, for example, an integer of 0 to 4 (preferably an integer of 0 to 2). When n3 is 2 or more, multiple Rf's may be different, and multiple Rf's may combine to form a ring.
Rg, Rg ¹ and Rg ² each independently represent a hydrogen atom or a substituent. Substituents represented by Rg, Rg ¹ and Rg ² include those similar to the substituent (Rb ₂ ) in the lactone structure.
In the following formulas (AT1-1) to (AT1-3), any one or more (preferably two or more) of Rg ¹ represents a hydrogen atom, and by removing the hydrogen atom, the general formula (A1 ) is preferably formed. It is also preferable that Rg ² represents a hydrogen atom, and removal of this hydrogen atom forms a bond with the group represented by YL- in general formula (A1). The ring represented by the following general formula (AT1-1) has 9,10-dihydroanthracene as its basic skeleton.

R represents an acid-decomposable group. Examples of the acid-decomposable group represented by R include the above-described acid-decomposable groups, and the preferred embodiments are also the same.

　p represents an integer of 1 or more. As p, 2 to 6 are preferable, 2 to 4 are more preferable, and 2 is even more preferable in that the effects of the present invention are more excellent.

Specific examples of the specific monomer A (group A and group B) are shown below, but are not limited thereto. All of the compounds belonging to (Group A) of the specific monomer A shown below correspond to compounds having 9,10-dihydroanthracene as a basic skeleton.
(Group A)

(Group B)

<<Repeating unit of specific acid-decomposable resin A>>
<Repeating unit derived from specific monomer A (acid-decomposable repeating unit)>
The specific acid-decomposable resin A contains repeating units derived from the specific monomer A as acid-decomposable repeating units.
The repeating units derived from the specific monomer A may be used alone or in combination of two or more.
The lower limit of the content of repeating units derived from the specific monomer A is preferably 10% by mass or more, more preferably 20% by mass or more, and 30% by mass or more, based on the total repeating units of the specific acid-decomposable resin A. is more preferable, and 40% by mass or more is particularly preferable. Moreover, as an upper limit, 100 mass % or less is preferable, 90 mass % or less is more preferable, and 85 mass % or less is still more preferable.

<Other acid-decomposable repeating units>
The specific acid-decomposable resin A may contain acid-decomposable repeating units other than the repeating units derived from the specific monomer A as acid-decomposable repeating units. Other acid-decomposable repeating units include repeating units derived from the above-mentioned acid-decomposable group-containing (meth)acrylic compounds.

<Repeating unit having an acid group>
The specific acid-decomposable resin A may have a repeating unit having an acid group.
The repeating unit having an acid group is preferably a repeating unit different from the repeating units described above.
As the acid group, an acid group having a pKa of 13 or less is preferable. As described above, the acid dissociation constant of the acid group is preferably 13 or less, more preferably 3-13, and even more preferably 5-10.
When the specific acid-decomposable resin A has an acid group with a pKa of 13 or less, the content of the acid group in the specific acid-decomposable resin A is not particularly limited, but may be 0.2 to 6.0 mmol/g. many. Among them, 0.8 to 6.0 mmol/g is preferable, 1.2 to 5.0 mmol/g is more preferable, and 1.6 to 4.0 mmol/g is even more preferable. If the content of the acid group is within the above range, the development proceeds satisfactorily, the formed pattern shape is excellent, and the resolution is also excellent.
The acid group is preferably, for example, a carboxyl group, a hydroxyl group, an aromatic hydroxyl group (phenolic hydroxyl group), a fluorinated alcohol group (preferably a hexafluoroisopropanol group), a sulfonic acid group, a sulfonamide group, or an isopropanol group. .
In the hexafluoroisopropanol group, one or more (preferably 1 to 2) fluorine atoms may be substituted with a group other than a fluorine atom (such as an alkoxycarbonyl group). —C(CF ₃ )(OH)—CF ₂ — thus formed is also preferred as an acid group. Also, one or more of the fluorine atoms may be substituted with a group other than a fluorine atom to form a ring containing -C(CF ₃ )(OH)-CF ₂ -.
A repeating unit having an acid group may have a fluorine atom or an iodine atom.

The repeating unit having an acid group is preferably a repeating unit represented by general formula (B).

R ₃ represents a hydrogen atom or an organic group optionally having a fluorine atom or an iodine atom.
The organic group optionally having a fluorine atom or an iodine atom is preferably a group represented by -L ₄ -R ₈ . _L4 represents a single bond or an ester group. R ₈ is an alkyl group optionally having a fluorine atom or an iodine atom, a cycloalkyl group optionally having a fluorine atom or an iodine atom, an aryl group optionally having a fluorine atom or an iodine atom, Alternatively, a group obtained by combining these may be mentioned.

_R4 and _R5 each independently represent a hydrogen atom, a fluorine atom, an iodine atom, or an alkyl group optionally having a fluorine atom or an iodine atom.

L ₂ is a single bond, an ester group, or —CO—, —O—, or an alkylene group (preferably having 1 to 6 carbon atoms. It may be linear or branched. In addition, —CH ₂ — is optionally substituted with a halogen atom) represents a divalent group formed by combining.
L ₃ represents an (n+m+1)-valent aromatic hydrocarbon ring group or an (n+m+1)-valent alicyclic hydrocarbon ring group. Aromatic hydrocarbon ring groups include a benzene ring group and a naphthalene ring group. The alicyclic hydrocarbon ring group may be monocyclic or polycyclic, and examples thereof include cycloalkyl ring groups, norbornene ring groups, and adamantane ring groups.

_R6 represents a hydroxyl group or a fluorinated alcohol group. The fluorinated alcohol group is preferably a group represented by the following formula (3L).
*-L _6X -R _6X (3L)
_L6X represents a single bond or a divalent linking group. Although the divalent linking group is not particularly limited, examples thereof include -CO-, -O-, -SO-, -SO ₂ -, -NR ^A -, an alkylene group (preferably having 1 to 6 carbon atoms, linear or a branched chain), and a divalent linking group combining a plurality of these. ^RA includes a hydrogen atom or an alkyl group having 1 to 6 carbon atoms. Moreover, the said alkylene group may have a substituent. Examples of substituents include halogen atoms (preferably fluorine atoms) and hydroxyl groups. _R6X represents a hexafluoroisopropanol group.
When R ₆ is a hydroxyl group, L ₃ is also preferably an (n+m+1)-valent aromatic hydrocarbon ring group.

_R7 represents a halogen atom.
m represents an integer of 1 or more. m is preferably an integer of 1-3, more preferably an integer of 1-2.
n represents an integer of 0 or 1 or more. n is preferably an integer of 1-4.
(n+m+1) is preferably an integer of 1-5.

The repeating unit having an acid group is also preferably a repeating unit represented by general formula (A2).
The repeating unit represented by general formula (A2) is a repeating unit having an aromatic hydroxyl group as an acid group.

In general formula (A2), R ₁₀₁ , R ₁₀₂ and R ₁₀₃ each independently represent a hydrogen atom, an alkyl group (which may be linear or branched; for example, 1 to 6 carbon atoms), or a cycloalkyl group. (monocyclic or polycyclic; for example, 3 to 15 ring members), halogen atom, cyano group, or alkoxycarbonyl group (for example, 2 to 7 carbon atoms; the alkyl group portion may be linear or branched) represents

In general formula ( _A2 ), LA represents a single bond or a divalent linking group.
Examples of the divalent linking group represented by LA in the general formula ( _A2 ) include -CO-, -NR-, -CO-, -O-, -S-, -SO-, _-SO2 -, an alkylene group (preferably having 1 to 6 carbon atoms, which may be linear or branched), a cycloalkylene group (preferably having 3 to 15 carbon atoms), an alkenylene group (preferably having 2 to 6 carbon atoms), 2 a valent aliphatic heterocyclic group (preferably a ring having 5 to 10 ring-member atoms having at least one nitrogen atom, oxygen atom, sulfur atom or selenium atom as a ring-member atom), divalent aromatic heterocyclic group Ring group (preferably at least one nitrogen atom, oxygen atom, sulfur atom, or a ring having 5 to 10 ring-member atoms having a selenium atom as a ring-member atom), a divalent aromatic hydrocarbon ring group (preferably rings having 6 to 10 ring member atoms), and divalent linking groups combining a plurality of these. R in -NR- above represents a hydrogen atom or an organic group. The organic group is preferably an alkyl group (eg, 1 to 6 carbon atoms).

Ar _A represents an aromatic ring group (such as a benzene ring group).
The aromatic ring group may be monocyclic or polycyclic, and may or may not have one or more (eg, 1 to 3) heteroatoms as ring member atoms. The number of ring member atoms of the aromatic ring group is preferably 5-15.

In general formula (A2), k represents an integer of 1-5.

However, R ₁₀₂ may be bonded to Ar 2 _A , in which case R ₁₀₂ represents a single bond or an alkylene group (either linear or branched, having 1 to 6 carbon atoms, for example).
In this case, the aromatic ring group represented by Ar 1 _A is bonded to the carbon atom constituting the main chain (the carbon atom to which R ₁₀₁ is bonded) via the above single bond or the above alkylene group.

Examples of repeating units having an acid group are shown below.

In the following examples, a represents 1 or 2.

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

The repeating units having an acid group may be used alone or in combination of two or more.
The content of repeating units having an acid group is preferably 5 to 80% by mass, more preferably 5 to 60% by mass, and still more preferably 10 to 50% by mass, based on the total repeating units of the specific acid-decomposable resin A. , 15 to 50% by weight are particularly preferred.

<Repeating Unit Having Lactone Group>
The specific acid-decomposable resin A also preferably has a repeating unit having a lactone group.
The repeating unit having a lactone group is preferably a repeating unit different from the repeating units described above.
Moreover, the repeating unit having a lactone group may also serve as the above-described repeating unit (for example, the repeating unit having an acid-decomposable group).

The lactone group may have a lactone structure. The lactone structure is preferably a 5- to 7-membered ring lactone structure. Among them, those in which a 5- to 7-membered lactone structure is condensed with another ring structure to form a bicyclo structure or a spiro structure are more preferable.
The specific acid-decomposable resin A has a lactone group obtained by extracting one or more (for example, one or two) hydrogen atoms from a lactone structure represented by any of the following formulas (LC1-1) to (LC1-21). It is preferable to have a repeating unit having
Alternatively, the lactone group may be directly attached to the main chain. For example, the ring member atoms of the lactone group may constitute the main chain of the specific acid-decomposable resin A.

The lactone structure may have a substituent (Rb ₂ ). Examples of the substituent (Rb ₂ ) include an alkyl group having 1 to 8 carbon atoms, a cycloalkyl group having 4 to 7 carbon atoms, an alkoxy group having 1 to 8 carbon atoms, an alkoxycarbonyl group having 1 to 8 carbon atoms, and carboxyl. group, a halogen atom, a hydroxyl group, a cyano group, a group containing an acid-decomposable group (which may be the acid-decomposable group itself), and a group consisting of a combination thereof. 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.
Among the ring member atoms of the lactone structure, one or more (eg, 1 to 2) methylene groups not adjacent to -COO- or -O- may be replaced with heteroatoms such as -O- or -S- good.

Examples of repeating units having a lactone group include repeating units represented by the following general formula (AI).

In general formula (AI), Rb ₀ represents a hydrogen atom, a halogen atom, or an alkyl group having 1 to 4 carbon atoms.
Preferred substituents that the alkyl group of Rb ₀ may have include a hydroxyl group and a halogen atom.
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 obtained by removing one hydrogen atom from a ring member atom of the lactone structure represented by any one of formulas (LC1-1) to (LC1-21).

A repeating unit having a lactone group may be, for example, a repeating unit represented by general formula (AII) or (AIII).

In general formulas (AII) and (AIII), each RIII independently represents a hydrogen atom or a substituent.
RIII is preferably a hydrogen atom.
In general formula (AII), ahd ₁ is a group obtained by extracting hydrogen atoms one by one from adjacent ring member atoms of the lactone structure represented by any one of formulas (LC1-1) to (LC1-21). represents
In general formula (AIII), ahd ₂ is a group obtained by removing two hydrogen atoms from one of the ring member atoms of the lactone structure represented by any one of formulas (LC1-1) to (LC1-21). show.

Examples of repeating units having a lactone group are shown below.

When an optical isomer exists in the repeating unit having a lactone group, any optical isomer 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.

A repeating unit having a lactone group may be used singly or in combination of two or more.
The content of repeating units having a lactone group is preferably 1 to 50% by mass, more preferably 3 to 40% by mass, and further preferably 5 to 30% by mass, based on the total repeating units in the specific acid-decomposable resin A. Preferably, 5 to 20% by weight is particularly preferred.

In addition, the specific acid-decomposable resin A may contain other repeating units. Other repeating units include, for example, repeating units listed in paragraphs [0074] to [0079], [0090] to [0100], and [0103] to [0133] of WO2018/193954, Repeating units listed in paragraphs [0152] to [00173] of WO2020/004306, sultone groups or carbonate groups listed in paragraphs [0042] to [0059] of WO2019/167481 and a repeating unit having

In addition to the above repeating structural units, the specific acid-decomposable resin A has various repeating structures for the purpose of adjusting dry etching resistance, standard developer suitability, substrate adhesion, resist profile, resolution, heat resistance, sensitivity, etc. May have units.

The specific acid-decomposable resin A can be synthesized according to a conventional method (for example, radical polymerization).
The weight-average molecular weight of the specific acid-decomposable resin A is preferably from 1,000 to 200,000, more preferably from 3,000 to 20,000, and further from 5,000 to 15,000 as a polystyrene equivalent value by the GPC method. preferable. By setting the weight-average molecular weight of the specific acid-decomposable resin A within the above range, deterioration of heat resistance and dry etching resistance can be further suppressed. In addition, it is possible to further suppress the deterioration of the developability and the deterioration of the film formability due to an increase in viscosity.
The dispersion degree (molecular weight distribution) of the specific acid-decomposable resin A is usually 1.0 to 5.0, preferably 1.0 to 3.0, more preferably 1.2 to 3.0, and 1.2. ~2.0 is more preferred. The smaller the degree of dispersion, the better the resolution and resist shape, the smoother the side walls of the resist pattern, and the better the roughness.

The specific acid-decomposable resin A may be used singly or in combination of two or more.
In the resist composition of the first embodiment, the content of the specific acid-decomposable resin A is preferably 10 to 99.9% by mass, more preferably 60 to 99.5% by mass, based on the total solid content of the composition. Preferably, 70 to 99% by mass is more preferable, and 80 to 99% by mass is particularly preferable.
In addition, solid content intends the component which forms a resist film, and does not include a solvent. In addition, as long as it is a component that forms a resist film, it is regarded as a solid content even if its property is liquid.

[Photoacid generator]
The resist composition of the first embodiment contains a photoacid generator.
A photoacid generator is a compound that generates an acid upon exposure to actinic rays or radiation.

The photoacid generator is preferably a low-molecular-weight compound, and its molecular weight is preferably 3,000 or less, more preferably 2,000 or less, and even more preferably 1,000 or less. The lower limit of the molecular weight is, for example, 100 or more.
Although the photoacid generator is not particularly limited, a compound that generates an organic acid upon exposure to actinic rays or radiation (preferably electron beams or extreme ultraviolet rays) or heating is preferred.
As the organic acid, for example, at least one of sulfonic acid, bis(alkylsulfonyl)imide, and tris(alkylsulfonyl)methide is preferable.

The photoacid generator may be an ionic compound or a nonionic compound.

<Photoacid generator that is an ionic compound>
The photoacid generator that is an ionic compound may be an onium salt photoacid generator or an inner salt (betaine compound).

(Photoacid generator that is an onium salt)
Photoacid generators that are onium salts usually have a cation site and an anion site.
Photoacid generators that are onium salts include, for example, compounds represented by “M ^p+ _m X ^q− _n ”.
In “M ^p+ _m X ^q− _n ”, p, q, m and n each independently represent an integer of 1 or more (preferably 1 to 8).
M ^p+ represents an organic cation with charge p. The organic cation may contain a cation site as a part thereof, or may be the cation site itself. The organic cation is preferably the cation site itself.
X ^q- represents an organic anion with charge q. The organic anion may contain an anion site as a part thereof, or may be the anion site itself. The organic anion preferably contains an anion site as part.
M ^p+ and X ^q− may be the same or different when there are a plurality of them.
The value obtained by multiplying the average value of p in M ^p+ , which may exist in plural numbers, by m is the same value as the value obtained by multiplying the average value of q in X ^q− , which may exist in plural numbers, by n.
Among them, p is preferably 1.
For example, it is preferred that all of p, q, m and n are 1.
In addition, it is also preferable that p is 1, q is 2 to 8, m is the same as q, and n is 1.

-Organic cation The cation site is a structural site containing a positively charged atom or atomic group, and is preferably, for example, a monovalent organic cation.
The organic cations are each independently preferably an organic cation represented by the formula (ZaI) (cation (ZaI)) or an organic cation represented by the formula (ZaII) (cation (ZaII)).

In the above formula (ZaI),
R ²⁰¹ , R ²⁰² and R ²⁰³ each independently represent an organic group.
The number of carbon atoms in the organic group 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 group, an amide group, or a carbonyl group. Groups formed by combining two of R ²⁰¹ to R ²⁰³ include, for example, an alkylene group (eg, a butylene group and a pentylene group), and —CH ₂ —CH ₂ —O—CH ₂ —CH ₂ — are mentioned.

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

First, the cation (ZaI-1) will be described.
Cation (ZaI-1) is an arylsulfonium cation in which at least one of R ²⁰¹ to R ²⁰³ in formula (ZaI) above is an aryl group.
In the arylsulfonium cation, all of R ₂₀₁ to R ₂₀₃ may be aryl groups, or part of R ₂₀₁ to R ₂₀₃ may be aryl groups and the rest may be alkyl groups or cycloalkyl groups.
In addition, one of R ₂₀₁ to R ₂₀₃ may be an aryl group, and the remaining two of R ²⁰¹ to R ²⁰³ may combine to form a ring structure, in which an oxygen atom, a sulfur atom, It may contain an ester group, an amide group, or a carbonyl group.
Examples of groups formed by combining two of R ²⁰¹ to R ²⁰³ include alkylene group AL, -aromatic ring group-alkylene group AL-aromatic ring group-, -aromatic ring group-aromatic ring group-, and , -aromatic ring group -O-aromatic ring group-. The alkylene group AL is an alkylene group which may be linear or branched. Also, one or more methylene groups constituting the alkylene group AL may be substituted with an oxygen atom, a sulfur atom, an ester group, an amide group and/or a carbonyl group. The alkylene group AL includes, for example, a butylene group, a pentylene group, and —CH ₂ —CH ₂ —O—CH ₂ —CH ₂ —).
Arylsulfonium cations include, for example, triarylsulfonium cations, diarylalkylsulfonium cations, aryldialkylsulfonium cations, diarylcycloalkylsulfonium cations, and aryldicycloalkylsulfonium cations.
Two of the aryl groups in the triarylsulfonium cation, the diarylalkylsulfonium cation, and the diarylcycloalkylsulfonium cation are a single bond or a divalent linking group (—O—, —S—, an alkylene group, or group consisting of a combination of these, etc.).

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

The substituents that the aryl group, alkyl group and cycloalkyl group of R ²⁰¹ to R ²⁰³ may have are each independently an alkyl group (eg, having 1 to 15 carbon atoms) or a cycloalkyl group (eg, having 1 to 15 carbon atoms). 3 to 15), aryl groups (eg, 6 to 14 carbon atoms), alkoxy groups (eg, 1 to 15 carbon atoms), cycloalkylalkoxy groups (eg, 1 to 15 carbon atoms), cycloalkylsulfonyl groups (eg, 1 to 15 carbon atoms). 15), halogen atoms (eg, fluorine, iodine), hydroxyl groups, carboxyl groups, ester group-containing groups, sulfinyl group-containing groups, sulfonyl group-containing groups, alkylthio groups, phenylthio groups, and the like are preferred.
The above substituents may further have a substituent if possible. For example, the above alkyl group may have a halogen atom as a substituent to form a halogenated alkyl group such as a trifluoromethyl group. preferable.
Moreover, it is also preferable that the above substituents form an acid-decomposable group by any combination.
The acid-decomposable group is intended to be a group that is decomposed by the action of an acid to generate a polar group, and preferably has a structure in which the polar group is protected by a leaving group that is eliminated by the action of an acid. The polar group and leaving group are as described above.

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

In formula (ZaI-3b),
R _1c to R _5c each independently represent a hydrogen atom, an alkyl group, a cycloalkyl group, an aryl group, an alkoxy group, an aryloxy group, an alkoxycarbonyl group, an alkylcarbonyloxy group, a cycloalkylcarbonyloxy group, a halogen atom, or a hydroxyl group , represents a nitro group, an alkylthio group, or an arylthio group.
R _6c and R _7c each independently represent a hydrogen atom, an alkyl group (such as a t-butyl group), a cycloalkyl group, a halogen atom, a cyano group, or an aryl group.
R _x and R _y each independently represent an alkyl group, a cycloalkyl group, a 2-oxoalkyl group, a 2-oxocycloalkyl group, an alkoxycarbonylalkyl group, an allyl group, or a vinyl group.
It is also preferable that the substituents of R _1c to R _7c , R _x and R _y independently form an acid-decomposable group by any combination of substituents.

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

Examples of groups formed by bonding two or more of R _1c to R _5c , R _6c and R _7c , and R _x and R _y include alkylene groups such as a butylene group and a pentylene group. A methylene group in this alkylene group may be substituted with a heteroatom such as an oxygen atom.
The group formed by combining R _5c and R _6c and R _5c and R _x is preferably a single bond or an alkylene group. The alkylene group includes a methylene group, an ethylene group, and the like.

R _1c to R _5c , R _6c , R _7c , R _x , R _y , and two or more of R _1c to R _5c , R _5c and R _6c , R _6c and R _7c , R _5c and R _x , and the ring formed by combining R _x and R _y with each other may have a substituent.

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

In formula (ZaI-4b),
l represents an integer of 0 to 2;
r represents an integer of 0 to 8;
R ₁₃ is a hydrogen atom, a halogen atom (e.g., fluorine atom, iodine atom, etc.), a hydroxyl group, an alkyl group, a halogenated alkyl group, an alkoxy group, a carboxyl group, an alkoxycarbonyl group, or a group having a cycloalkyl group (cyclo It may be an alkyl group itself, or a group partially containing a cycloalkyl group). These groups may have a substituent.
R ₁₄ is a hydroxyl group, a halogen atom (e.g., fluorine atom, iodine atom, etc.), an alkyl group, a halogenated alkyl group, an alkoxy group, an alkoxycarbonyl group, an alkylcarbonyl group, an alkylsulfonyl group, a cycloalkylsulfonyl group, or a cyclo It represents a group having an alkyl group (either a cycloalkyl group itself or a group partially containing a cycloalkyl group). These groups may have a substituent. R ₁₄ each independently represent the above groups such as a hydroxyl group when there are more than one.
Each _R15 independently represents an alkyl group, a cycloalkyl group, or a naphthyl group. Two R ₁₅ may be joined together to form a ring. When two R ₁₅ are combined to form a ring, the ring skeleton may contain a heteroatom such as an oxygen atom or a nitrogen atom.
In one aspect, two R ₁₅ are alkylene groups, preferably joined together to form a ring structure. The ring formed by combining the alkyl group, the cycloalkyl group, the naphthyl group, and the two R ₁₅ groups may have a substituent.

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

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

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

Organic anions Examples of organic anions include phenolic hydroxyl anions, sulfonate anions (aliphatic sulfonate anions, aromatic sulfonate anions, camphorsulfonate anions, etc.), carboxylate anions (aliphatic carboxylate anions, aromatic carboxylate anion, aralkyl carboxylate anion, formate anion, hydrogen carbonate anion, etc.), carbonylsulfonylimidate anion, bis(sulfonyl)imide anion (bis(alkylsulfonyl)imide anion, etc.), bis(carbonyl)imide anions and tris(alkylsulfonyl)methide anions.

The aliphatic moiety in the aliphatic sulfonate anion and the aliphatic carboxylate anion may be an alkyl group or a cycloalkyl group, a linear or branched alkyl group having 1 to 30 carbon atoms, or , is preferably a cycloalkyl group having 3 to 30 carbon atoms.
The alkyl group may be, for example, a fluoroalkyl group (which may or may not have a substituent other than a fluorine atom, and may be a perfluoroalkyl group).
The above cycloalkyl group may be monocyclic or polycyclic, and one or more (preferably 1 to 2) —CH ₂ — constituting the ring structure is a hetero atom (—O— or —S—, etc.), — It may be substituted with SO ₂ —, —SO ₃ —, an ester group, or a carbonyl group.

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

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

The aralkyl group in the aralkylcarboxylate anion is preferably an aralkyl group having 7 to 14 carbon atoms, such as a benzyl group, a phenethyl group, a naphthylmethyl group, a naphthylethyl group, and a naphthylbutyl group.

　Sulfonylimide anions include, for example, saccharin anions.

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

Examples of organic anions include aliphatic sulfonate anions in which at least the α-position of a sulfonic acid is substituted with a fluorine atom (aliphatic sulfonate anions in which one or two fluorine atoms are substituted in the α-position, etc.), Aliphatic sulfonate anions not substituted with fluorine atoms (aliphatic sulfonate anions not substituted with fluorine atoms at the α-position and substituted with 0 to 3 fluorine atoms or perfluoroalkyl groups at the β-position, etc.) , an aromatic sulfonate anion substituted with a fluorine atom or a group having a fluorine atom, a bis(alkylsulfonyl)imide anion having an alkyl group substituted with a fluorine atom, or a tris(alkyl Sulfonyl)methide anions are also preferred.

In addition, as the organic anion, an anion represented by the following formula (AN) is also preferable.

In formula (AN), o represents an integer of 0 to 5. p represents an integer from 0 to 10; q represents an integer from 0 to 10;

In formula (AN), AX represents -SO ₃ ^- or -COO ^- .

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

_In formula (AN), _R4 and R5 each independently represent a hydrogen atom, a fluorine atom, an alkyl group, or an alkyl group substituted with at least one fluorine atom. When multiple R ₄ and R ₅ are present, each of R ₄ and R ₅ may be the same or different.
The alkyl groups represented by R ₄ and R ₅ may have substituents other than fluorine atoms, and preferably have 1 to 4 carbon atoms.
Specific examples and preferred aspects of the alkyl group substituted with at least one fluorine atom are the same as those of Xf.
R ₄ and R ₅ are preferably hydrogen atoms.
It is also preferred that one of R ₄ and R ₅ bonded to the same carbon atom is a hydrogen atom and the other is a fluorine atom or an alkyl group substituted with at least one fluorine atom. Among them, the —C(R ₄ )(R ₅ )— at the first and/or second closest position to AX are bonded to the same carbon atom, and one of R ₄ and R ₅ is a hydrogen atom, is also preferably a fluorine atom or an alkyl group substituted with at least one fluorine atom. Moreover, in —C(R ₄ )(R ₅ )— at the first and/or second closest position to AX, R ₄ and R ₅ are each independently a hydrogen atom or an alkyl group (a substitution other than a fluorine atom). may have a group) is also preferred.

In formula (AN), L represents a divalent linking group. When there are multiple L's, each L may be the same or different.
Examples of divalent linking groups include -O-CO-O-, -COO-, -OCO-, -CONH-, -NHCO-, -CO-, -O-, -S-, -SO-, —SO ₂ —, an alkylene group (preferably having 1 to 6 carbon atoms), a cycloalkylene group (preferably having 3 to 15 carbon atoms), an alkenylene group (preferably having 2 to 6 carbon atoms), and combinations of these A divalent linking group and the like are included. Among them, -O-CO-O-, -COO-, -OCO-, -CONH-, -NHCO-, -CO-, -O-, -SO ₂ -, -O-CO-O-alkylene group- , -alkylene group -O-CO-O-, -COO-alkylene group -, -OCO-alkylene group -, -CONH-alkylene group -, or -NHCO-alkylene group - is preferred, -O-CO-O -, -O-CO-O-alkylene group-, -alkylene group -O-CO-O-, -COO-, -OCO-, -CONH-, -SO ₂ -, -COO-alkylene group-, or, -OCO-alkylene group- is more preferred.

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

Aryl groups may be monocyclic or polycyclic. This aryl group includes, for example, a phenyl group, a naphthyl group, a phenanthryl group, and an anthryl group.
A heterocyclic group may be monocyclic or polycyclic. Moreover, the heterocyclic group may or may not have aromaticity. Heterocyclic rings having aromaticity include, for example, furan ring, thiophene ring, benzofuran ring, benzothiophene ring, dibenzofuran ring, dibenzothiophene ring, and pyridine ring. Non-aromatic heterocycles include, for example, a tetrahydropyran ring, a lactone ring, a sultone ring, and a decahydroisoquinoline ring. As the heterocyclic ring in the heterocyclic group, a furan ring, thiophene ring, pyridine ring, or decahydroisoquinoline ring is particularly preferred.

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

Examples of anions represented by the formula (AN) include AX-CF ₂ -CH ₂ -OCO-(L)q'-W, AX-CF ₂ -CHF-CH ₂ -OCO-(L)q'-W, AX-CF2 _- COO-(L)q'-W, AX-CF2 _- CF2 _- _CH2 _- CH2-(L)qW, or AX-CF2 _- CH( _CF3 )-OCO -(L)q'-W is preferred. Here, AX, L, q and W are the same as in Formula (AN). q' represents an integer from 0 to 10;

(Photoacid generator that is an inner salt)
The photoacid generator, which is an inner salt, preferably has a sulfonate anion or a carboxylate anion (preferably an aromatic sulfonate or an aromatic carboxylate anion), and further has a sulfonium cation or an iodine cation. It is also preferable to have
Examples of photoacid generators that are inner salts include compound (ZbI) and compound (ZbII).
The above compound (ZbI) is characterized in that one of R ²⁰¹ to R ²⁰³ in the above general formula (ZaI) is an aryl group having a group containing —SO ₃ ^— ^or —COO— as a substituent. It is a compound represented by a newly defined general formula.
The above compound (ZbII) is characterized in that, in the above general formula (ZaII), one of R ²⁰⁴ and R ²⁰⁵ is an aryl group having a group containing -SO ₃ ^- ^or -COO- as a substituent. It is a compound represented by a newly defined general formula.
The group containing —SO ₃ ^— or —COO ^— in the compound (ZbI) and the compound (ZbII) is, for example, an organic anion represented by the formula (AN) shown in the explanation of the organic anion. A group to be excluded (a group represented by "AX-[C(Xf)(Xf)] _o- [C( _R4 ) ₍ R5)] _p- (L) _q- ") can be mentioned.

A photoacid generator that is an inner salt is exemplified.
In the following photoacid generators, the numerical value shown near the site where the hydrogen atom of the acid group is substituted with a cation (anionic functional group) is the acid formed assuming that the hydrogen atom is not substituted with a cation. The pKa of the groups are shown.
In other words, the pKa shown below is the acid group (anionic functional group group).

As the photoacid generator, paragraphs [0368] to [0377] of JP-A-2014-41328 and paragraphs [0240]-[0262] of JP-A-2013-228681 (corresponding US Patent Application Publication No. [0339] of 2015/004533) can be cited, the contents of which are incorporated herein.

In addition, the following compounds can also be used as photoacid generators.

The photoacid generator may be used singly or in combination of two or more.
The content of the photoacid generator in the resist composition of the first embodiment is preferably 0.5 to 40% by mass, more preferably 0.5 to 30% by mass, based on the total solid content of the resist composition. , 1 to 30 mass % is more preferable.

[Hydrophobic resin]
The resist composition of the first embodiment may contain a hydrophobic resin different from the specific acid-decomposable resin A in addition to the specific acid-decomposable resin A.
The hydrophobic resin is preferably designed to be unevenly distributed on the surface of the resist film. may not contribute to
Effects of the addition of the hydrophobic resin include control of the static and dynamic contact angles of the resist film surface with respect to water, suppression of outgassing, and the like.

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

When the resist composition of the first embodiment contains a hydrophobic resin, the content of the hydrophobic resin is preferably 0.01 to 20% by mass, more preferably 0.1 to 15% by mass, based on the total solid content of the resist composition. % by mass is more preferred, 0.1 to 10% by mass is even more preferred, and 0.1 to 5.0% by mass is particularly preferred.

[Surfactant]
The resist composition of the first embodiment may contain a surfactant. When a surfactant is contained, the adhesion is better and a pattern with fewer development defects can be formed.
The surfactant is preferably a fluorine-based and/or silicon-based surfactant.
As fluorine-based and/or silicon-based surfactants, for example, surfactants disclosed in paragraphs [0218] and [0219] of WO2018/19395 can be used.
When the resist composition of the first embodiment contains a surfactant, its content is preferably 0.0001 to 2% by mass, more preferably 0.0005 to 1% by mass, based on the total solid content of the composition. preferable.
One type of surfactant may be used alone, or two or more types may be used. When two or more are used, the total content is preferably within the range of the preferred content.

〔solvent〕
The resist composition of the first embodiment may contain a solvent.
Solvents include (M1) propylene glycol monoalkyl ether carboxylate and (M2) propylene glycol monoalkyl ether, lactate, acetate, alkoxypropionate, linear ketone, cyclic ketone, lactone, and alkylene carbonate. It is preferable to include at least one selected from the group consisting of: This solvent may further contain components other than components (M1) and (M2).

The present inventors have found that the use of such a solvent in combination with the resin described above improves the coatability of the composition and enables the formation of a pattern with fewer development defects. Although the reason for this is not necessarily clear, these solvents have a good balance of the solubility, boiling point, and viscosity of the resins described above, so that unevenness in the film thickness of the composition film and generation of precipitates during spin coating can be suppressed. The inventors believe that this is due to
Details of component (M1) and component (M2) are described in paragraphs [0218] to [0226] of WO2020/004306.

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

A solvent may be used individually by 1 type, and may use 2 or more types.
The content of the solvent in the resist composition of the first embodiment is preferably determined so that the solid content concentration is 30% by mass or less, more preferably 10% by mass or less, and 2% by mass or less. It is more preferable to define as follows. The lower limit is preferably 0.05% by mass or more, more preferably 0.1% by mass or more, and more preferably 0.5% by mass or more. More preferred.
By doing so, the coatability of the resist composition can be further improved.
In other words, the solvent content in the resist composition of the first embodiment is preferably 70 to 99.95% by mass, more preferably 90 to 99.9% by mass, relative to the total mass of the resist composition. 98 to 99.5% by mass is more preferable.

[Other additives]
The resist composition of the first embodiment includes an acid diffusion control agent, a dissolution inhibiting compound, a dye, a plasticizer, a photosensitizer, a light absorber, and/or a compound that promotes solubility in a developer (carboxylic acid group alicyclic or aliphatic compounds containing) may further be included.

The resist composition of the first embodiment may further contain a dissolution inhibiting compound. The term "dissolution inhibiting compound" as used herein means a compound having a molecular weight of 3000 or less, which is decomposed by the action of an acid to reduce its solubility in an organic developer.

The resist composition of the first embodiment is also suitably used as a photosensitive composition for EUV exposure or a photosensitive composition for electron beam exposure.

EUV light and electron beams are greatly affected by "photon shot noise" in which the number of photons stochastically varies, and are likely to cause deterioration of LER and bridge defects. To reduce the photon shot noise, there is a method of increasing the number of incident photons by increasing the amount of exposure, but this tends to be a trade-off with the demand for higher sensitivity.
When the A value obtained by the following formula (1) is high, the EUV and electron beam absorption efficiency of the resist film formed from the resist composition is high, which is effective in reducing photon shot noise. The A value represents the EUV and electron beam absorption efficiency of the mass ratio of the resist film.
Formula (1): A = ([H] x 0.04 + [C] x 1.0 + [N] x 2.1 + [O] x 3.6 + [F] x 5.6 + [S] x 1.5 + [I] × 39.5) / ([H] × 1 + [C] × 12 + [N] × 14 + [O] × 16 + [F] × 19 + [S] × 32 + [I] × 127)
The A value is preferably 0.120 or more. Although the upper limit is not particularly limited, if the A value is too large, the EUV and electron beam transmittance of the resist film will decrease, the optical image profile in the resist film will deteriorate, and as a result, it will be difficult to obtain a good pattern shape. , is preferably 0.240 or less, more preferably 0.220 or less.

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

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

[Resist film, pattern forming method]
Although the procedure of the pattern forming method using the resist composition of the first embodiment is not particularly limited, it preferably includes the following steps.
Step 1: Step of forming a resist film on a substrate using the resist composition of the first embodiment Step 2: Step of exposing the resist film Step 3: Step of developing the exposed resist film using a developer The procedure of each of the above steps will be described in detail below.

<Step 1: Resist film forming step>
Step 1 is a step of forming a resist film on a substrate using the resist composition of the first embodiment.
The definition of the resist composition of the first embodiment is as described above.

A method of forming a resist film on a substrate using the resist composition of the first embodiment includes, for example, a method of applying the resist composition of the first embodiment onto the substrate.
In addition, it is preferable to filter the resist composition of the first embodiment before application, if necessary. The pore size of the filter is preferably 0.1 µm or less, more preferably 0.05 µm or less, and even more preferably 0.03 µm or less. Moreover, the filter is preferably made of polytetrafluoroethylene, polyethylene, or nylon.

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

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

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

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

<Step 2: Exposure step>
Step 2 is a step of exposing the resist film.
Examples of the exposure method include a method of irradiating the formed resist film with actinic rays or radiation through a predetermined mask.
Actinic rays or radiation include infrared light, visible light, ultraviolet light, far ultraviolet light, extreme ultraviolet light, X-rays, and electron beams, preferably 250 nm or less, more preferably 220 nm or less, particularly preferably Far ultraviolet light with a wavelength of 1 to 200 nm, specifically, KrF excimer laser (248 nm), ArF excimer laser (193 nm), F2 excimer laser ₍ 157 nm), EUV (13 nm), X-rays, and electron beams mentioned.
Among them, the actinic ray or radiation used for exposure is preferably EUV or electron beam.

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

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

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

It is preferable to use an alkaline aqueous solution containing alkali as the alkaline developer. Although the type of alkaline aqueous solution is not particularly limited, for example, quaternary ammonium salts represented by tetramethylammonium hydroxide, inorganic alkalis, primary amines, secondary amines, tertiary amines, alcohol amines, or cyclic amines. and an alkaline aqueous solution containing Among others, the alkaline developer is preferably an aqueous solution of a quaternary ammonium salt represented by tetramethylammonium hydroxide (TMAH). Suitable amounts of alcohols, surfactants and the like may be added to the alkaline developer. The alkali concentration of the alkali developer is usually 0.1 to 20 mass %. Further, the pH of the alkaline developer is usually 10.0 to 15.0. The content of water in the alkaline developer is preferably 51 to 99.95% by mass.

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

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

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

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

The rinse solution used in the rinse step after the development step using the organic developer is not particularly limited as long as it does not dissolve the pattern, and a solution containing a general organic solvent can be used. The rinse solution used is a rinse solution containing at least one organic solvent selected from the group consisting of hydrocarbon-based solvents, ketone-based solvents, ester-based solvents, alcohol-based solvents, amide-based solvents, and ether-based solvents. is preferred.

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

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

Various materials used in the resist composition of the first embodiment and the pattern forming method using the resist composition of the first embodiment (e.g., solvent, developer, rinse, antireflection film-forming composition, The composition for forming a top coat, etc.) preferably does not contain impurities such as metals. The content of impurities contained in these materials is preferably 1 mass ppm or less, more preferably 10 mass ppb or less, still more preferably 100 mass ppt or less, particularly preferably 10 mass ppt or less, and most preferably 1 mass ppt or less. Here, examples of metal impurities include Na, K, Ca, Fe, Cu, Mg, Al, Li, Cr, Ni, Sn, Ag, As, Au, Ba, Cd, Co, Pb, Ti, V, W, Zn, and the like.

　An example of a method for removing impurities such as metals from various materials is filtration using a filter. Details of filtration using a filter are described in paragraph [0321] of WO2020/004306.

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

In addition to filter filtration, impurities may be removed with an adsorbent, or filter filtration and adsorbent may be used in combination. As the adsorbent, known adsorbents can be used. For example, inorganic adsorbents such as silica gel and zeolite, and organic adsorbents such as activated carbon can be used. In order to reduce impurities such as metals contained in the various materials described above, it is necessary to prevent metal impurities from entering during the manufacturing process. Whether the metal impurities are sufficiently removed from the manufacturing equipment can be confirmed by measuring the content of the metal component contained in the cleaning liquid used for cleaning the manufacturing equipment. The content of the metal component contained in the cleaning liquid after use is preferably 100 mass ppt (parts per trillion) or less, more preferably 10 mass ppt or less, and even more preferably 1 mass ppt or less.

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

[Second Embodiment of 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 “resist composition of the second embodiment”) is a polymerizable compound represented by the general formula (1) described later (hereinafter “specific Also referred to as "monomer B"), a resin having a repeating unit derived from (hereinafter also referred to as "specific acid-decomposable resin B"), and a photoacid generator.

Although the action mechanism of the resist composition of the second embodiment is not clear, the inventors of the present invention presume as follows.
The specific acid-decomposable resin B contained in the resist composition of the second embodiment has repeating units derived from the specific monomer B. The specific monomer B has a high glass transition temperature due to having a predetermined polycyclic structure. Therefore, according to the resist composition of the second embodiment containing the specific acid-decomposable resin B, a pattern with high film strength can be formed. As a result, it is believed that the resist composition of the second embodiment has high resolution (in other words, the critical resolution (nm) is small). Further, since the specific monomer B has an acid-decomposable group at a predetermined position, the pattern formed by the resist composition of the second embodiment containing the specific acid-decomposable resin B exhibits excellent dissolution contrast. obtain. As a result, it is believed that the pattern formed by the resist composition of the second embodiment has excellent LWR performance. That is, it is presumed that due to the structure of the specific monomer B, the resist composition of the second embodiment has excellent high resolution and the formed pattern has excellent LWR performance.
Hereinafter, higher resolution of the resist composition and/or better LWR performance of the pattern formed by the resist composition may be referred to as "more excellent effect of the present invention".

The resist composition of the second embodiment will be described in detail below.
The resist composition of the second embodiment 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 resist composition of the second embodiment is typically a chemically amplified resist composition.
The resist composition of the second embodiment has the same structure as the resist composition of the first embodiment except that the specific acid-decomposable resin B is used instead of the specific acid-decomposable resin A. The preferred embodiments are also the same.
In addition, the resist film and pattern forming method using the resist composition of the second embodiment are the same as those of the first embodiment except that the resist composition of the second embodiment is used in place of the resist composition of the first embodiment. It has the same configuration as the resist film and pattern forming method using the resist composition of the embodiment, and the preferred aspects thereof are also the same.

[Specific acid-decomposable resin B]
The resist composition of the second embodiment contains a resin (specific acid-decomposable resin B) having repeating units derived from a polymerizable compound (specific monomer B) represented by the following general formula (1).
The specific acid-decomposable resin B is a resin that is decomposed by the action of an acid to increase its polarity.
That is, in the pattern forming method using the resist composition of the second embodiment, typically, when an alkaline developer is employed as the developer, a positive pattern is preferably formed, and the organic developer is used as the developer. When a developer is used, a negative pattern is preferably formed.
The specific monomer B will be described below. The specific acid-decomposable resin B has the same structure as the specific acid-decomposable resin A except that it contains repeating units derived from the specific monomer B instead of the repeating units derived from the specific monomer A. A preferred embodiment is also the same. Therefore, only the specific monomer B will be described in the following description.

The specific monomer B will be described below.
The specific monomer B is a polymerizable compound represented by the following general formula (1).

In the formula, L ¹ represents -CR ³ =CR ⁴ - or -CR ⁵ R ⁶ -CR ⁷ R ⁸ -.
X ¹ represents -O-, -CR ⁹ R ¹⁰ -, or =CR ¹¹ -.
X ² represents -O-, -CO-, -CR ¹² R ¹³ -, or =CR ¹⁴ -.
The solid-dotted bond between X ¹ and X ² represents a single bond or a double bond. However, when the bond between X ¹ and X ² represents a double bond, X ¹ represents =CR ¹¹ - and X ² represents =CR ¹⁴ -. Further, when the bond between X ¹ and X ² represents a single bond, X ¹ represents -O- or -CR ⁹ R ¹⁰ -, and X ² represents -O-, -CO- or -CR represents ¹² R ¹³ -.
R ¹ to R ¹⁴ each independently represent a hydrogen atom or a substituent. In addition, R ³ and R ⁴ may combine with each other to form a ring. In addition, one of R ⁵ and R ⁶ and one of R ⁷ and R ⁸ may combine with each other to form a ring. Further, when X ¹ represents =CR ¹¹ - and X ² represents =CR ¹⁴ -, R ¹¹ and R ¹⁴ may combine with each other to form a ring. When X ¹ represents -CR ⁹ R ¹⁰ - and X ² represents -CR ¹² R ¹³ -, any one of R ⁹ and R ¹⁰ and any one of R ¹² and R ¹³ are bonded to each other. may form a ring.
R ^X1 to R ^X4 each independently represent a hydrogen atom or a substituent. However, at least one of R ^X1 to R ^X4 represents an acid-decomposable group. Any one of R 1 ^X1 and R 1 ^X2 and either one of R 1 ^X3 and R 1 ^X4 may combine with each other to form a ring.
However, the polymerizable compound represented by the general formula (1) contains a monovalent substituent represented by the following general formula (2) in the molecule.

In the formula, L2 represents a single bond or a ^divalent linking group. Y represents a polymerizable group. * represents a binding position.

In formula (1), the substituents represented by R ¹ to R ¹⁴ are not particularly limited, and examples include halogen atoms, hydroxyl groups, nitro groups, cyano groups, alkyl groups, alkoxy groups, alkoxycarbonyl groups, and cycloalkyl groups. , an aromatic ring group, and a monovalent substituent represented by the general formula (2).

The alkyl group may be linear or branched, and preferably has 1 to 5 carbon atoms. Examples of the alkyl group include methyl group, ethyl group, n-propyl group, isopropyl group, n-butyl group, isobutyl group, and t-butyl group.
Examples of the alkyl group portion in the alkoxy group and the alkoxycarbonyl group include the same groups as the alkyl group.
The cycloalkyl group preferably has 3 to 15 ring member atoms. The cycloalkyl is a monocyclic cycloalkyl group such as a cyclopentyl group or a cyclohexyl group, or a polycyclic cycloalkyl group such as a norbornyl group, a tetracyclodecanyl group, a tetracyclododecanyl group, or an adamantyl group. is preferred. In the cycloalkyl group, for example, one or more (eg, 1 to 3) ring-constituting methylene groups are heteroatoms (—O— or —S—, etc.), —SO ₂ —, —SO ₃ — , an ester group, a carbonyl group, or a vinylidene group. Further, in these cycloalkyl groups, one or more (eg, 1 to 2) ethylene groups constituting the cycloalkane ring may be replaced with a vinylene group.
An aromatic ring (such as a benzene ring) may be fused to the cycloalkyl group.
The aromatic ring group may be monocyclic or polycyclic, and preferably has 5 to 15 ring member atoms. The aromatic ring group may have one or more (eg, 1 to 5) heteroatoms (eg, oxygen atom, sulfur atom, nitrogen atom, etc.) as ring member atoms. Examples of the aromatic ring group include benzene ring group, naphthalene ring group, anthracene ring group, thiazole ring group, and benzothiazole ring group.

The alkyl group, the alkoxy group, the alkoxycarbonyl group, and the alkenyl group may further have a substituent. Examples of substituents include halogen atoms (such as fluorine atoms), hydroxyl groups, nitro groups, cyano groups, cycloalkyl groups, and aromatic ring groups.
The cycloalkyl group and the aromatic ring group may further have a substituent. Substituents include, for example, halogen atoms, hydroxyl groups, nitro groups, cyano groups, alkyl groups, alkoxy groups, alkoxycarbonyl groups, alkenyl groups, aromatic ring groups (which may be monocyclic or polycyclic, for example, having 5 to 15), and cycloalkyl groups (which may be monocyclic or polycyclic and have, for example, 3 to 15 ring members).

The ring specified in formula (1) (the carbon atom to which R ¹ is bonded, the carbon atom to which R ² is bonded, L ¹ , X ¹ and X ² ) is a 6-membered ring.
Here, when L ¹ represents -CR ³ =CR ⁴ -, R ³ and R ⁴ may combine with each other to form a ring. Further, when X ¹ represents =CR ¹¹ - and X ² represents =CR ¹⁴ -, R ¹¹ and R ¹⁴ may combine with each other to form a ring. ^The ring formed here is preferably an alicyclic ring containing ^an unsaturated bond corresponding to the site of L1 and the bonding site between X1 and X2, or ^an aromatic ring.

The aromatic ring may be monocyclic or polycyclic, and preferably has 5 to 20 (preferably 6 to 10) member atoms. The aromatic ring group may have one or more (eg, 1 to 5) heteroatoms (oxygen, sulfur, nitrogen, etc.) as ring member atoms.
Examples of aromatic rings include benzene ring, naphthalene ring, tolylene ring, anthracene ring, thiophene ring, furan ring, pyrrole ring, benzothiophene ring, benzofuran ring, benzopyrrole ring, triazine ring, imidazole ring, benzimidazole ring, and triazole. A ring, a thiadiazole ring, a thiazole ring and the like can be mentioned, and a benzene ring is preferred.
Moreover, the aromatic ring may further have a substituent. Examples of substituents include those exemplified for the substituents represented by R ¹ to R ¹⁴ .

The alicyclic ring may be monocyclic or polycyclic, and preferably has 5 to 20 (preferably 6 to 10) member atoms. The alicyclic ring may have one or more (eg, 1 to 5) heteroatoms (oxygen, sulfur, nitrogen, etc.) as ring member atoms. The alicyclic ring contains unsaturated bonds at positions corresponding to the L ¹ site and the X ¹ and X ² bonding sites in the ring. In addition, the alicyclic ring may further contain an unsaturated bond. In addition, the alicyclic ring may have a carbon atom in the ring substituted with a carbonyl carbon.
Alicyclic rings include, for example, cyclopentene, cyclohexene, cycloheptene, and cyclooctadiene.
Moreover, the alicyclic ring may further have a substituent. Examples of substituents include those exemplified for the substituents represented by R ¹ to R ¹⁴ .

Further, when L ¹ represents -CR ⁵ R ⁶ -CR ⁷ R ⁸ -, any one of R ⁵ and R ⁶ and any one of R ⁷ and R ⁸ are bound to each other to form a ring good too. When X ¹ represents -CR ⁹ R ¹⁰ - and X ² represents -CR ¹² R ¹³ -, any one of R ⁹ and R ¹⁰ and any one of R ¹² and R ¹³ are bonded to each other. may form a ring. The ring formed here is preferably an alicyclic ring. The alicyclic ring may be monocyclic or polycyclic, and preferably has 5 to 20 (preferably 6 to 10) member atoms. The alicyclic ring may have one or more (eg, 1 to 5) heteroatoms (oxygen, sulfur, nitrogen, etc.) as ring member atoms. The alicyclic ring may contain an unsaturated bond at a position other than the L ¹ site and the bonding site between X ¹ and X ² in the ring. In addition, the alicyclic ring may have a carbon atom in the ring substituted with a carbonyl carbon.
Alicyclic rings include, for example, cyclopentane, cyclohexane, cycloheptane, and cyclooctane.
Moreover, the alicyclic ring may further have a substituent. Examples of substituents include those exemplified for the substituents represented by R ¹ to R ¹⁴ .

In general formula (1), the substituents represented by R ^X1 to R ^X4 include acid-decomposable groups and the substituents exemplified for the substituents represented by R ¹ to R ¹⁴ .
The acid-decomposable group has the same definition as the acid-decomposable group described in the specific acid-decomposable resin A of the first embodiment, and the preferred embodiment is also the same. The specific acid-decomposable resin B formed from the specific monomer B having an acid-decomposable group has a repeating unit having an acid-decomposable group (acid-decomposable repeating unit). Due to the presence of this acid-decomposable repeating unit, the specific acid-decomposable resin B exhibits properties such that the action of an acid increases the polarity, increases the solubility in an alkaline developer, and decreases the solubility in an organic solvent.

At least one of R ^X1 to R ^X4 represents an acid-decomposable group. At least two of R ^X1 to R ^X4 preferably represent an acid-decomposable group, more preferably two of R ^X1 to R ^X4 represent an acid-decomposable group, from the viewpoint that the effects of the present invention are more excellent. More preferably, R ^X1 and R ^X3 represent an acid-decomposable group.
Either one of R 1 ^X1 and R 1 ^X2 and either one of R 1 ^X3 and R 1 ^X4 may combine with each other to form a ring. The ring formed here is preferably an alicyclic ring. The alicyclic ring may be monocyclic or polycyclic, and preferably has 5 to 20 (preferably 5 to 10) member atoms. The alicyclic ring may have one or more (eg, 1 to 5) heteroatoms (oxygen, sulfur, nitrogen, etc.) as ring member atoms. The alicyclic ring may contain an unsaturated bond within the ring. In addition, the alicyclic ring may have a carbon atom in the ring substituted with a carbonyl carbon.
Note that when two of R ^X1 to R ^X4 represent an acid-decomposable group, the other two preferably represent a hydrogen atom from the viewpoint that the effects of the present invention are more excellent.

In general formula ( ² ), L2 represents a single bond or a divalent linking group.
Examples of the divalent linking group represented by L ² include -CO-, -NR ^d -, -O-, -S-, -SO-, -SO ₂ -, alkylene group, cycloalkylene group, alkenylene groups, divalent aliphatic heterocyclic groups, divalent aromatic heterocyclic groups, divalent aromatic hydrocarbon ring groups, and divalent linking groups combining a plurality of these. The alkylene group, cycloalkylene group, alkenylene group, divalent aliphatic heterocyclic group, divalent aromatic heterocyclic group, and divalent aromatic hydrocarbon ring group described above further have a substituent. may be R ^d in —NR ^d — above represents a hydrogen atom or an organic group. The organic group is preferably an alkyl group (eg, 1 to 6 carbon atoms).

The alkylene group may be linear or branched. Also, the number of carbon atoms is preferably 1 to 6.
The cycloalkylene group preferably has 3 to 15 carbon atoms.
The alkenylene group preferably has 2 to 6 carbon atoms.
The divalent aliphatic heterocyclic group is preferably a ring having 5 to 10 ring member atoms and having a heteroatom selected from the group consisting of a nitrogen atom, an oxygen atom, and a sulfur atom as a ring member atom. .
The divalent aromatic heterocyclic group is preferably a ring having 5 to 10 ring-member atoms having a heteroatom selected from the group consisting of a nitrogen atom, an oxygen atom, and a sulfur atom as a ring-member atom. .
Examples of the divalent aromatic hydrocarbon ring group include rings having 6 to 10 ring members.

The divalent linking group represented by L ² includes, among others, —CO—, —NR ^d —, —O—, —S—, —SO—, —SO ₂ —, an alkylene group, and a divalent aromatic Group hydrocarbon ring groups and divalent linking groups combining a plurality of these groups are preferred.
Examples of the above-mentioned "a divalent linking group combining a plurality of these" include -alkylene group -O-alkylene group -phenylene group- and the like.
In the divalent linking group represented by L ² , the positions adjacent to the polymerizable group represented by Y are —CO—, —NR ^d —, —O—, —S—, —SO—, or -SO ₂ -.

The polymerizable group represented by Y includes, for example, a radically polymerizable group and a cationic polymerizable group, preferably a radically polymerizable group, and more preferably an ethylenically unsaturated group.
Types of ethylenically unsaturated groups include, for example, a vinyl group, a maleimide group, and CH ₂ ═CR ^T — (R ^T represents a halogen atom (eg, a fluorine atom, a chlorine atom, a bromine atom, and an iodine atom). ), CH ₂ ═CR ^Q —CO—O— (R ^Q is an alkyl group having 1 to 6 carbon atoms optionally substituted with a halogen atom (e.g., fluorine atom, chlorine atom, bromine atom, and iodine atom) , or represents a hydrogen atom, when R ^Q represents a methyl group or a hydrogen atom, CH ₂ =CR ^Q -CO-O- corresponds to a (meth)acryl group, and when R ^Q represents a chlorine atom, (CH ₂ ═CR ^Q —CO—O— corresponds to an α-chloroacryl group), etc., and (meth)acryl groups are preferred in that the effects of the present invention are more excellent. That is, the specific monomer B is preferably a (meth)acrylic compound. Among them, the polymerizable group is more preferably a methacryl group because the effects of the present invention are more excellent.
The specific monomer B is preferably a monofunctional monomer.

The specific monomer B contains a monovalent substituent represented by the general formula (2) in the molecule. ^In the specific monomer B ^, the introduction position of the ^monovalent substituent represented by the general formula ( ² ) is not particularly limited. is introduced on the ring formed by bonding together, or is introduced on the ring formed by bonding R ¹¹ and R ¹⁴ together, or any one of R ⁵ and R ⁶ and R ⁷ and R ⁸ on the ring formed by combining any one of R 9 and R 10 with each other, or on the ring formed by combining any one of R ⁹ and R ¹⁰ and any one of R ¹² and R ¹³ with each other can be introduced.
The specific monomer B is preferably a monofunctional monomer. That is, the specific monomer B preferably has one monovalent substituent represented by the general formula (2).

In formula (1), a suitable combination (L ¹ , X ¹ , X ² ) of L ¹ , X ¹ and X ² is (-CR ³ =CR ⁴ -, =CR ¹¹ -, = CR ¹⁴ -), (-CR ³ =CR ⁴ -, -O-, -CO-), and (-CR ³ =CR ⁴ -, -CO-, -O-).
Specific examples of the specific monomer B when (L ¹ , X ¹ , X ² ) are (-CR ³ =CR ⁴ -, =CR ¹¹ -, =CR ¹⁴ -) include the following general formula A compound represented by (AX) can be mentioned. The polymerizable compound represented by the following general formula (AX) has 9,10-dihydroanthracene as its basic skeleton.

In general formula (AX), R ¹ , R ² , and R ^X1 to R ^X4 are each independently synonymous with R ¹ , R ² and R ^X1 to R ^X4 in general formula (1), and preferred embodiments are also are the same.
^R22 and ^R23 each independently represent a substituent. Examples of the substituents represented by R ²² and R ²³ include those exemplified for the substituents represented by R ¹ to R ¹⁴ .
m and n each independently represent an integer of 0 to 4;
However, the polymerizable compound represented by the above general formula (AX) contains a monovalent substituent represented by the above general formula (2) in the molecule. Specifically, it is preferably introduced at any position of R ¹ , R ² , R ²² and R ²³ .

A preferred embodiment of the specific monomer B includes a polymerizable compound represented by the following general formula (3) and a polymerizable compound represented by the following general formula (4).

The polymerizable compound represented by the general formula (3) has the same meaning as the general formula (1) except that it has a monovalent substituent represented by the general formula (2) at the position of R ¹ and is a preferred embodiment. is the same. In addition, the polymerizable compound represented by the general formula (3) is preferably a monofunctional monomer.

The polymerizable compound represented by general formula (4) has the same definition and preferred embodiment as general formula (1), except that L ¹ represents -CR ³ =CR ⁴ -. In addition, the polymerizable compound represented by the general formula (4) is preferably a monofunctional monomer.

In general formula (4), the introduction position of the monovalent substituent represented by general formula (2) is, for example, any one of R ¹ to R ⁴ , or R ³ and R ⁴ is preferably introduced on the ring formed by combining with each other.
A preferred embodiment of the polymerizable compound represented by the general formula (4) is an embodiment in which X ¹ represents -O- and X ² represents -CO-.
Further, as another preferred embodiment of the polymerizable compound represented by the general formula (4), X ¹ represents -O-, X ² represents -CO-, and R ³ and R ⁴ are bonded to each other and form an alicyclic ring.
Another preferable aspect of the polymerizable compound represented by the general formula (4) is an aspect in which X ¹ represents --CO-- and X ² represents --O--.
Further, as another preferred embodiment of the polymerizable compound represented by the general formula (4), X ¹ represents —CO—, X ² represents —O—, and R ³ and R ⁴ are bonded to each other and form an alicyclic ring.

As the polymerizable compound represented by the above general formula (3), a polymerizable compound represented by the following general formula (5) is preferable. The polymerizable compound represented by the following general formula (5) has 9,10-dihydroanthracene as its basic skeleton.

In general formula (5), R ²⁴ and R ^X1 to R ^X4 are each independently synonymous with R ² and R ^X1 to R ^X4 in general formula (1), and preferred embodiments are also the same.
^R21 represents a hydrogen atom or a substituent. Examples of substituents represented by R ²¹ include alkyl groups having 1 to 6 carbon atoms optionally substituted with halogen atoms (eg, fluorine atom, chlorine atom, bromine atom and iodine atom). R ²¹ is preferably a hydrogen atom or a methyl group, more preferably a methyl group.
^R22 and ^R23 each independently represent a substituent. Examples of the substituents represented by R ²² and R ²³ include those exemplified for the substituents represented by R ¹ to R ¹⁴ .
m and n each independently represent an integer of 0 to 4;
^L21 includes a single bond or a divalent linking group.
The divalent linking group represented by L21 includes the same divalent linking groups as the divalent linking group represented by L2 in formula ⁽ ² ), and preferred embodiments are also the same.

The specific monomer B is preferably a polymerizable compound whose homopolymer has a glass transition temperature of 220°C or higher. The glass transition temperature of the homopolymer of the specific monomer B is intended to be the value obtained by the measurement method described above as the glass transition temperature of the homopolymer of the specific monomer A.

The glass transition temperature of the homopolymer of the specific monomer B is more preferably 250° C. or higher, still more preferably 280° C. or higher, and particularly 300° C. or higher, from the viewpoint that the effects of the present invention are more excellent. preferable. Although the upper limit is not particularly limited, it is preferably 400° C. or less.

The protective group value of the specific monomer B is preferably 3.40 mmol/g or more from the viewpoint that the effects of the present invention are more excellent. The protective group value represents the molar amount (mmol/g) of the acid-decomposable group relative to the mass of the specific monomer B (polymerizable compound). Although the upper limit is not particularly limited, it is preferably 6.0 mmol/g or less. The protective group value is more preferably 3.50 mmol/g or more, still more preferably 3.60 mmol/g or more, from the viewpoint that the effects of the present invention are more excellent.

Although the molecular weight of the specific monomer B is not particularly limited, it is preferably 400 or more, for example. The upper limit is preferably 1,000 or less, more preferably 800 or less, and even more preferably 700 or less.

The specific monomer B can be synthesized by a known method. Specifically, it can be obtained by a method of forming an unsaturated 6-membered ring structure by adding an alkene compound to a conjugated diene compound by Diels-Alder reaction.

Specific examples of the specific monomer B (group A and group B) are shown below, but are not limited thereto. All of the compounds belonging to (Group A) of the specific monomer A shown below correspond to compounds having 9,10-dihydroanthracene as a basic skeleton.
(Group A)

(Group B)

[Method for manufacturing electronic device]
The present invention also relates to an electronic device manufacturing method including a pattern forming method using the resist compositions of the first and second embodiments, and an electronic device manufactured by this manufacturing method.
The electronic device of the present invention is preferably mounted in electric/electronic equipment (household appliances, OA (Office Automation), media-related equipment, optical equipment, communication equipment, etc.).

[Compound]
The present invention also relates to the polymerizable compound (specific monomer B) represented by the general formula (1) described above. Specific monomer B is as described above.

[resin]
The present invention also relates to a resin (specific acid-decomposable resin B) having a repeating unit derived from the polymerizable compound (specific monomer B) represented by the general formula (1) described above. Specific acid-decomposable resin B is as described above.

The present invention will be described in more detail below based on examples. The materials, amounts used, proportions, processing details, processing procedures, etc. 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 to be limited by the examples shown below.

[Various Components of Actinic Ray-Sensitive or Radiation-Sensitive Resin Composition]
〔resin〕
The resins (A-1 to A-23, B-1 to B-10) shown in Table 5 are shown below. The resins A-1 to A-23 and B-1 to B-10 were synthesized according to the synthesis method described below for resin A-10.
Table 1 shows the mass ratio, weight average molecular weight (Mw), and dispersity (Mw/Mn) of the repeating units constituting the resins (A-1 to A-23, B-1 to B-10) shown in Table 5. ).
Incidentally, the weight average molecular weight (Mw) and the degree of dispersion (Mw/Mn) of the resins A-1 to A-23 and B-1 to B-10 were measured by GPC (carrier: tetrahydrofuran (THF)), and the polystyrene equivalent amount was is shown as

Tables 2 to 4 show the structures of the monomers (polymerizable compounds) used to synthesize the resins A-1 to A-23 and B-1 to B-10 shown in Table 1. Among the monomers shown below, M-55 to M-73 are monomers (specific monomer A ).
Further, among the following monomers M-55 to M-73, M-55, M-58 to M-61, and M-67 to M-72 are polymerizable represented by the above general formula (1) It corresponds to a compound (specific monomer B).

Monomers M-55 to M-73 were synthesized according to the synthesis method described below for resin M-55.

Tables 2 to 4 also show the glass transition temperature and protective group value (mmol equivalent per 1 g of monomer (mmol/g)) of the homopolymer of each monomer.
The glass transition temperature of the homopolymer of each monomer shown in Tables 2 to 4 is a value measured by the following method.

<<Method for measuring the glass transition temperature (Tg) of the homopolymer of each monomer shown in Tables 2 to 4>>
<1> Each monomer shown in Tables 2 to 4 is synthesized with a charging composition of 30% by mass and cyclohexyl methacrylate is 70% by mass, and a weight average molecular weight of 60,000 or more (specifically, a weight average molecular weight of 60 ,000 to 100,000) is obtained.
<2> Tg of the obtained copolymer P2 is evaluated with a differential calorimeter ("Differential scanning calorimeter DSC-60 Plus measurement system" manufactured by Shimadzu Corporation).
In addition, in measuring Tg, the following measurement conditions were used.
Measurement conditions: Temperature was raised from room temperature to 150°C under an air current. A heating rate of 5° C./min was repeated for two cycles to obtain the Tg of copolymer P2.
<3> Calculate the Tg of the homopolymer of each monomer shown in Tables 2 to 4 using the following formula (1) based on the Fox formula, with the Tg of the homopolymer of cyclohexyl methacrylate set to 98°C.

Formula (1) 1/Tg=w1/Tg1+w2/Tg2
In formula (1), Tg represents the Tg (K) of copolymer P2. Tg1 represents the homopolymer Tg (K) of each monomer shown in Tables 2-4. Tg2 represents the homopolymer Tg(K) of cyclohexyl methacrylate. w1 represents the mass fraction of repeating units derived from each monomer shown in Tables 2 to 4 with respect to all repeating units in copolymer P2. w2 represents the mass fraction of repeating units derived from the homopolymer of cyclohexyl methacrylate to all repeating units in copolymer P2. In calculating the homopolymer Tg of each monomer, w1 is 0.3 and w2 is 0.7.

The following monomers M-55, M-59 to M-61, M-67 to M-69, and M-71 to M-72 are all compounds having 9,10-dihydroanthracene as a basic skeleton. corresponds to

<<Synthesis example>>
<Synthesis Example 1: Synthesis of M-55>
(First step: Synthesis of fumaric acid ester)

A mixed solution of potassium t-butoxy (146.8 g) and t-butanol (1300 g) was heated to 35° C. under a stream of nitrogen. While stirring this liquid, fumaric chloride (100.0 g) was added dropwise, and after completion of the dropwise addition, the temperature was raised to 50° C. and the mixture was stirred for 4 hours.
After allowing the resulting liquid to cool to room temperature, 200 ml of saturated aqueous sodium bicarbonate was added dropwise with stirring to terminate the reaction. After that, residual t-BuOH was removed by an evaporator. Then, 1200 ml of ethyl acetate and 1200 ml of water were used for liquid separation, and the separated ethyl acetate layer was dried over magnesium sulfate. After drying, filtration was performed, and the filtered liquid was concentrated by an evaporator. After 50 ml of isopropanol was added to the obtained concentrate and dissolved by heating, 50 ml of water was added to crystallize. The obtained crystallized product (powder) was collected by filtration to obtain the desired product (FA-TBm: yield: 70.1 g, yield: 47%).

(Second step: Synthesis of precursor compound (M'-55))

Anthracenemethanol (50.0 g) and FA-TBm (65.8 g) were added to toluene (250 ml), heated to 115° C. in an oil bath, and reacted under reflux for 16 hours. Toluene was removed by an evaporator, 36 ml of methanol was added, and the mixture was stirred while cooling with ice. The precipitated powder was filtered to obtain the desired product (M'-55: yield 80 g, yield 76.3%).

(Third step: Synthesis of compound M-55)

M'-55 (80 g) was dissolved in tetrahydrofuran (185 ml), and methacrylic acid chloride (46 g) was added dropwise while cooling with ice, followed by triethylamine (44.5 g). After the dropwise addition, the resulting reaction solution was further reacted for 1 hour, then added to 1200 ml of ethyl acetate and 1200 ml of saturated aqueous sodium bicarbonate, and stirred overnight. After that, the ethyl acetate layer was extracted by a liquid separation operation and dried with magnesium sulfate. Filtration was performed after drying, and then the filtered liquid was concentrated by an evaporator. 360 ml of methanol was added to the resulting concentrate and stirred to crystallize. The obtained crystallized product (powder) was collected by filtration to obtain the desired product (M-55: yield: 75.8 g, yield: 82%).
FIG. 1 shows the ¹ H-NMR chart of the obtained M-55.

<Synthesis Example 2: Synthesis of Resin A-10>
Cyclohexanone (15.2 g) was heated to 85° C. under a stream of nitrogen. While stirring this liquid, the following monomer M-19 (31.3 g, 50.4% by mass PGMEA solution), the following monomer M-60 (29.3 g), cyclohexanone (27.1 g), and 2,2' A mixed solution of dimethyl azobisisobutyrate [V-601, manufactured by Wako Pure Chemical Industries, Ltd.] in cyclohexanone [10% by mass] (33.8 g) was added dropwise over 6 hours to obtain a reaction solution. After the dropwise addition was completed, the reaction solution was stirred at 85° C. for another 2 hours. The obtained reaction solution was left to cool, reprecipitated with a large amount of heptane/ethyl acetate (mass ratio 9:1), filtered, and the resulting solid was dried under vacuum to obtain resin A-10 (39 g). got All the above operations were performed under a yellow light.

[Photoacid generator]
The structures of the photoacid generators (B-1 to B-11) shown in Table 5 are shown below.

[Hydrophobic resin]
The structures, weight average molecular weights (Mw), and dispersities (Mw/Mn) of the hydrophobic resins (P-1 to P-3) shown in Table 5 are shown below.
The weight average molecular weight (Mw) and the degree of dispersion (Mw/Mn) of the hydrophobic resins P-1 to P-3 were measured by GPC (carrier: THF) and shown as polystyrene equivalents.
- Hydrophobic resin P-1: a polymer (Mw: 8,700, Mw/Mn: 1.56) made from the following monomer ME-1
- Hydrophobic resin P-2: a polymer (Mw: 7,600, Mw/Mn: 1.62) made from the following monomer ME-5
Hydrophobic resin P-3: polymer (Mw: 5,800, Mw/Mn: 1.55) made from the following monomer ME-2

[Surfactant]
The surfactants shown in Table 5 are shown below.
H-1: Megafac F176 (manufactured by DIC Corporation, fluorine-based surfactant)

〔solvent〕
The solvents shown in Table 5 are shown below.
G-1: Propylene glycol monomethyl ether acetate (PGMEA)
G-2: Propylene glycol monomethyl ether (PGME)
G-5: cyclopentanone G-8: γ-butyrolactone

[Preparation and pattern formation of actinic ray-sensitive or radiation-sensitive resin composition: EUV exposure]
[Preparation of actinic ray-sensitive or radiation-sensitive resin composition]
Each component shown in Table 5 was mixed so that the solid content concentration was 1.4% by mass. Next, the resulting mixed solution is first filtered through a polyethylene filter with a pore size of 50 nm, then through a nylon filter with a pore size of 10 nm, and finally through a polyethylene filter with a pore size of 5 nm. Photosensitive or radiation-sensitive resin compositions (hereinafter also referred to as "resist compositions") (Re-1 to Re-23, HRe-1 to HRe-10) were prepared. In addition, solid content means all the components other than a solvent. The resulting resist compositions were used in Examples and Comparative Examples.

Table 5 is shown below.
The "content" column of each component in the table indicates the content (% by mass) of each component with respect to the total solid content. The "mixing ratio" in the "solvent" column indicates the mixing ratio (mass ratio) of each solvent.

[Pattern formation and evaluation (1): EUV exposure, alkali development]
<Pattern formation>
An underlayer film forming composition AL412 (manufactured by BrewerScience) was applied onto a silicon wafer with a diameter of 12 inches and baked at 205° C. for 60 seconds to form an underlayer film with a thickness of 20 nm. The resist composition prepared as described above was applied thereon and baked at 100° C. for 60 seconds to form a resist film having a thickness of 20 nm.
Using an EUV exposure machine (manufactured by ASML; NXE3350, NA 0.33, Dipole 45°, outer sigma 0.87, inner sigma 0.60), line size = 20 nm, and line: space = 1: 1 Exposure was made through a reflective mask.
Next, it was developed with a 2.38% by mass TMAH (tetramethylammonium hydroxide) aqueous solution for 30 seconds and rinsed with water for 20 seconds. Subsequently, the wafer was rotated at a rotational speed of 2000 rpm for 40 seconds to form a positive pattern with a line size of 20 nm and a line:space ratio of 1:1.

<Evaluation>
(Line width roughness (LWR performance, nm))
The pattern obtained by the above method was observed from above using a scanning electron microscope (SEM (Hitachi Ltd. S-9380II)). The line width of the pattern was observed at 250 points, and the measurement variation was evaluated by 3σ to obtain LWR (nm). The smaller the value of LWR, the better the LWR performance. Table 6 shows the results.
The LWR performance is preferably less than 4.00 nm, more preferably 3.50 nm or less, and even more preferably 3.00 nm or less.

(Evaluation of resolution (limiting resolution, nm))
In the above <pattern formation>, the exposure is performed at the optimum exposure dose Eop (μC/cm ² ) (the exposure dose when the pattern formed using the resist composition reproduces the pattern of the mask used for exposure). ing.
Next, a test was conducted in which a line-and-space pattern was formed by gradually changing the exposure amount from the optimum exposure amount Eop. At this time, the minimum dimension of the pattern that can be resolved without collapsing was determined using a scanning electron microscope (SEM (Hitachi Ltd. S-9380II)). This was defined as "limiting resolution (nm)". The smaller the limit resolution value, the better the resolution. Table 6 shows the results.
The resolution is preferably less than 15.0 nm, more preferably 13.0 nm or less, and even more preferably 12.0 nm or less.

From the results shown in the table, it was confirmed that the resist compositions of Examples are excellent in resolution and also in LWR performance of the formed patterns.

(Results for specific monomer A)
Further, from the comparison of each example, the raw material monomer of the acid-decomposable repeating unit in the acid-decomposable resin contained in the resist composition has a glass transition temperature of 300° C. or higher in a homopolymer and a protective group value of 3.40 mmol/g or more (preferably, a homopolymer having a glass transition temperature of 300°C or more and a protecting group value of 3.50 mmol/g or more) , it was confirmed that the resist composition is superior in resolution and the LWR performance of the formed pattern is also superior.
Further, when the polar group protected by the protecting group in the structure of the acid-decomposable repeating unit is a carboxyl group, the resist composition is superior in resolution, and the LWR performance of the formed pattern is also superior. was confirmed.

(Results for specific monomer B)
Further, for example, when the results of Examples 4 and 8 are compared, the raw material monomer of the acid-decomposable repeating unit in the acid-decomposable resin contained in the resist composition is represented by the general formula (1) described above. Among the polymerizable compounds, in particular, when the structure is represented by the general formula (AX) described above, the resist composition is superior in resolution, and it is confirmed that the LWR performance of the formed pattern is also superior. was done.
Further, for example, when comparing the results of Example 1, Example 6, and Example 7, in the polymerizable compound represented by the general formula (1) described above, when the polymerizable group is a (meth) acrylic group It was confirmed that the resist composition was superior in resolution and LWR performance of the formed pattern (preferably in the case of methacrylic groups).

In addition, from the comparison of Example 1, Example 11, Example 21, and Example 22, in the polymerizable compound represented by the above general formula (1), the type of acid-decomposable group is the above general formula ( O1) and two of R ₁₁ to R ₁₃ do not bond to each other to form a ring, the resist composition is superior in resolution and the LWR performance of the formed pattern is improved. was also found to be superior.

Further, from the comparison between Example 1 and Example 13, in the polymerizable compound represented by the above general formula (1), when the number of acid-decomposable groups is 2, the resist composition is superior in resolution. Moreover, it was confirmed that the LWR performance of the formed pattern was also superior.

Further, from a comparison of Examples 1, 9, and 14, two of R ^X1 to R ^X4 in the polymerizable compound represented by the above general formula (1) represent an acid-decomposable group. , and the other two represent hydrogen atoms, it was confirmed that the resist composition was superior in resolution and the LWR performance of the formed pattern was also superior.

On the other hand, the desired performance was insufficient in the resist composition of the comparative example.

[Pattern formation and evaluation (2): EUV exposure, organic solvent development]
<Pattern formation>
An underlayer film forming composition AL412 (manufactured by Brewer Science) was applied onto a silicon wafer with a diameter of 12 inches and baked at 205° C. for 60 seconds to form an underlayer film with a thickness of 20 nm. A resist composition shown in Table 7 was applied thereon and baked at 100° C. for 60 seconds to form a resist film having a thickness of 30 nm.
A pattern obtained for a silicon wafer having a resist film obtained using an EUV exposure apparatus (Exitech, Micro Exposure Tool, NA 0.3, Quadrupole, outer sigma 0.68, inner sigma 0.36) The pattern irradiation was carried out so that the average line width of was 20 nm. As the reticle, a mask having a line size of 20 nm and a line:space ratio of 1:1 was used.
The exposed resist film was baked at 90° C. for 60 seconds, developed with n-butyl acetate for 30 seconds, and spin-dried to obtain a negative pattern.

<Evaluation>
The resulting negative pattern was evaluated for line width roughness (LWR performance, nm) and resolution in the same manner as in [Pattern formation and evaluation (1): EUV exposure, alkali development]. (limiting resolution, nm) was performed. Table 7 shows the results.

From the results shown in the table, it was confirmed that according to the resist compositions of the examples, patterns with excellent LWR and resolution can be formed.

(Results for specific monomer B)
Further, for example, when the results of Examples 24 and 28 are compared, the raw material monomer of the acid-decomposable repeating unit in the acid-decomposable resin contained in the resist composition is represented by the general formula (1) described above. Among the polymerizable compounds, in particular, when the structure is represented by the general formula (AX), the resist composition is superior in resolution, and it was confirmed that the LWR performance of the formed pattern is also superior. .
Further, for example, when comparing the results of Example 21, Example 26, and Example 27, in the polymerizable compound represented by the general formula (1) described above, when the polymerizable group is a (meth) acrylic group It was confirmed that the resist composition was superior in resolution and LWR performance of the formed pattern (preferably in the case of methacrylic groups).

Further, from the comparison of Example 21, Example 31, Example 41, and Example 42, in the polymerizable compound represented by the above-described general formula (1), the type of acid-decomposable group is the above-described general formula ( O1) and two of R ₁₁ to R ₁₃ do not bond to each other to form a ring, the resist composition is superior in resolution and the LWR performance of the formed pattern is improved. was also found to be superior.

Further, from the comparison between Example 21 and Example 33, in the polymerizable compound represented by the general formula (1) described above, when the number of acid-decomposable groups is two, the resist composition is superior in resolution. Moreover, it was confirmed that the LWR performance of the formed pattern was also superior.

Further, from a comparison of Examples 21, 29, and 34, in the polymerizable compound represented by the general formula (1), two of R ^X1 to R ^X4 represent an acid-decomposable group. , and the other two represent hydrogen atoms, it was confirmed that the resist composition was superior in resolution and the LWR performance of the formed pattern was also superior.

Claims

An actinic ray- or radiation-sensitive resin composition comprising a resin having repeating units derived from a polymerizable compound having an acid-decomposable group and a photoacid generator,
The polymerizable compound is a polymerizable compound whose homopolymer has a glass transition temperature of 220° C. or higher,
Actinic ray-sensitive or radiation-sensitive resin composition, wherein the molar amount of the acid-decomposable group relative to the mass of the polymerizable compound is 3.40 mmol/g or more.
The actinic ray-sensitive or radiation-sensitive resin composition according to claim 1, wherein the polymerizable compound contains one or more of an aromatic ring and an aliphatic heterocycle.
The actinic ray-sensitive or radiation-sensitive resin composition according to claim 1 or 2, wherein the polymerizable compound has a polycyclic structure.
The actinic ray-sensitive or sensitive according to claim 1 or 2, wherein the polymerizable compound is a polymerizable compound having an aliphatic heterocyclic ring of a polycyclic structure, or a polymerizable compound having an aromatic ring. A radioactive resin composition.
The actinic ray-sensitive or radiation-sensitive resin composition according to any one of claims 1 to 4, wherein the polymerizable compound has at least two acid-decomposable groups.
The actinic ray-sensitive or radiation-sensitive resin composition according to any one of claims 1 to 5, wherein the polymerizable compound is an acrylic compound or a methacrylic compound.
An actinic ray-sensitive or radiation-sensitive resin composition comprising a resin having a repeating unit derived from a polymerizable compound represented by the following general formula (1) and a photoacid generator.

In the formula, L 1 represents -CR 3 =CR 4 - or -CR 5 R 6 -CR 7 R 8 -.
X 1 represents -O-, -CR 9 R 10 -, or =CR 11 -.
X 2 represents -O-, -CO-, -CR 12 R 13 -, or =CR 14 -.
The solid-dotted bond between X 1 and X 2 represents a single bond or a double bond. However, when the bond between X 1 and X 2 represents a double bond, X 1 represents =CR 11 - and X 2 represents =CR 14 -. Further, when the bond between X 1 and X 2 represents a single bond, X 1 represents -O- or -CR 9 R 10 -, and X 2 represents -O-, -CO- or -CR represents 12 R 13 -.
R 1 to R 14 each independently represent a hydrogen atom or a substituent. In addition, R 3 and R 4 may combine with each other to form a ring. In addition, one of R 5 and R 6 and one of R 7 and R 8 may combine with each other to form a ring. Further, when X 1 represents =CR 11 - and X 2 represents =CR 14 -, R 11 and R 14 may combine with each other to form a ring. When X 1 represents -CR 9 R 10 - and X 2 represents -CR 12 R 13 -, any one of R 9 and R 10 and any one of R 12 and R 13 are bonded to each other. may form a ring.
R X1 to R X4 each independently represent a hydrogen atom or a substituent. However, at least one of R X1 to R X4 represents an acid-decomposable group. Any one of R 1 X1 and R 1 X2 and either one of R 1 X3 and R 1 X4 may combine with each other to form a ring.
However, the polymerizable compound represented by the general formula (1) contains a monovalent substituent represented by the following general formula (2) in the molecule.

In the formula, L2 represents a single bond or a divalent linking group. Y represents a polymerizable group. * represents a binding position.
The actinic ray-sensitive or radiation-sensitive resin composition according to claim 7, wherein the polymerizable compound represented by the general formula (1) is a polymerizable compound represented by the following general formula (3).

In the formula, L 1 represents -CR 3 =CR 4 - or -CR 5 R 6 -CR 7 R 8 -.
X 1 represents -O-, -CR 9 R 10 -, or =CR 11 -.
X 2 represents -O-, -CO-, -CR 12 R 13 -, or =CR 14 -.
The solid-dotted bond between X 1 and X 2 represents a single bond or a double bond. However, when the bond between X 1 and X 2 represents a double bond, X 1 represents =CR 11 - and X 2 represents =CR 14 -. Further, when the bond between X 1 and X 2 represents a single bond, X 1 represents -O- or -CR 9 R 10 -, and X 2 represents -O-, -CO- or -CR represents 12 R 13 -.
R 2 to R 14 each independently represent a hydrogen atom or a substituent. In addition, R 3 and R 4 may combine with each other to form a ring. In addition, one of R 5 and R 6 and one of R 7 and R 8 may combine with each other to form a ring. Further, when X 1 represents =CR 11 - and X 2 represents =CR 14 -, R 11 and R 14 may combine with each other to form a ring. When X 1 represents -CR 9 R 10 - and X 2 represents -CR 12 R 13 -, any one of R 9 and R 10 and any one of R 12 and R 13 are bonded to each other. may form a ring.
R X1 to R X4 each independently represent a hydrogen atom or a substituent. However, at least one of R X1 to R X4 represents an acid-decomposable group. Any one of R X1 and R X2 and R X3
and any one of R 1 X4 may combine with each other to form a ring.
L2 represents a single bond or a divalent linking group.
Y represents a polymerizable group.
The actinic ray-sensitive or radiation-sensitive resin composition according to claim 7, wherein the polymerizable compound represented by the general formula (1) is a polymerizable compound represented by the following general formula (4).

In the formula, X 1 represents -O-, -CR 9 R 10 -, or =CR 11 -.
X 2 represents -O-, -CO-, -CR 12 R 13 -, or =CR 14 -.
The solid-dotted bond between X 1 and X 2 represents a single bond or a double bond. However, when the bond between X 1 and X 2 represents a double bond, X 1 represents =CR 11 - and X 2 represents =CR 14 -. Further, when the bond between X 1 and X 2 represents a single bond, X 1 represents -O- or -CR 9 R 10 -, and X 2 represents -O-, -CO- or -CR represents 12 R 13 -.
R 1 to R 4 and R 9 to R 14 each independently represent a hydrogen atom or a substituent. In addition, R 3 and R 4 may combine with each other to form a ring. Further, when X 1 represents =CR 11 - and X 2 represents =CR 14 -, R 11 and R 14 may combine with each other to form a ring. When X 1 represents -CR 9 R 10 - and X 2 represents -CR 12 R 13 -, any one of R 9 and R 10 and any one of R 12 and R 13 are bonded to each other. may form a ring.
R X1 to R X4 each independently represent a hydrogen atom or a substituent. However, at least one of R X1 to R X4 represents an acid-decomposable group. Either one of R 1 X1 and R 1 X2 and either one of R 1 X3 and R 1 X4 may combine with each other to form a ring.
However, the polymerizable compound represented by the general formula (4) contains a monovalent substituent represented by the following general formula (2) in the molecule.

In the formula, L2 represents a single bond or a divalent linking group. Y represents a polymerizable group. * represents a binding position.
The actinic ray-sensitive or radiation-sensitive resin composition according to any one of claims 7 to 9, wherein at least two of R X1 to R X4 represent an acid-decomposable group.
The actinic ray-sensitive or radiation-sensitive resin composition according to claim 7, wherein the polymerizable compound represented by the general formula (1) is a polymerizable compound represented by the following general formula (5).

In the formula, L21 represents a single bond or a divalent linking group. R X1 and R X3 each independently represent an acid-decomposable group. R X2 and R X4 each independently represent a hydrogen atom or a substituent. R 1 X2 and R 1 X4 may combine with each other to form a ring. R21 represents a hydrogen atom or a substituent. R22 and R23 each independently represent a substituent. m and n each independently represent an integer of 0 to 4; R24 represents a hydrogen atom or a substituent.
A resist film formed using the actinic ray-sensitive or radiation-sensitive resin composition according to any one of claims 1 to 11.
forming a resist film on a substrate using the actinic ray-sensitive or radiation-sensitive resin composition according to any one of claims 1 to 11;
exposing the resist film;
a step of developing the exposed resist film using a developer;
A pattern forming method.
A method for manufacturing an electronic device, including the pattern forming method according to claim 13.
A polymerizable compound represented by the following general formula (1).

In the formula, L 1 represents -CR 3 =CR 4 - or -CR 5 R 6 -CR 7 R 8 -.
X 1 represents -O-, -CR 9 R 10 -, or =CR 11 -.
X 2 represents -O-, -CO-, -CR 12 R 13 -, or =CR 14 -.
The solid-dotted bond between X 1 and X 2 represents a single bond or a double bond. However, when the bond between X 1 and X 2 represents a double bond, X 1 represents =CR 11 - and X 2 represents =CR 14 -. Further, when the bond between X 1 and X 2 represents a single bond, X 1 represents -O- or -CR 9 R 10 -, and X 2 represents -O-, -CO- or -CR represents 12 R 13 -.
R 1 to R 14 each independently represent a hydrogen atom or a substituent. In addition, R 3 and R 4 may combine with each other to form a ring. In addition, one of R 5 and R 6 and one of R 7 and R 8 may combine with each other to form a ring. Further, when X 1 represents =CR 11 - and X 2 represents =CR 14 -, R 11 and R 14 may combine with each other to form a ring. When X 1 represents -CR 9 R 10 - and X 2 represents -CR 12 R 13 -, any one of R 9 and R 10 and any one of R 12 and R 13 are bonded to each other. may form a ring.
R X1 to R X4 each independently represent a hydrogen atom or a substituent. However, at least one of R X1 to R X4 represents an acid-decomposable group. Any one of R 1 X1 and R 1 X2 and either one of R 1 X3 and R 1 X4 may combine with each other to form a ring.
However, the polymerizable compound represented by the general formula (1) contains a monovalent substituent represented by the following general formula (2) in the molecule.

In the formula, L2 represents a single bond or a divalent linking group. Y represents a polymerizable group. * represents a binding position.
A resin having a repeating unit derived from a polymerizable compound represented by the following general formula (1).

In the formula, L 1 represents -CR 3 =CR 4 - or -CR 5 R 6 -CR 7 R 8 -.
X 1 represents -O-, -CR 9 R 10 -, or =CR 11 -.
X 2 represents -O-, -CO-, -CR 12 R 13 -, or =CR 14 -.
The solid-dotted bond between X 1 and X 2 represents a single bond or a double bond. However, when the bond between X 1 and X 2 represents a double bond, X 1 represents =CR 11 - and X 2 represents =CR 14 -. Further, when the bond between X 1 and X 2 represents a single bond, X 1 represents -O- or -CR 9 R 10 -, and X 2 represents -O-, -CO- or -CR represents 12 R 13 -.
R 1 to R 14 each independently represent a hydrogen atom or a substituent. In addition, R 3 and R 4 may combine with each other to form a ring. In addition, one of R 5 and R 6 and one of R 7 and R 8 may combine with each other to form a ring. Further, when X 1 represents =CR 11 - and X 2 represents =CR 14 -, R 11 and R 14 may combine with each other to form a ring. When X 1 represents -CR 9 R 10 - and X 2 represents -CR 12 R 13 -, any one of R 9 and R 10 and any one of R 12 and R 13 are bonded to each other. may form a ring.
R X1 to R X4 each independently represent a hydrogen atom or a substituent. However, at least one of R X1 to R X4 represents an acid-decomposable group. Any one of R 1 X1 and R 1 X2 and either one of R 1 X3 and R 1 X4 may combine with each other to form a ring.
However, the polymerizable compound represented by the general formula (1) contains a monovalent substituent represented by the following general formula (2) in the molecule.

In the formula, L2 represents a single bond or a divalent linking group. Y represents a polymerizable group. * represents a binding position.