WO2024038802A1

WO2024038802A1 - Active light-sensitive or radiation-sensitive resin composition, resist film, method for forming pattern, and method for producing electronic device

Info

Publication number: WO2024038802A1
Application number: PCT/JP2023/028936
Authority: WO
Inventors: 三千紘白川
Original assignee: 富士フイルム株式会社
Priority date: 2022-08-15
Filing date: 2023-08-08
Publication date: 2024-02-22

Abstract

A problem addressed by the present invention is to provide an active light-sensitive or radiation-sensitive resin composition which is capable of forming a pattern that exhibits excellent resolution performance. In addition, the present invention addresses another problem of providing a resist film, a method for forming a pattern, and a method for producing an electronic device.　An active light-sensitive or radiation-sensitive resin composition according to the present invention satisfies a prescribed requirement 1 or a prescribed requirement 2.

Description

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

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

In order to miniaturize semiconductor devices, the wavelength of exposure light sources has become shorter and the numerical aperture (NA) of projection lenses has become higher.Currently, exposure machines using ArF excimer lasers with a wavelength of 193 nm as light sources have been developed. ing. Furthermore, recently, a pattern forming method using extreme ultraviolet (EUV) light and electron beam (EB) as a light source is also being considered.
Under these current circumstances, various configurations have been proposed as actinic ray-sensitive or radiation-sensitive resin compositions.

For example, Patent Document 1 discloses a two-stage exposure lithography process using a photosensitized chemically amplified resist material.

Japanese Patent Application Publication No. 2015-172741

The present inventor prepared and studied a photosensitized chemically amplified resist material with reference to Patent Document 1, and found that there was room for further improvement in resolution.

Therefore, an object of the present invention is to provide an actinic ray-sensitive or radiation-sensitive resin composition that can form a pattern with excellent resolution.
Another object of the present invention is to provide a resist film, a pattern forming method, and an electronic device manufacturing method.

The present inventor has discovered that the above problem can be solved by the following configuration.

[1] An actinic ray- or radiation-sensitive resin composition that satisfies Requirement 1 or Requirement 2.
Requirement 1: The composition includes a resin XA, an onium salt XB that generates an acid upon irradiation with light, and a sensitizer precursor XC that generates a sensitizer by the action of the acid,
The resin XA has an interactive group that interacts with the onium salt XB, or the resin XA and the onium salt XB are bonded via a covalent bond,
The onium salt XB is a compound that acts on the sensitizer precursor XC to generate an acid capable of producing a sensitizer, or
When the onium salt XB is a compound that does not generate an acid capable of producing a sensitizer by acting on the sensitizer precursor XC, the composition further acts on the sensitizer precursor XC. Contains a photoacid generator XD capable of generating an acid capable of producing a sensitizer, or the sensitizer precursor XC generates an acid capable of producing the sensitizer upon irradiation with light,
The content of the repeating unit having a group that decomposes to produce a polar group under the action of an acid in the resin XA is 0 to 20 mol % based on the total repeating units of the resin XA.
Note that the sensitizer precursor XC may be bonded to the resin XA via a covalent bond. Further, the photoacid generator XD may be bonded to the resin XA via a covalent bond.
Requirement 2: Contains resin YA and compound YB, which has an onium salt structure that generates an acid when irradiated with light and generates a sensitizer by the action of the acid,
The resin YA has an interactive group that interacts with the compound YB, or the resin YA and the compound YB are bonded via a covalent bond,
The onium salt structure is a structure that generates the acid that can generate the sensitizer, or
When the onium salt structure is not a structure that generates the acid that can generate the sensitizer, the composition further includes a photoacid generator YC that can generate the acid that can generate the sensitizer,
The content of the repeating unit having a group that decomposes to produce a polar group by the action of an acid in the resin YA is 0 to 20 mol % based on the total repeating units of the resin YA.
Note that the photoacid generator YC may be bonded to the resin YA via a covalent bond.
[2] The actinic ray- or radiation-sensitive resin according to [1], wherein the resin XA and the resin YA are resins whose main chains are cleaved by the action of exposure, acid, base, or heating, resulting in a decrease in molecular weight. resin composition.
[3] The actinic ray- or radiation-sensitive resin composition according to [1] or [2], wherein the resin XA and the resin YA have a weight average molecular weight of 40,000 or more.
[4] The actinic ray- or radiation-sensitive resin composition according to any one of [1] to [3], wherein the polydispersity of the resin XA and the resin YA is 1.7 or less.
[5] A resist film formed using the actinic ray- or radiation-sensitive resin composition according to any one of [1] to [4].
[6] Step 1 of forming a resist film using the actinic ray- or radiation-sensitive resin composition according to any one of [1] to [4];
Step 2 of exposing the resist film in a pattern to light having a wavelength of 200 nm or less to generate a sensitizer;
Step 3 of flood-exposing the resist film obtained in Step 2 with light having a wavelength of more than 200 nm and sensitizing the sensitizer;
A pattern forming method comprising a step 4 of performing a development process using a developer on the resist film obtained in step 3 above to form a pattern,
When the composition used in the above step 1 is a composition that satisfies the above requirement 1, in the above step 2, the above resist film is pattern-exposed to light having a wavelength of 200 nm or less, and the onium salt XB, the above-mentioned A step of decomposing the photoacid generator XD or the sensitizing precursor XC to generate an acid, and generating a sensitizer from the sensitizer precursor XC by the action of the acid,
When the composition used in step 1 is a composition that satisfies requirement 2, in step 2, the resist film is pattern-exposed with light having a wavelength of 200 nm or less to form an onium salt structure in compound YB. Or a pattern forming method, which is a step of decomposing the photoacid generator YC to generate an acid and producing a sensitizer from the compound YB by the action of the acid.
[7] After the above step 2, further includes a heating step 2-A of heating the resist film obtained in step 2, or
After the above step 3, further includes a heating step 3-A of heating the resist film obtained in step 3, or
The pattern forming method according to [6], which includes both the above step 2-A and the above step 3-A.
[8] After the above step 4, the method according to [6] or [7] further includes step 4-A of rinsing the resist film obtained in the above step 4 using a rinsing liquid. The pattern formation method described.
[9] The developer solution is a chemical solution containing an organic solvent, or
After the above step 4, the method further includes a step 4-A of rinsing the resist film obtained in the above step 4 using a rinsing liquid, and the rinsing liquid contains an organic solvent. The pattern forming method according to [6] or [7], which is a chemical solution.
[10] The pattern forming method according to [9], wherein the chemical solution containing an organic solvent is a chemical solution containing two or more types of organic solvents.
[11] The pattern forming method according to [10], wherein the chemical solution containing the two or more organic solvents contains an organic solvent with a boiling point of 120° C. or higher.
[12] The chemical solution containing two or more organic solvents contains organic solvent A and organic solvent B,
The boiling point of the organic solvent A is higher than the boiling point of the organic solvent B,
The pattern forming method according to [10] or [11], wherein the ClogP value of the organic solvent A is larger than the ClogP value of the organic solvent B.
[13] A method for manufacturing an electronic device, comprising the pattern forming method according to any one of [6] to [12].

According to the present invention, it is possible to provide an actinic ray-sensitive or radiation-sensitive resin composition that can form a pattern with excellent resolution.
Further, according to the present invention, a resist film, a pattern forming method, and an electronic device manufacturing method can be provided.

The present invention will be explained in detail below.
Although the description of the constituent elements described below may be made based on typical embodiments of the present invention, the present invention is not limited to such embodiments.
Regarding the notation of groups (atomic groups) in this specification, unless it goes against the spirit of the present invention, the notation that does not indicate substituted or unsubstituted includes groups having a substituent as well as groups having no substituent. do. For example, the term "alkyl group" includes not only an alkyl group without a substituent (unsubstituted alkyl group) but also an alkyl group having a substituent (substituted alkyl group). Furthermore, the term "organic group" as used herein refers to a group containing at least one carbon atom.
Unless otherwise specified, the substituent is preferably a monovalent substituent.
In this specification, "active rays" or "radiation" include, for example, the bright line spectrum of a mercury lamp, far ultraviolet rays typified by excimer lasers, extreme ultraviolet (EUV), X-rays, and electron beams (EB: electron beam) etc. "Light" in this specification means actinic rays or radiation.
In this specification, "exposure" refers not only to exposure to the bright line spectrum of a mercury lamp, far ultraviolet rays typified by excimer lasers, extreme ultraviolet rays, X-rays, and EUV light, but also to electron beams and It also includes drawing using particle beams such as ion beams. Note that in this specification, "light irradiation" has the same meaning as exposure.
In the present specification, "~" is used to include the numerical values described before and after it as a lower limit value and an upper limit value.
The direction of bonding of the divalent groups described herein is not limited unless otherwise specified. For example, when Y in the compound represented by the formula "X-Y-Z" is -COO-, Y may be -CO-O- or -O-CO- Good too. Further, the above compound may be "X-CO-O-Z" or "X-O-CO-Z".

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) apparatus (HLC-8120GPC manufactured by Tosoh). ) GPC measurement (solvent: tetrahydrofuran, flow rate (sample injection amount): 10 μL, column: Tosoh TSK gel Multipore HXL-M, column temperature: 40°C, flow rate: 1.0 mL/min, detector: differential refractive index Defined as a polystyrene equivalent value determined by a Refractive Index Detector.

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

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

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

As mentioned above, pKa in this specification refers to a value obtained by calculating a value based on Hammett's substituent constant and a database of known literature values using software package 1. If calculation is not possible, a value obtained by Gaussian 16 based on DFT (density functional theory) is used.
In addition, pKa in this specification refers to "pKa in an aqueous solution" as mentioned above, but if pKa in an aqueous solution cannot be calculated, "pKa in dimethyl sulfoxide (DMSO) solution" is adopted. It shall be.

In this specification, examples of the halogen atom include a fluorine atom, a chlorine atom, a bromine atom, and an iodine atom.

In this specification, the solid content is intended to be a component that forms a resist film, and does not include a solvent. Furthermore, if the component forms a resist film, it is considered to be a solid component even if the component is liquid.

In this specification, boiling point means the boiling point under 1 atmosphere (760 mmHg).

[[Acinic ray-sensitive or radiation-sensitive resin composition]]
The actinic ray-sensitive or radiation-sensitive resin composition (hereinafter also referred to as "composition") of the present invention satisfies Requirement 1 or Requirement 2 below.
[Requirement 1]
The above composition includes a resin XA, an onium salt XB (hereinafter abbreviated as "onium salt XB") that generates an acid upon irradiation with light, and a sensitizer precursor XC (hereinafter abbreviated as "onium salt XB") that generates a sensitizer by the action of the acid. (hereinafter abbreviated as "sensitizer precursor XC"),
The resin XA has an interactive group that interacts with the onium salt XB, or the resin XA and the onium salt XB are bonded via a covalent bond,
The onium salt XB is a compound that acts on the sensitizer precursor XC to generate an acid capable of producing a sensitizer, or
When the onium salt XB is a compound that does not generate an acid capable of producing a sensitizer by acting on the sensitizer precursor XC, the composition further acts on the sensitizer precursor XC. It contains a photoacid generator XD (hereinafter abbreviated as "photoacid generator XD") capable of generating an acid capable of producing a sensitizer, or the sensitizer precursor generates an acid capable of producing an agent;
The content of repeating units having a group that decomposes under the action of acid to produce a polar group (hereinafter also referred to as "acid-decomposable group") in the resin XA is based on the total repeating units of the resin XA, It is 0 to 20 mol%.
Note that the sensitizer precursor XC may be bonded to the resin XA via a covalent bond. Further, the photoacid generator XD may be bonded to the resin XA via a covalent bond.

In addition, "the content of repeating units having an acid-decomposable group in resin XA is 0 to 20 mol% with respect to all repeating units of resin XA" means that resin XA is acid-decomposable If the resin XA does not contain a repeating unit having a group, or if the resin XA contains a repeating unit having an acid-decomposable group, the content of the repeating unit having an acid-decomposable group is 20 It is intended to be less than or equal to mol%.

[Requirement 2]
Comprising resin YA and compound YB (hereinafter abbreviated as "compound YB"), which has an onium salt structure that generates an acid upon light irradiation and generates a sensitizer by the action of the acid,
The resin YA has an interactive group that interacts with the compound YB, or the resin YA and the compound YB are bonded via a covalent bond,
The onium salt structure is a structure that generates the acid that can generate the sensitizer, or
When the onium salt structure is not a structure that generates the acid that can generate the sensitizer, the composition further includes a photoacid generator YC (hereinafter referred to as "photoacid generator") that can generate the acid that can generate the sensitizer. (abbreviated as “acid generator YC”),
The content of repeating units having a group that decomposes under the action of an acid to produce a polar group (hereinafter also referred to as "acid-decomposable group") in the resin YA is based on the total repeating units of the resin YA. It is 0 to 20 mol%.
Note that the photoacid generator YC may be bonded to the resin YA via a covalent bond.

Note that "the content of repeating units having acid-decomposable groups in resin YA is 0 to 20 mol% with respect to all repeating units of resin YA" means that resin YA is acid-decomposable If the resin YA does not contain a repeating unit having a group, or if the resin YA contains a repeating unit having an acid-decomposable group, the content of the repeating unit having an acid-decomposable group is 20% of the total repeating units of the resin YA. It is intended to be less than or equal to mol%.

With the above structure, the resist composition of the present invention can form a pattern with excellent resolution.
The assumed mechanism of action of the resist composition of the present invention will be explained below.
The resist film formed from the composition of the present invention is characterized in that a resin and an onium salt or a predetermined compound containing an onium salt structure in its molecule interact with an interactive group contained in the resin and an onium salt or an onium salt contained in the predetermined compound. The resin exists by forming an association structure (hereinafter abbreviated as "association structure") due to electrostatic interaction with the structure, or the resin and the onium salt or a predetermined compound containing an onium salt structure in the molecule They exist as a single body (hereinafter also referred to as a "combined body") by being bound through covalent bonds. In other words, in the resist film formed from the composition of requirement 1, resin XA and onium salt XB exist by forming an association structure due to electrostatic interaction between the interactive group contained in resin XA and onium salt XB. or the resin XA and the onium salt XB exist as a conjugate (if the resin XA has an interactive group, in the conjugate, the interactive group of the resin XA and the onium salt XB (A further association structure may also be formed between the two.) In the resist film formed from the composition of requirement 2, resin YA and compound YB form an association structure due to electrostatic interaction between the interactive group of resin YA and the onium salt structure in compound YB. or the resin YA and the compound YB exist as a conjugate (if the resin YA has an interactive group, in the conjugate, the interactive group of the resin YA and the compound YB Furthermore, an associated structure may also be formed with the onium salt structure in the molecule).
When the resist film is subjected to Step 2 (pattern exposure step) described below, first, a sensitizer is generated from the sensitizer precursor XC or compound YB contained in the resist composition (requirement 1 In the resist film formed by the composition, a sensitizer is generated from the sensitizer precursor XC by the action of the onium salt XB, the photoacid generator XD, or the acid generated by the sensitizer precursor XC. Furthermore, in the resist film formed using the composition of requirement 2, a sensitizer is generated from compound YB by the action of the acid generated by compound YB or the photoacid generator YC). In step 2 (pattern exposure step), by controlling the exposure amount, in the exposed region, the lower molecular weight and polarity change of the resin occur due to release of the association structure described below and cleavage of the onium salt or onium salt structure in the above-mentioned bond. The progression of the disease is generally suppressed. That is, in the exposed region of step 2 (pattern exposure step), only a part of the acid-generating component is cleaved, and a sensitizer can be generated from the sensitizer precursor.
Next, when the resist film is subjected to Step 3 (flood exposure) described below, the onium salt or onium salt structure is selectively cleaved in the exposed region of Step 2 (pattern exposure step) due to the action of the sensitizer. The molecular weight of the resin decreases and the polarity changes due to the release of the association structure or the cleavage of the onium salt or onium salt structure in the bond. On the other hand, in the non-exposed region in step 2 (pattern exposure step), the sensitizer is not produced, so the above-mentioned association structure is released due to the cleavage of the onium salt or the onium salt structure, or the above-mentioned association structure in the above-mentioned conjugate is Lower molecular weight and polarity change of the resin due to cleavage of the onium salt or onium salt structure do not proceed.
Due to the above mechanism of action, a difference in solubility in the developer (dissolution contrast) occurs between the exposed area and the unexposed area in step 2 (pattern exposure process) of the resist film, resulting in a pattern with excellent resolution. It becomes possible to form

Hereinafter, the fact that the effect of resolution (limit resolution) is more excellent is also referred to as "the effect of the present invention is more excellent."

Below, the composition meeting requirement 1 and the composition meeting requirement 2 will be explained for each composition.

[Composition of requirement 1]
An example of an embodiment of a composition satisfying Requirement 1 will be shown below.
・Aspect X1
A composition comprising a resin XA, an onium salt XB, and a sensitizer precursor XC,
The resin XA has an interactive group that interacts with the onium salt XB,
The onium salt XB is a compound that acts on the sensitizer precursor XC to generate an acid capable of producing a sensitizer,
The content of the repeating unit having a group that decomposes to produce a polar group under the action of an acid in the resin XA is 0 to 20 mol % based on the total repeating units of the resin XA.
・Aspect X2
A composition comprising a resin XA, an onium salt XB, and a sensitizer precursor XC,
The resin XA has an interactive group that interacts with the onium salt XB,
The onium salt XB is a compound that does not generate an acid capable of producing a sensitizer by acting on the sensitizer precursor XC, and the composition further contains a photoacid generator XD, or The sensitizer precursor XC generates an acid capable of producing a sensitizer upon irradiation with light,
The content of the repeating unit having a group that decomposes to produce a polar group under the action of an acid in the resin XA is 0 to 20 mol % based on the total repeating units of the resin XA.
・Aspect X3
A composition comprising a resin XA, an onium salt XB, and a sensitizer precursor XC,
The resin XA and the onium salt XB are bonded via a covalent bond,
The onium salt XB is a compound that acts on the sensitizer precursor XC to generate an acid capable of producing a sensitizer,
The content of the repeating unit having a group that decomposes to produce a polar group under the action of an acid in the resin XA is 0 to 20 mol % based on the total repeating units of the resin XA.
・Aspect X4
A composition comprising a resin XA, an onium salt XB, and a sensitizer precursor XC,
The resin XA and the onium salt XB are bonded via a covalent bond,
The onium salt XB is a compound that does not generate an acid capable of producing a sensitizer by acting on the sensitizer precursor XC, and the composition further contains a photoacid generator XD, or The sensitizer precursor XC generates an acid capable of producing the sensitizer by light irradiation,
The content of the repeating unit having a group that decomposes to produce a polar group under the action of an acid in the resin XA is 0 to 20 mol % based on the total repeating units of the resin XA.

Note that in embodiments X1 to X4, the sensitizer precursor XC may be bonded to the resin XA via a covalent bond. Moreover, the photoacid generator XD may be bonded to the resin XA via a covalent bond.

In addition, when the onium salt XB is bonded to the resin XA via a covalent bond, the composition includes a resin in which the resin XA and the onium salt XB are bonded via a covalent bond.
Furthermore, when the sensitizer precursor XC is bonded to the resin XA via a covalent bond, the composition includes a resin in which the resin XA and the sensitizer precursor XC are bonded via a covalent bond.
In addition, when the photoacid generator XD is bonded to the resin XA via a covalent bond, the composition includes a resin in which the resin XA and the photoacid generator XD are bonded via a covalent bond.

[Composition of aspect X1]
Hereinafter, various components included in aspect X1 will be explained.

<Resin XA>
(interactive group)
Resin XA has an interactive group that interacts (for example, electrostatic interaction) with onium salt XB, which will be described later.
The interactive group is preferably a group capable of forming an association structure through interaction with the onium salt XB, and more preferably a group having proton donor properties or proton acceptor properties. The group having proton donor properties is a group having a free hydrogen atom, and the group having proton acceptor properties includes, for example, a group having a lone pair of electrons such as a nitrogen atom and an oxygen atom. As the interactive group, a phenolic hydroxyl group, a carboxy group, a sulfonic acid group, an amide group, or a sulfonamide group is particularly preferable, since the interaction with the onium salt XB is more excellent.
The above-mentioned phenolic hydroxyl group refers to a hydroxyl group substituted on a ring member atom of an aromatic ring.
The aromatic ring is not limited to a benzene ring, and may be either an aromatic hydrocarbon ring or an aromatic heterocycle. Moreover, the aromatic ring may be either monocyclic or polycyclic.

The above amide group is not particularly limited, but includes, for example, -C(=O)-NHR ^A and -NH-C(=O) ^{-RA (RA} ^is a hydrogen atom or an alkyl group having 1 to 5 carbon atoms). ).
The above-mentioned sulfonamide group is not particularly limited, but includes, for example, -S(=O) ₂ -NHR ^B (R ^B represents a hydrogen atom or an alkyl group having 1 to 5 carbon atoms).

(Repeating unit with acid-decomposable group)
The resin XA may include a repeating unit having a group (acid-decomposable group) that decomposes under the action of an acid to produce a polar group. However, when resin XA contains a repeating unit having an acid-decomposable group, its content is 20 mol% or less, preferably 15 mol% or less, and 10 mol% or less, based on the total repeating units of resin XA. The following is more preferable, 5 mol% or less is still more preferable, and 3 mol% or less is particularly preferable. Note that the lower limit is 0 mol% or more.

The acid-decomposable group typically has a structure in which a polar group is protected by a leaving group that is eliminated by the action of an acid, and includes, for example, those having the following structure.
The polar group is preferably an alkali-soluble group, such as carboxyl group, phenolic hydroxyl group, fluorinated alcohol group, sulfonic acid group, phosphoric acid group, sulfonamide group, 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) Examples include acidic groups such as methylene group and tris(alkylsulfonyl)methylene group, and alcoholic hydroxyl group.
As the polar group, a carboxyl group, a phenolic hydroxyl group, a fluorinated alcohol group (preferably a hexafluoroisopropanol group), or a sulfonic acid group is particularly preferable.

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

In formulas (Y1) and (Y2), Rx ₁ to Rx ₃ each independently represent an alkyl group (linear or branched chain), a cycloalkyl group (monocyclic or polycyclic), an alkenyl group (straight chain or branched chain), or an aryl group (monocyclic or polycyclic). Note that when all of Rx ₁ to Rx ₃ are alkyl groups (linear or branched), it is preferable that at least two of Rx ₁ to Rx ₃ are methyl groups.
Among these, it is preferable that Rx ₁ to Rx ₃ each independently represent a linear or branched alkyl group, and Rx ₁ to Rx ₃ each independently represent a linear alkyl group. is more preferable.
Two of Rx ₁ to Rx ₃ may be combined to form a monocyclic ring or a polycyclic ring.
As the alkyl group for Rx ₁ to Rx ₃ , an alkyl group having 1 to 5 carbon atoms such as a methyl group, ethyl group, n-propyl group, isopropyl group, n-butyl group, isobutyl group, and t-butyl group is preferable. .
Examples of the cycloalkyl group for Rx ₁ to Rx ₃ include monocyclic cycloalkyl groups such as cyclopentyl group and cyclohexyl group, and polycyclic groups such as norbornyl group, tetracyclodecanyl group, tetracyclododecanyl group, and adamantyl group. A cycloalkyl group is preferred.
The aryl group for Rx ₁ to Rx ₃ is preferably an aryl group having 6 to 10 carbon atoms, such as a phenyl group, a naphthyl group, an anthryl group, and the like.
As the alkenyl group for Rx ₁ to Rx ₃ , a vinyl group is preferred.
The ring formed by bonding two of Rx ₁ to Rx ₃ is preferably a cycloalkyl group. The cycloalkyl group formed by combining two of Rx ₁ to Rx ₃ is a cyclopentyl group or a monocyclic cycloalkyl group such as 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 a monocyclic cycloalkyl group having 5 to 6 carbon atoms is more preferable.
The cycloalkyl group formed by bonding two of Rx ₁ to Rx ₃ is, for example, a group in which one of the methylene groups constituting the ring has a hetero atom such as an oxygen atom, a hetero atom such as a carbonyl group, or a group in which one of the methylene groups constituting the ring has a hetero atom such as a carbonyl group, or May be substituted with a group. Further, in these cycloalkyl groups, one or more of the ethylene groups constituting the cycloalkane ring may be replaced with a vinylene group.
The group represented by formula (Y1) or formula (Y2) is, for example, an embodiment in which Rx ₁ is a methyl group or an ethyl group, and Rx ₂ and Rx ₃ are bonded to form the above-mentioned cycloalkyl group. is preferred.

In formula (Y3), R ₃₆ to R ₃₈ each independently represent a hydrogen atom or a monovalent organic group. R ₃₇ and R ₃₈ may be combined with each other to form a ring. Examples of monovalent organic groups include alkyl groups, cycloalkyl groups, aryl groups, aralkyl groups, and alkenyl groups. It is also preferable that R ₃₆ is a hydrogen atom.
Note that the above alkyl group, cycloalkyl group, aryl group, and aralkyl group may contain a group having a hetero atom such as an oxygen atom and/or a hetero atom such as a carbonyl group. For example, in the above alkyl group, cycloalkyl group, aryl group, and aralkyl group, one or more methylene groups are replaced with a group having a hetero atom such as an oxygen atom and/or a hetero atom such as a carbonyl group. Good too. Examples of such groups include alkylcarbonyl groups and the like.

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

Here, L ₁ and L ₂ each independently represent a hydrogen atom, an alkyl group, a cycloalkyl group, an aryl group, or a group combining these (for example, a group combining an alkyl group and an aryl group).
M represents a single bond or a divalent linking group.
Q is an alkyl group that may contain a hetero atom, a cycloalkyl group that may contain a hetero atom, an aryl group that may contain a hetero atom, an amino group, an ammonium group, a mercapto group, a cyano group, an aldehyde represents a group or a group combining these (for example, a group combining an alkyl group and a cycloalkyl group).
In the alkyl group and cycloalkyl group, for example, one of the methylene groups may be replaced with a hetero atom such as an oxygen atom, or a group having a hetero atom such as a carbonyl group.
It is preferable that one of L ₁ and L ₂ is a hydrogen atom, and the other is an alkyl group, a cycloalkyl group, an aryl group, or a combination of an alkylene group and an aryl group.
At least two of Q, M, and L ₁ may be combined to form a ring (preferably a 5-membered or 6-membered ring).

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

Other leaving groups that are eliminated by the action of acids include 2-cyclopentenyl groups having substituents (alkyl groups, etc.) such as 3-methyl-2-cyclopentenyl groups, and 1,1,4, It may also be a cyclohexyl group having a substituent (alkyl group, etc.) such as 4-tetramethylcyclohexyl group.

(Preferred embodiment of resin XA)
As the resin XA, it is preferable to use a resin (main chain cleaved resin) whose main chain is cleaved by the action of exposure, acid, base, or heating and whose molecular weight decreases, since the effects of the present invention are more excellent. . Examples of the resin XA, which is a main chain cleavage type resin, include resin XA-1.

《Resin XA-1》
Resin XA-1 contains an interactive group, and includes a repeating unit represented by the following formula (XP) and a repeating unit represented by the following formula (XQ). However, when resin XA-1 contains a repeating unit having an acid-decomposable group, its content is 20 mol% or less based on all repeating units.
Note that in resin XA-1, the interactive group may be contained in any position. In resin XA-1, the interactive group may be contained in the repeating unit represented by formula (XP) and/or the repeating unit represented by formula (XQ), or may be contained in the repeating unit represented by formula (XP). and the repeating unit represented by formula (XQ), and the other repeating unit may contain an interactive group.

In formula (XP), X ^p represents a halogen atom. L ^p represents a single bond or a divalent linking group. R ^p represents a substituent.

In formula (XQ), R ^q1 represents an alkyl group that may have a substituent. L ^q represents a single bond or a divalent linking group. R ^q2 represents a substituent.

In the resin XA-1, at least one of the substituent represented by R ^p in formula (XP) and the substituent represented by R ^q2 in formula (XQ) has an interactive group, Alternatively, it is preferable that it contains a repeating unit other than the repeating unit represented by the formula (XP) and the repeating unit represented by the formula (XQ), and the other repeating unit has an interactive group.

In resin XA-1, the total content of the repeating unit represented by the above formula (XP) and the repeating unit represented by the above formula (XQ) is 90 mol% or more based on all repeating units. The content is preferably 95 mol% or more, and more preferably 95 mol% or more. In addition, as an upper limit, 100 mol% or less is preferable.

In addition, in resin XA-1, the repeating unit represented by the above formula (XP) and the repeating unit represented by the above formula (XQ) are a random copolymer, a block copolymer, and an alternating copolymer ( It may be in any form such as ABAB...), but among these, an alternating copolymer is preferable.
A preferred embodiment of the resin XA-1 is an embodiment in which the proportion of the alternating copolymer in the resin X is 90% by mass or more (preferably 100% by mass or more) based on the total mass of the resin XA-1. Certain embodiments may also be mentioned.

In resin XA-1, the content of the repeating unit represented by the above formula (XP) is preferably 10 to 90 mol%, and preferably 30 to 70 mol%, based on the total repeating units. More preferred. In resin XA-1, the repeating unit represented by the above formula (XQ) preferably accounts for 10 to 90 mol%, more preferably 30 to 70 mol%, based on all repeating units. .

In the resin XA-1, only one type of repeating unit represented by the above formula (XP) may be included, or two or more types may be included. In addition, only one type of repeating unit represented by the above formula (XQ) may be included, or two or more types may be included.

In the above formula (XP), the halogen atom represented by ^Xp is preferably a fluorine atom or a chlorine atom, and more preferably a chlorine atom, since the effects of the present invention are more excellent.
In the above formula (XP), the divalent linking group represented by L ^p is not particularly limited, but includes, for example, -CO-, -O-, -SO-, -SO ₂ -, -NR ^A -, alkylene group (preferably has 1 to 6 carbon atoms, may be linear or branched), cycloalkylene group (preferably has 3 to 15 carbon atoms), divalent aromatic hydrocarbon ring group (6 to 10-membered ring) (6-membered rings are preferred, and 6-membered rings are more preferred), and divalent linking groups that are a combination of a plurality of these. Further, the alkylene group, the cycloalkylene group, and the divalent aromatic hydrocarbon ring group may have a substituent. Examples of the substituent include an alkyl group, a halogen atom, and a hydroxyl group. Examples of R ^A include a hydrogen atom or an alkyl group having 1 to 6 carbon atoms.
A preferred embodiment of the divalent linking group represented by L ^p is an embodiment in which the position bonded to the main chain in the divalent linking group represented by L ^p is -COO-.

In the above formula (XP), the substituent represented by R ^p is not particularly limited and includes, for example, an alkyl group, a cycloalkyl group, an aryl group, an aralkyl group, an alkenyl group, an alkoxy group, an acyloxy group, a cyano group, a nitro groups, halogen atoms, ester groups (-OCOR'' or -COOR'': R'' represents an alkyl group or a fluorinated alkyl group), lactone groups, alcoholic hydroxyl groups, interactive groups, etc. It will be done.
Note that the alcoholic hydroxyl group is to be distinguished from the phenolic hydroxyl group, and in this specification, a hydroxyl group that is substituted for an aliphatic hydrocarbon group is intended.

The alkyl group, cycloalkyl group, aryl group, aralkyl group, alkenyl group, alkoxy group, acyloxy group, ester group, and lactone group may further have a substituent. Examples of substituents include halogen atoms and interactive groups. Note that when the alkyl group has a fluorine atom, it may be a perfluoroalkyl group.

The alkyl group may be either linear or branched. Further, the number of carbon atoms is not particularly limited, but is preferably from 1 to 20, more preferably from 1 to 10, and even more preferably from 1 to 6.
The above cycloalkyl group may be monocyclic or polycyclic. Further, the number of carbon atoms is not particularly limited, but is preferably from 5 to 15, more preferably from 5 to 10, for example. Examples of the cycloalkyl group include monocyclic cycloalkyl groups such as cyclopentyl group and cyclohexyl group, and polycyclic cycloalkyl groups such as norbornyl group, tetracyclodecanyl group, tetracyclododecanyl group, and adamantyl group. .
The above aryl group may be monocyclic or polycyclic. Further, the number of carbon atoms is not particularly limited, but is preferably 6 to 15, more preferably 6 to 10. As the aryl group, a phenyl group, a naphthyl group, or an anthranyl group is preferable, and a phenyl group is more preferable.
The aralkyl group preferably has a structure in which one of the hydrogen atoms in the alkyl group described above is substituted with the aryl group described above. The number of carbon atoms in the aralkyl group is preferably 7 to 20, more preferably 7 to 15.
The alkenyl group may be linear, branched, or cyclic. Further, the number of carbon atoms is not particularly limited, but is preferably from 2 to 20, more preferably from 2 to 10, even more preferably from 2 to 6.
The alkoxy group may be linear, branched, or cyclic, and has preferably 1 to 20 carbon atoms, more preferably 1 to 10 carbon atoms, and even more preferably 1 to 6 carbon atoms.
The above acyloxy group may be linear, branched, or cyclic, and has preferably 2 to 20 carbon atoms, more preferably 2 to 10 carbon atoms, and still more preferably 2 to 6 carbon atoms.
Further, the number of carbon atoms in the alkyl group or fluorinated alkyl group represented by R'' is preferably 1 to 20, more preferably 1 to 10, and even more preferably 1 to 6.
The lactone group is preferably a 5- to 7-membered lactone group, more preferably one in which another ring structure is fused to the 5- to 7-membered lactone ring to form a bicyclo structure or a spiro structure.
The interactive group is as described above.

The repeating unit represented by formula (XP) is preferably a repeating unit represented by formula (XP1) below.

In formula (XP1), X ^p1 has the same meaning as X ^p in formula (XP) above, and preferred embodiments are also the same.

Y ^p1 represents a single bond or -COO-.

L ^p1 represents a single bond or a divalent linking group.
The divalent linking group represented by L ^p1 is not particularly limited, but includes, for example, -CO-, -O-, -SO-, -SO ₂ -, -NR ^A -, alkylene group (preferably one carbon number to 6) (which may be linear or branched), and divalent linking groups that are a combination of two or more of these. Further, the alkylene group may have a substituent. Examples of the substituent include a halogen atom and a hydroxyl group. Examples of R ^A include a hydrogen atom or an alkyl group having 1 to 6 carbon atoms.

Ar ^p1 represents a (p2+1)-valent aromatic ring group or alicyclic group.
When p2 is 1, the divalent aromatic ring group includes, for example, an arylene group having 6 to 18 carbon atoms such as a phenylene group, tolylene group, naphthylene group, and anthracenylene group, or a thiophene ring, a furan ring, and a pyrrole ring. , a benzothiophene ring, a benzofuran ring, a benzopyrrole ring, a triazine ring, an imidazole ring, a benzimidazole ring, a triazole ring, a thiadiazole ring, and a divalent aromatic ring group containing a heterocycle such as a thiazole ring. Among these, an arylene group is preferred, a phenylene group, a naphthalene group, or an anthracenylene group is more preferred, and a phenylene group or a naphthalene group is even more preferred.

Specific examples of (p2+1)-valent aromatic ring groups in the case where p2 is an integer of 2 or more include (p2-1) arbitrary hydrogen atoms removed from the above-mentioned specific examples of divalent aromatic ring groups. The following groups are mentioned.

The (p2+1)-valent alicyclic group represented by Ar ^p1 may contain a heteroatom such as an oxygen atom or a carbonyl carbon. The (p2+1)-valent alicyclic group represented by Ar ^p1 is, for example, one in which (p2+1) arbitrary hydrogen atoms are removed from polycyclic cycloalkanes such as norbornene, tetracyclodecane, tetracyclododecane, and adamantane. The following groups are mentioned. Further, the (p2+1)-valent alicyclic group represented by Ar ^p1 includes a group obtained by removing (p2+1) arbitrary hydrogen atoms from a lactone ring or a sultone ring. The lactone ring and sultone ring are preferably 5- to 7-membered lactone rings and sultone rings, and other ring structures are fused to the 5- to 7-membered lactone and sultone rings to form a bicyclo or spiro structure. A ring is more preferable.

The (p2+1)-valent aromatic ring group and alicyclic group may have a substituent other than R ^p1 .

p1 represents 0 or 1.
If p1 is 0, p2 represents 1. When p1 is 1, p2 represents an integer from 0 to 4.

R ^p1 represents a substituent. Examples of the substituent represented by R ^p1 include those similar to R ^p in the above formula (XP), and among them, an alkyl group or an interactive group which may have a substituent is preferable. As the substituent, a halogen atom is preferred.

In formula (XQ), the alkyl group represented by R ^q1 may be linear, branched, or cyclic. The number of carbon atoms in the alkyl group is preferably 1 to 12, more preferably 1 to 6, and even more preferably 1 to 3.
Further, the alkyl group represented by R ^q1 may have a substituent. Substituents include, but are not particularly limited to, halogen atoms, hydroxyl groups, and the like.
In the formula (XQ), the divalent linking group represented by ^Lq includes the same divalent linking group as the divalent linking group represented by ^Lp in the above formula (XP).
In formula (XQ), the substituent represented by R ^q2 includes the same substituent as the substituent represented by R ^p in formula (XP) above.

The repeating unit represented by formula (XQ) is preferably a repeating unit represented by formula (XQ1) below.

In formula (XQ1), R ^q11 has the same meaning as R ^q1 in formula (XQ) above, and preferred embodiments are also the same.

Y ^q1 represents a single bond or -COO-.

L ^q1 represents a single bond or a divalent linking group.
The divalent linking group represented by L ^q1 is not particularly limited, but includes, for example, -CO-, -O-, -SO-, -SO ₂ -, -NR ^A -, alkylene group (preferably one carbon number to 6) (which may be linear or branched), and divalent linking groups that are a combination of two or more of these. Further, the alkylene group may have a substituent. Examples of the substituent include a halogen atom and a hydroxyl group. Examples of R ^A include a hydrogen atom or an alkyl group having 1 to 6 carbon atoms.

Ar ^q1 represents a (q2+1)-valent aromatic ring group or alicyclic group.
Examples of the divalent aromatic ring group when q2 is 1 include arylene groups having 6 to 18 carbon atoms such as phenylene group, tolylene group, naphthylene group, and anthracenylene group, or thiophene ring, furan ring, and pyrrole ring. , a benzothiophene ring, a benzofuran ring, a benzopyrrole ring, a triazine ring, an imidazole ring, a benzimidazole ring, a triazole ring, a thiadiazole ring, and a divalent aromatic ring group containing a heterocycle such as a thiazole ring. Among these, an arylene group is preferred, and a phenylene group or a naphthalene group is more preferred.

As a specific example of a (q2+1)-valent aromatic ring group when q2 is an integer of 2 or more, (q2-1) arbitrary hydrogen atoms are removed from the above-mentioned specific example of a divalent aromatic ring group. The following groups are mentioned.

The (q2+1)-valent alicyclic group represented by Ar ^q1 may contain a heteroatom such as an oxygen atom or a carbonyl carbon. The (q2+1)-valent alicyclic group represented by Ar ^q1 includes, for example, polycyclic cycloalkanes such as norbornene, tetracyclodecane, tetracyclododecane, and adamantane from which (q2+1) arbitrary hydrogen atoms have been removed. The following groups are mentioned. Further, the (q2+1)-valent alicyclic group represented by Ar ^q1 includes a group obtained by removing (q2+1) arbitrary hydrogen atoms from a lactone ring or a sultone ring. The lactone ring and sultone ring are preferably 5- to 7-membered lactone rings and sultone rings, and other ring structures are fused to the 5- to 7-membered lactone ring and sultone ring to form a bicyclo structure or a spiro structure. A ring is more preferable.

The (q2+1)-valent aromatic ring group and alicyclic group may have a substituent other than R ^q12 .

q1 represents 0 or 1.
If q1 is 0, q2 represents 1. When q1 is 1, q2 represents an integer from 0 to 4.

R ^q12 represents a substituent. Examples of the substituent represented by R ^q12 include those similar to R ^p in the above formula (XP), and among them, an alkyl group or an interactive group which may have a substituent is preferable. As the substituent, a halogen atom is preferred.

The above-mentioned resin XA-1 may contain repeating units other than the above-mentioned repeating units as long as the effects of the present invention are not impaired.

Resin XA can be synthesized by conventional methods (eg, radical polymerization).
The weight average molecular weight (Mw) of the resin XA is preferably 15,000 or more, more preferably 20,000 or more, even more preferably 30,000 or more, and particularly preferably 40,000 or more. The upper limit is, for example, preferably 200,000 or less, more preferably 150,000 or less, and even more preferably 100,000 or less.

The polydispersity (Mw/Mn) of the resin XA is not particularly limited, but is preferably 2.5 or less, more preferably 2.0 or less, and even more preferably 1.7 or less. The lower limit value is not particularly limited, and may be 1.0 or more.

In the composition of aspect X1, the lower limit of the content of resin XA is preferably 30.0% by mass or more, more preferably 45.0% by mass or more, and 65.0% by mass based on the total solid content of the composition. % or more is more preferable. In addition, as an upper limit, 99.9 mass % or less is preferable, for example. Moreover, resin XA may be used alone or in combination. When two or more types are used, it is preferable that the total content is within the above-mentioned preferred content range.

<Onium salt XB>
The composition of embodiment X1 comprises onium salt XB. Onium salt XB is an onium salt compound (photodegradable onium salt compound) that generates an acid upon irradiation with light.
Specifically, the onium salt XB is preferably a compound that has at least one salt structure site composed of an anion site and a cation site and is decomposed by light irradiation to generate an acid. The above-mentioned salt structure part of onium salt It is preferable that it consists of a part.
The above-mentioned salt structure site may be a part of the onium salt XB or the entire onium salt XB. In addition, the case where the salt structure site is a part of the onium salt XB corresponds to, for example, a structure in which two or more salt structure sites are connected.
The number of salt structural moieties in onium salt XB is not particularly limited, but is preferably 1 to 10, more preferably 1 to 6, and even more preferably 1 to 3.

Examples of organic acids generated from onium salt XB upon irradiation with light include sulfonic acids (aliphatic sulfonic acids, aromatic sulfonic acids, camphor sulfonic acids, etc.), carbonylsulfonylimidic acids, bis(alkylsulfonyl)imide acids, and tris(alkylsulfonyl)methide acid.
Note that the acid generated from the onium salt XB upon light irradiation may be an inorganic acid (for example, a hydroxide ion).
Further, the organic acid generated from the onium salt XB by light irradiation may be a polyacid having two or more acid groups.

In onium salt XB, the cation moiety constituting the salt structure moiety is preferably an organic cation moiety, particularly an organic cation (cation (ZaI)) represented by the formula (ZaI) or a formula (ZaII). The organic cation represented (cation (ZaII)) is preferred.

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 preferably 1 to 30, more preferably 1 to 20. Furthermore, two of R ²⁰¹ to R ²⁰³ may be combined to form a ring structure, and the ring may contain an oxygen atom, a sulfur atom, an ester group, an amide group, or a carbonyl group. Examples of the group formed by combining two of R ²⁰¹ to R ²⁰³ include an alkylene group (for example, a butylene group and a pentylene group), and -CH ₂ -CH ₂ -O-CH ₂ -CH ₂ -. Can be mentioned.

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

First, the cation (ZaI-1) will be explained.
The cation (ZaI-1) is an arylsulfonium cation in which at least one of R ²⁰¹ to R ²⁰³ in the above formula (ZaI) is an aryl group.
In the arylsulfonium cation, all of R ²⁰¹ to R ²⁰³ may be an aryl group, or some of R ²⁰¹ to R ²⁰³ may be an aryl group, and the remainder may be an alkyl group or a cycloalkyl group.
Further, one of R ²⁰¹ to R ²⁰³ may be an aryl group, and the remaining two of R ²⁰¹ to R ²⁰³ may be bonded to form a ring structure, with an oxygen atom, a sulfur atom, It may contain an ester group, an amide group, or a carbonyl group. The group formed by combining two of R ²⁰¹ to R ²⁰³ includes, for example, one or more methylene groups substituted with an oxygen atom, a sulfur atom, an ester group, an amide group, and/or a carbonyl group. and alkylene groups (eg, butylene group, pentylene group, or -CH ₂ -CH ₂ -O-CH ₂ -CH ₂ -).
Examples of the arylsulfonium cation include triarylsulfonium cation, diarylalkylsulfonium cation, aryldialkylsulfonium cation, diarylcycloalkylsulfonium cation, and aryldicycloalkylsulfonium cation.

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

The substituents that the aryl group, alkyl group, and cycloalkyl group of R ²⁰¹ to R ²⁰³ may each independently include an alkyl group (for example, carbon number 1 to 15), a cycloalkyl group (for example, carbon number 3-15), aryl group (e.g. 6-14 carbon atoms), alkoxy group (e.g. 1-15 carbon atoms), cycloalkylalkoxy group (e.g. 1-15 carbon atoms), halogen atom (e.g. fluorine, iodine), hydroxyl group , a carboxyl group, an ester group, a sulfinyl group, a sulfonyl group, an alkylthio group, a phenylthio group, and the like.
The above substituent may further have a substituent if possible. For example, the above alkyl group may have a halogen atom as a substituent to become a halogenated alkyl group such as a trifluoromethyl group. preferable.

Next, the cation (ZaI-2) will be explained.
The cation (ZaI-2) is a cation in which R ²⁰¹ to R ²⁰³ in the formula (ZaI) each independently represent an organic group having no aromatic ring. Here, the aromatic ring includes an aromatic ring containing a hetero atom.
The carbon number of the organic group having no aromatic ring as R ²⁰¹ to R ²⁰³ is preferably 1 to 30, more preferably 1 to 20.
R ²⁰¹ to R ²⁰³ are each independently preferably an alkyl group, a cycloalkyl group, an allyl group, or a vinyl group, and a linear or branched 2-oxoalkyl group, a 2-oxocycloalkyl group, or an alkoxy A carbonylmethyl group is more preferred, and a linear or branched 2-oxoalkyl group is even more preferred.

Examples of the alkyl group and cycloalkyl group of R ²⁰¹ to R ²⁰³ include a linear alkyl group having 1 to 10 carbon atoms or a branched alkyl group having 3 to 10 carbon atoms (for example, methyl group, ethyl group, propyl group). group, butyl group, and pentyl group), and cycloalkyl groups having 3 to 10 carbon atoms (eg, cyclopentyl group, cyclohexyl group, and norbornyl group).
R ²⁰¹ to R ²⁰³ may be further substituted with a halogen atom, an alkoxy group (for example, having 1 to 5 carbon atoms), a hydroxyl group, a cyano group, or a nitro group.

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, and 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.

Any two or more of R _1c to R _5c , R _5c and R _6c , R _6c and R _7c , R _5c and R _x , and R _x and R _y may be bonded to each other to form a ring. Often, the rings may each independently contain an oxygen atom, a sulfur atom, a ketone group, an ester bond, or an amide bond.
Examples of the above-mentioned ring include an aromatic or non-aromatic hydrocarbon ring, an aromatic or non-aromatic heterocycle, and a polycyclic condensed ring formed by combining two or more of these rings. Examples of the ring include a 3- to 10-membered ring, preferably a 4- to 8-membered ring, and more preferably a 5- or 6-membered ring.

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

R _1c to R _5c , R _6c , R _7c , R _x , R _y , and 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 the ring formed by bonding R _x and R _y to 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 from 0 to 2.
r represents an integer from 0 to 8.
_R13 is a group having a hydrogen atom, a halogen atom (e.g., a fluorine atom, an iodine atom, etc.), a hydroxyl group, an alkyl group, a halogenated alkyl group, an alkoxy group, a carboxyl group, an alkoxycarbonyl group, or a cycloalkyl group (cycloalkyl It may be a group itself or a group partially containing a cycloalkyl group). These groups may have substituents.
_R14 is a hydroxyl group, a halogen atom (e.g., a fluorine atom, an iodine atom, etc.), an alkyl group, a halogenated alkyl group, an alkoxy group, an alkoxycarbonyl group, an alkylcarbonyl group, an alkylsulfonyl group, a cycloalkylsulfonyl group, or a cycloalkyl group. Represents a group having a group (which may be a cycloalkyl group itself or a group partially containing a cycloalkyl group). These groups may have substituents. When a plurality of R _14s exist, each R 14 independently represents the above group such as a hydroxyl group.
Each R ₁₅ independently represents an alkyl group, a cycloalkyl group, or a naphthyl group. Two R _15s may be bonded to each other to form a ring. When two R _15s combine with each other to form a ring, the ring skeleton may contain a heteroatom such as an oxygen atom or a nitrogen atom. In one embodiment, two R _15s are alkylene groups and are preferably bonded to each other to form a ring structure. The ring formed by bonding the alkyl group, cycloalkyl group, naphthyl group, and two R _15s to each other may have a substituent.

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

Next, formula (ZaII) will be explained.
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, and more preferably a phenyl group. The aryl group of R ²⁰⁴ and R ²⁰⁵ may be an aryl group having a heterocycle having an oxygen atom, a nitrogen atom, a sulfur atom, or the like. Examples of the skeleton of the aryl group having a heterocycle include pyrrole, furan, thiophene, indole, benzofuran, and benzothiophene.
The alkyl group and cycloalkyl group of R ²⁰⁴ and R ²⁰⁵ include a linear alkyl group having 1 to 10 carbon atoms or a branched alkyl group having 3 to 10 carbon atoms (for example, a methyl group, an ethyl group, a propyl group, butyl group or pentyl group), or a cycloalkyl group having 3 to 10 carbon atoms (eg, cyclopentyl group, cyclohexyl group, or norbornyl group).

The aryl group, alkyl group, and cycloalkyl group of R ²⁰⁴ and R ²⁰⁵ may each independently have a substituent. Examples of substituents that the aryl group, alkyl group, and cycloalkyl group of R ²⁰⁴ and R ²⁰⁵ may have include an alkyl group (for example, having 1 to 15 carbon atoms), a cycloalkyl group (for example, having 3 to 15 carbon atoms), 15), an aryl group (for example, having 6 to 15 carbon atoms), an alkoxy group (for example, having 1 to 15 carbon atoms), a halogen atom, a hydroxyl group, and a phenylthio group.

An example of a preferred embodiment of the onium salt XB is an onium salt compound represented by "M ⁺ X ^- ", which generates an organic acid upon irradiation with light (hereinafter also referred to as "onium salt .
In the compound represented by "M ⁺ X ^- ", M ⁺ represents an organic cation and X ^- represents an organic anion.
Onium salt XB1 will be explained below.

The organic cation represented by M ⁺ in onium salt )) is preferred.

The organic anion represented by X ^- in the onium salt XB1 is preferably a non-nucleophilic anion (an anion with extremely low ability to cause a nucleophilic reaction).
Examples of non-nucleophilic anions include sulfonate anions (aliphatic sulfonate anions, aromatic sulfonate anions, camphorsulfonate anions, etc.), sulfonylimide anions, bis(alkylsulfonyl)imide anions, and tris( Examples include alkylsulfonyl)methide anions.

The aliphatic moiety in the aliphatic sulfonic acid anion may be an alkyl group or a cycloalkyl group, and may be a linear or branched alkyl group having 1 to 30 carbon atoms, or a linear or branched alkyl group having 3 to 30 carbon atoms. A cycloalkyl group is preferred.
The alkyl group may be, for example, a fluoroalkyl group (which may or may not have a substituent other than a fluorine atom; it may also be a perfluoroalkyl group).

The aryl group in the aromatic sulfonic acid 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. Substituents are not particularly limited, but specifically include 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), Alkyl group (preferably 1 to 10 carbon atoms), cycloalkyl group (preferably 3 to 15 carbon atoms), aryl group (preferably 6 to 14 carbon atoms), alkoxycarbonyl group (preferably 2 to 7 carbon atoms), Acyl group (preferably 2 to 12 carbon atoms), alkoxycarbonyloxy group (preferably 2 to 7 carbon atoms), alkylthio group (preferably 1 to 15 carbon atoms), alkylsulfonyl group (preferably 1 to 15 carbon atoms) , an alkyliminosulfonyl group (preferably having 1 to 15 carbon atoms), and an aryloxysulfonyl group (preferably having 6 to 20 carbon atoms).

Examples of the sulfonylimide anion include saccharin anion.

The alkyl group in the bis(alkylsulfonyl)imide anion and tris(alkylsulfonyl)methide anion is preferably an alkyl group having 1 to 5 carbon atoms. Substituents for these alkyl groups include halogen atoms, alkyl groups substituted with halogen atoms, alkoxy groups, alkylthio groups, alkyloxysulfonyl groups, aryloxysulfonyl groups, and cycloalkylaryloxysulfonyl groups, and fluorine An alkyl group substituted with an atom or a fluorine atom is preferred.
Furthermore, the alkyl groups in the bis(alkylsulfonyl)imide anion may be bonded to each other to form a ring structure.

Onium salts It is also preferable to use the photoacid generators disclosed in paragraphs [0018] to [0075] and [0334] to [0335].

The molecular weight of the onium salt XB1 is preferably 3000 or less, more preferably 2000 or less, and even more preferably 1000 or less.

Furthermore, as the onium salt XB, in addition to the above-mentioned onium salt XB1, for example, compounds exemplified in paragraphs [0023] to [0095] of International Publication No. 2020/158313 can also be cited.

When the sensitizer precursor XC is a compound having a site that can be deprotected by the action of an acid, such as a ketal structure or an acetal structure as described below, in order to generate a carbonyl compound by the deprotection reaction, it is necessary to use the compound generated from the onium salt XB. The pKa of the generated acid is preferably 2.0 or less, more preferably 1.0 or less, and even more preferably 0.0 or less. Note that the lower limit is preferably −15.0 or more.

In the composition of aspect X1, the lower limit of the content of onium salt XB is preferably 0.5% by mass or more, more preferably 1.0% by mass or more, based on the total solid content of the composition.5. More preferably, it is 0% by mass or more. Further, the upper limit of the content is preferably 40.0% by mass or less, more preferably 30.0% by mass or less. Onium salts XB may be used alone or in combination of two or more. When two or more types are used, it is preferable that the total content is within the above-mentioned preferred content range.

<Sensitizer precursor XC>
The composition of embodiment X1 comprises a sensitizer precursor XC. The sensitizer precursor XC is a compound that generates a sensitizer by the action of an acid.
The sensitizer produced from the sensitizer precursor XC is preferably a sensitizer (photosensitizer) that absorbs light with a wavelength of more than 200 nm (preferably 250 nm or more). When the sensitizer produced from the sensitizer precursor XC has the above wavelength characteristics, in step 3 (flood exposure step) of the pattern forming method described below, the absorption wavelength of the sensitizer precursor XC itself and the sensitizer precursor The difference between the absorption wavelength of the sensitizer produced from the sensitizer precursor XC widens (in other words, the absorption wavelength shifts significantly before and after the structural change from the sensitizer precursor XC to the sensitizer), and the absorption wavelength of the sensitizer precursor XC increases. Unnecessary exposure to light can be suppressed. As a result, the sensitizer can be selectively exposed in step 3 (flood exposure step), and the resolution of the formed pattern is better.

The structure of the sensitizer produced from the sensitizer precursor XC is preferably a carbonyl compound, since the effects of the present invention are more excellent. Examples of the carbonyl compound include aldehydes, ketones, carboxylic acids or salts thereof (eg, chlorides), carboxylic acid anhydrides, and carboxylic acid esters. Further, the carbonyl compound is preferably a compound that absorbs light on the long wavelength side, exceeding a wavelength of 200 nm.
Examples of the carbonyl compound include benzophenone derivatives, xanthone derivatives, thioxanthone derivatives, coumarin derivatives, acridone derivatives, naphthalene derivatives, anthracene derivatives, and acridone derivatives.

The sensitizer precursor XC is preferably a compound that produces a sensitizer having the above-mentioned structure upon the action of an acid.
Such a sensitizer precursor XC includes an alcohol compound represented by the following formula (VI), a ketal compound, an acetal compound, or an orthoester compound in which the hydrogen atom of an alcoholic hydroxyl group in the alcohol compound is substituted. (For example, a ketal compound, an acetal compound, or an orthoester compound in which a hydrogen atom of a hydroxy group in an alcohol compound represented by the following formula (VI) is substituted).
Further, the sensitizer precursor XC may be a thiol compound in which the alcoholic hydroxyl group (hydroxy group) in the following formula (VI) is a thiol group. Specific examples of thiol compounds include compounds in which the hydroxy group in the alcohol compound represented by the following formula (VI) is replaced with a thiol group.
Further, the sensitizer precursor XC may be a thioketal compound or a thioacetal compound in which the oxygen atom bonded to R ²³ and/or R ²⁴ in the following formula (XXXVI) is replaced with sulfur.

In addition, when the sensitizer precursor XC is a ketal compound or an acetal compound, in order to further accelerate the hydrolysis reaction to a carbonyl compound by the acid generated during pattern exposure, step 2 (pattern exposure step) is performed as described below. ) and Step 3 (flood exposure step), it is also preferable to carry out step 2A (heating step).

In formula (VI), R ⁸ , R ⁹ and R ¹⁰ each independently represent a hydrogen atom; a phenyl group; a naphthyl group; an anthracenyl group; an alkoxy group having 1 to 5 carbon atoms; an alkylthio group having 1 to 5 carbon atoms; Phenoxy group; naphthoxy group; anthracenoxy group; amino group; amide group; halogen atom; linear, branched or cyclic saturated or unsaturated hydrocarbon group having 1 to 30 carbon atoms (preferably 1 to 5 carbon atoms) (preferably an alkyl group); a linear, branched or cyclic saturated or unsaturated hydrocarbon group (preferably an alkyl group) having 1 to 30 carbon atoms (preferably 1 to 5 carbon atoms); C1-C5 alkoxy group substituted with 5 alkoxy group, amino group, amide group, or hydroxy group; C1-C30 (preferably C1-5) linear, branched or a cyclic saturated or unsaturated hydrocarbon group (preferably an alkyl group), an alkylthio group having 1 to 5 carbon atoms substituted with an alkoxy group having 1 to 5 carbon atoms, an amino group, an amide group, or a hydroxy group; carbon A phenoxy group substituted with an alkoxy group having 1 to 5 carbon atoms, a hydroxy group, an amino group, an amide group, or an alkyl group having 1 to 5 carbon atoms; a straight chain having 1 to 30 carbon atoms (preferably 1 to 5 carbon atoms) a phenyl group substituted with a shaped, branched or cyclic saturated or unsaturated hydrocarbon group (preferably an alkyl group), an alkoxy group having 1 to 5 carbon atoms, an amino group, an amide group, or a hydroxy group; a phenyl group having 1 carbon number; -5 alkoxy group, alkyl group having 1 to 5 carbon atoms, amino group, amide group, or naphthoxy group substituted with a hydroxy group; alkoxy group having 1 to 5 carbon atoms, alkyl group having 1 to 5 carbon atoms, amino anthracenoxy group substituted with a group, an amide group, or a hydroxy group; an anthracenoxy group substituted with an alkoxy group having 1 to 5 carbon atoms, a phenoxy group, a naphthoxy group, an anthracenoxy group, an amino group, an amide group, or a hydroxy group having 1 carbon number ~30 (preferably 1 to 5 carbon atoms) linear, branched, or cyclic saturated or unsaturated hydrocarbon group (preferably an alkyl group); or carbonyl bonded to an alkyl group having 1 to 12 carbon atoms represents a group.
In addition, the hydrogen atom of the hydroxy group in the above formula (VI) can be a phenyl group; a halogen atom; A saturated hydrocarbon group (preferably an alkyl group); or a linear, branched or cyclic saturated or unsaturated hydrocarbon group (preferably an alkyl group) having 1 to 30 carbon atoms (preferably 1 to 5 carbon atoms); ), an alkoxy group having 1 to 5 carbon atoms, or a phenyl group substituted with a hydroxy group.
In the formula, any two or more groups among R ⁸ , R ⁹ , and R ¹⁰ are bonded by a single bond or double bond, or by -CH ₂ -, -O-, -S-, -SO ₂ - , -SO ₂ NH-, -CO-, -COO-, -NHCO-, -NHCO-NH-, -CHR ^g -, -CR ^g ₂ -, -NH- or -NR ^g - It may form a ring structure. R ^g represents a phenyl group; a phenoxy group; a halogen atom; a linear, branched or cyclic saturated or unsaturated hydrocarbon group having 1 to 30 carbon atoms (preferably 1 to 5 carbon atoms) (preferably an alkyl group); ); a phenoxy group substituted with an alkoxy group having 1 to 5 carbon atoms, a hydroxy group, or an alkyl group having 1 to 5 carbon atoms; or a straight chain having 1 to 30 carbon atoms (preferably 1 to 5 carbon atoms); , a branched or cyclic saturated or unsaturated hydrocarbon group (preferably an alkyl group), an alkoxy group having 1 to 5 carbon atoms, or a phenyl group substituted with a hydroxy group.
R ⁸ , R ⁹ and R ¹⁰ are each independently a hydrogen atom; a phenyl group; a phenoxy group; a phenoxy group substituted with an alkoxy group having 1 to 5 carbon atoms, a hydroxy group, or an alkyl group having 1 to 5 carbon atoms; or preferably represents a phenyl group substituted with an alkoxy group having 1 to 5 carbon atoms or a hydroxy group.

In addition, as the ketal compound or acetal compound in which the hydrogen atom of the hydroxy group in formula (VI) is substituted, a compound represented by the following formula (XXXVI) is preferable. In addition, when either one of R ⁹ and R ¹⁰ in the following formula (XXXVI) is a hydrogen atom, the compound represented by the following formula (XXXVI) corresponds to an acetal compound.

In formula (XXXVI), R ⁹ and R ¹⁰ have the same meanings as R ⁹ and R ¹⁰ in the above formula (VI), respectively. R ⁹ and R ¹⁰ may form a ring structure as described above.
In formula (XXXVI), R ²³ and R ²⁴ each independently represent a phenyl group; a halogen atom; a linear, branched, or cyclic saturated or Unsaturated hydrocarbon group (preferably an alkyl group); or a linear, branched or cyclic saturated or unsaturated hydrocarbon group having 1 to 30 carbon atoms (preferably 1 to 5 carbon atoms) (preferably an alkyl group); group), an alkoxy group having 1 to 5 carbon atoms, or a phenyl group substituted with a hydroxy group. R ²³ and R ²⁴ are represented by a single bond or a double bond, or -CH ₂ -, -O-, -S-, -SO ₂ -, -SO ₂ NH-, -CO-, -COO-, - A ring structure may be formed through a bond containing NHCO-, -NHCO-NH-, -CHR ^g -, -CR ^g ₂ -, -NH- or -NR ^g -. R ^g has the same meaning as R ^g in the above formula (VI).

Ketal compounds and acetal compounds are obtained by reacting a carbonyl compound with an alcohol. That is, in the above formula (XXXVI), R ²³ and R ²⁴ correspond to protective groups for a carbonyl group. In addition, below, the reaction to obtain a sensitizer by removing a protecting group from a sensitizer precursor may be referred to as a "deprotection reaction." Note that the deprotection reaction of ketal compounds and acetal compounds can usually proceed by the action of an acid.

Examples of ketal compounds that are sensitizer precursors include compounds represented by the following formulas (XXVII) to (XXX).

In formulas (XXVII) to (XXX), R ²³ and R ²⁴ have the same meanings as R ²³ and R ²⁴ in formula (XXXVI), respectively. In formulas (XXVII) to (XXX), the hydrogen atom of the aromatic ring may be substituted with an alkoxy group having 1 to 5 carbon atoms or an alkyl group having 1 to 5 carbon atoms, and the aromatic ring is bonded to another aromatic ring. may be used to form a naphthalene ring or anthracene ring. R ²⁵ represents an alkyl group having 1 to 5 carbon atoms. When the compounds represented by the above formulas (XXVII) to (XXX) are used as the sensitizer precursor XC, the shift width of the absorption wavelength before and after the structural change from the sensitizer precursor XC to the sensitizer is more This allows a more selective sensitization reaction to occur in step 3 (flood exposure step).

Note that the orthoester compound in which the hydrogen atom of the hydroxy group in formula (VI) is substituted is also preferably a compound represented by the following formula (XLVI).

In formula (XLVI), R ⁹ has the same meaning as R ⁹ in formula (VI) above. In formula (XLVI), R ³⁸ to R ⁴⁰ each independently represent a phenyl group; a halogen atom; a linear, branched, or cyclic saturated or Unsaturated hydrocarbon group (preferably an alkyl group); or a linear, branched or cyclic saturated or unsaturated hydrocarbon group having 1 to 30 carbon atoms (preferably 1 to 5 carbon atoms) (preferably an alkyl group); group), an alkoxy group having 1 to 5 carbon atoms, or a phenyl group substituted with a hydroxy group. R ³⁸ to R ⁴⁰ are represented by a single bond or double bond, or -CH ₂ -, -O-, -S-, -SO ₂ -, -SO ₂ NH-, -CO-, -COO-, - A ring structure may be formed through a bond containing NHCO-, -NHCO-NH-, -CHR ^g -, -CR ^g ₂ -, -NH- or -NR ^g -. R ^g has the same meaning as R ^g in the above formula (VI).

The orthoester compound is decomposed by a deprotection reaction under the action of an acid, and becomes, for example, a carboxylic acid ester or carboxylic acid containing a carbonyl group. The orthoester compound is, for example, a carboxy group-containing sensitizer with OBO (for example, 4-methyl 2,6,7-trioxabicyclo[2.2.2]octan-1-yl). A substituted (protected) OBO ester compound represented by the following formula (XLVII) is also preferred.

In formula (XLVII), R ⁴¹ and R ⁴² each independently represent a hydrogen atom; phenyl group; naphthyl group; anthracenyl group; phenoxy group; naphthoxy group; anthracenoxy group; amino group; amide group; halogen atom; carbon number 1 ~30 (preferably 1 to 5 carbon atoms) linear, branched or cyclic saturated or unsaturated hydrocarbon group (preferably an alkyl group); alkoxy group, hydroxy group, amino group having 1 to 5 carbon atoms , an amide group, or a phenoxy group substituted with an alkyl group having 1 to 5 carbon atoms; a linear, branched, or cyclic saturated or unsaturated carbonized group having 1 to 30 carbon atoms (preferably 1 to 5 carbon atoms); A phenyl group substituted with a hydrogen group (preferably an alkyl group), an alkoxy group having 1 to 5 carbon atoms, an amino group, an amide group, or a hydroxy group; an alkoxy group having 1 to 5 carbon atoms, an alkyl group having 1 to 5 carbon atoms or a naphthoxy group substituted with a hydroxy group; an alkoxy group having 1 to 5 carbon atoms, an alkyl group having 1 to 5 carbon atoms, an amino group, an amide group, or an anthracenoxy group substituted with a hydroxy group; anthracenoxy group having 1 to 5 carbon atoms; Linear or branched chain having 1 to 30 carbon atoms (preferably 1 to 5 carbon atoms) substituted with an alkoxy group, phenoxy group, naphthoxy group, anthracenoxy group, amino group, amide group, or hydroxy group of 5 or a cyclic saturated or unsaturated hydrocarbon group (preferably an alkyl group); or a carbonyl group to which an alkyl group having 1 to 12 carbon atoms is bonded. R ⁴¹ and R ⁴² are each independently preferably a hydrogen atom; a phenyl group; a phenoxy group; a phenoxy group substituted with an alkoxy group having 1 to 5 carbon atoms, a hydroxy group, or an alkyl group having 1 to 5 carbon atoms; ; or represents a phenyl group substituted with an alkoxy group having 1 to 5 carbon atoms or a hydroxy group;

Specific examples of the sensitizer precursor XC include compounds described in paragraphs [0067] to [0084] of JP-A No. 2015-172741.

In step 3 (flood exposure step) described below, energy transfer from the sensitizer generated from the sensitizer precursor XC to the onium salt XB progresses more easily, and while the onium salt XB is decomposed, the onium salt XB and the resin It is desirable that the energy level of the LUMO (Lowest Unoccupied Molecular Orbital) of the sensitizer is higher than that of the LUMO of the onium salt XB, since the interaction with XA can be more effectively released.

In the composition of aspect X1, the content of the sensitizer precursor XC is not particularly limited, but is preferably 0.5% by mass or more, more preferably 1.0% by mass or more, based on the total solid content of the composition. , more preferably 3.0% by mass or more. Further, the content is preferably 25.0% by mass or less, more preferably 20.0% by mass or less. The sensitizer precursors XC may be used alone or in combination of two or more. When two or more types are used, it is preferable that the total content is within the above-mentioned preferred content range.

<Surfactant>
The composition of aspect X1 may contain a surfactant. When a surfactant is included, a pattern with better adhesion and fewer development defects can be formed.
The surfactant is preferably a fluorine-based and/or silicon-based surfactant.
Examples of the fluorine-based and/or silicon-based surfactants include the surfactants disclosed in paragraphs [0218] and [0219] of International Publication No. 2018/193954.

These surfactants may be used alone or in combination of two or more.

When the composition of aspect preferable.

<Basic compound (quencher)>
The composition of aspect X1 also preferably contains a basic compound.
Examples of the basic compound include hydroxide compounds, carboxylate compounds, amine compounds (for example, primary to tertiary aliphatic amines, aromatic amines, heterocyclic amines, etc.), imine compounds, and amide compounds. .
As the basic compound, compounds known in resist compositions can be used. for example,

These basic compounds may be used alone or in combination of two or more.

When the composition of aspect preferable.

<Solvent>
The composition of aspect X1 may contain a solvent.
The solvent consists of (M1) propylene glycol monoalkyl ether carboxylate, and (M2) propylene glycol monoalkyl ether, lactic acid ester, acetate ester, alkoxypropionic acid ester, chain ketone, cyclic ketone, lactone, and alkylene carbonate. Preferably, at least one selected from the group . Note that this solvent may further contain components other than components (M1) and (M2).

When such a solvent and the above-mentioned resin are used in combination, the coating properties of the composition are improved and a pattern with a small number of development defects is easily formed. These solvents have a good balance between the solubility, boiling point, and viscosity of the resin mentioned above, so they can suppress unevenness in the thickness of the resist film and the generation of precipitates during spin coating, thereby reducing the number of development defects. It is assumed that fewer patterns can be formed.
Details of component (M1) and component (M2) are described in paragraphs [0218] to [0226] of International Publication No. 2020/004306.

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 based on the total amount of the solvent.

The content of the solvent in the composition of Embodiment X1 is preferably determined so that the solid content concentration is 0.5 to 30% by mass, more preferably 1 to 20% by mass. In this way, the applicability of the composition can be further improved.

<Other additives>
The composition of Embodiment or an aliphatic compound).

The composition of Embodiment X1 may further include a dissolution-inhibiting compound. Here, the term "dissolution-inhibiting compound" refers to a compound with a molecular weight of 3,000 or less that decomposes under the action of an acid and reduces its solubility in an organic solvent developer.

[Composition of aspect X2]
Hereinafter, various components included in aspect X2 will be explained.
In the composition of aspect Alternatively, the composition is the same as the composition of Embodiment X1 above, except that the sensitizer precursor XC itself is a compound that generates an acid capable of producing a sensitizer upon irradiation with light, and the preferred embodiments are also the same.

In the composition of aspect As mentioned above, the pKa of the acid generated from the onium salt XB is preferably about -15.0 to 2.0. The composition of aspect More preferably, this is the case when the onium salt is (more than 2.5).
Examples of such onium salts XB include onium salts in which weak acids such as carboxylic acid anions and phenolic acid anions are used as generated acids.
Specific examples of the onium salt XB that can be used in the composition of Embodiment X2 include compounds in which the anion in the onium salt XB of Embodiment X1 is changed to a carboxylic acid anion and a phenolic acid anion.
Examples of the carboxylic acid anion include an aliphatic carboxylic acid anion, an aromatic carboxylic acid anion, and an aralkylcarboxylic acid anion.

The aliphatic moiety in the aliphatic carboxylic acid anion may be an alkyl group or a cycloalkyl group, and may be a linear or branched alkyl group having 1 to 30 carbon atoms, or a linear or branched alkyl group having 3 to 30 carbon atoms. A cycloalkyl group is preferred.
The alkyl group may be, for example, a fluoroalkyl group (which may or may not have a substituent other than a fluorine atom; it may also be a perfluoroalkyl group).

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

The aralkyl group in the aralkylcarboxylic acid 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.

The phenolic acid anion may be one in which the benzene ring in the molecule is substituted with a substituent (provided, however, with a substituent other than -O ^{2 -} ) or unsubstituted. Examples of the substituent include those similar to the above-mentioned substituents that the carboxylic acid anion may have.

The composition of aspect Upon irradiation with light, it generates an acid that can produce a sensitizer.

As the photoacid generator XD, known photoacid generators such as oxime sulfonate compounds, triazine compounds, nitrobenzyl sulfonate compounds, disulfone compounds, and bissulfonyldiazomethane compounds can be used.
In addition, when the sensitizer precursor XC is a compound having a moiety that can be deprotected by the action of an acid, such as the above-mentioned ketal structure or acetal structure, photoacid generation is required to generate a carbonyl compound by the deprotection reaction. The pKa of the acid generated from agent XD is preferably 2.0 or less, more preferably 1.0 or less, and even more preferably 0.0 or less. Note that the lower limit is preferably −15.0 or more.

In the composition of aspect 2, the content of the photoacid generator XD is not particularly limited, but is preferably 1.0% by mass or more, more preferably 3.0% by mass or more, based on the total solid content of the composition. More preferably, the content is 5.0% by mass or more. Further, the content is preferably 40.0% by mass or less, more preferably 30.0% by mass or less. The photoacid generators XD may be used alone or in combination of two or more. When two or more types are used, it is preferable that the total content is within the above-mentioned preferred content range.

Furthermore, in the composition of aspect X2, the sensitizer precursor XC itself may be a compound that generates an acid capable of producing a sensitizer upon irradiation with light.
In addition, the sensitizer precursor XC is a compound that itself generates an acid capable of producing a sensitizer upon irradiation with light, and the compound has a ketal structure or an acetal structure as described above, and the action of the acid When the pKa of the generated acid generated from the sensitizer precursor XC is preferably 2.0 or less, and more preferably 1.0 or less, in order to generate a carbonyl compound by the deprotection reaction. It is preferably 0.0 or less, and more preferably 0.0 or less. Note that the lower limit is preferably −15.0 or more.
As such a sensitizer precursor XC, for example, a compound represented by the following formula (C1) or formula (C2) is preferable.

In formula (C1), R ^c1 represents an organic group.
Examples of the organic group include an alkyl group, an aryl group, and a heteroaryl group.
The alkyl group may be linear, branched, or cyclic. The number of carbon atoms in the alkyl group is preferably 1 to 30, more preferably 1 to 20, and even more preferably 1 to 12.
Examples of the aryl group include aryl groups having 6 to 30 carbon atoms.
The aryl group is preferably a phenyl group, p-methylphenyl group, p-chlorophenyl group, pentachlorophenyl group, pentafluorophenyl group, o-methoxyphenyl group, or p-phenoxyphenyl group.
Examples of the heteroaryl group include a thiophene ring group, a pyrrole ring group, a thiazole ring group, an imidazole ring group, a furan ring group, a benzothiophene ring group, a benzothiazole ring group, and a benzimidazole ring group.
The alkyl group, aryl group, and heteroaryl group may have a substituent. Examples of the substituent include a halogen atom, an alkyl group, an alkyloxy group, an aryloxy group, an alkylthio group, an arylthio group, an alkyloxycarbonyl group, an aryloxycarbonyl group, and an aminocarbonyl group.
In formula (C1), R ^c2 and R ^c3 have the same meanings as R ²³ and R ²⁴ in formula (XXXVI) above. Note that R ^c2 and R ^c3 may be bonded to each other to form a ring structure. Examples of the group in which R ^c2 and R ^c3 are connected to each other include the groups exemplified above, and among them, an alkylene group having 1 to 10 carbon atoms is preferable.
In formula (C1), R ^c4 represents a hydrogen atom or a substituent. Examples of the substituent represented by R ^c4 include those similar to those exemplified as the organic group represented by R ^c1 .
In formula (C1), p represents 0 or 1. In addition, when p is 0, the ring containing a nitrogen atom in the formula represents a 5-membered ring.
In formula (C1), W ^c1 represents an aromatic ring.
The aromatic ring may be either monocyclic or polycyclic. Further, the aromatic ring may be either an aromatic hydrocarbon ring or an aromatic heterocycle.
The aromatic ring represented by W ^c1 is preferably a benzene ring, a naphthalene ring, or an anthracene ring.
The aromatic ring represented by W ^c1 may further have a substituent. Examples of the substituent include a halogen atom, an alkyl group, an aryl group, a heteroaryl group, an alkyloxy group, an aryloxy group, an alkylthio group, an arylthio group, an alkyloxycarbonyl group, an aryloxycarbonyl group, and an aminocarbonyl group. Can be mentioned.
In formula (C1), Ar ^c1 represents an aromatic ring group.
The aromatic ring constituting the aromatic ring group may be either monocyclic or polycyclic. Further, the aromatic ring may be either an aromatic hydrocarbon ring or an aromatic heterocycle.
Examples of the aromatic ring constituting the aromatic ring group represented by Ar ^c1 include a benzene ring, a naphthalene ring, an anthracene ring, a carbazole ring, and a fluorene ring.
The aromatic ring group represented by Ar ^c1 may further have a substituent. Examples of the substituent include the same substituents as the substituent that the aromatic ring represented by W ^c1 may have.
In addition, in formula (C1), a substituent that the aromatic ring represented by W ^c1 may have and a substituent that the aromatic ring group represented by Ar ^c1 may combine with each other to form a ring. It's okay. The ring is preferably a 5- or 6-membered ring, and may contain a heteroatom (eg, a sulfur atom, an oxygen atom, etc.).
Furthermore, in formula (C1), a substituent that the aromatic ring represented by W ^c1 may have and a substituent represented by R ^c4 may be bonded to each other to form a ring. The ring is preferably a 5- or 6-membered ring, and may contain a heteroatom (eg, a sulfur atom, an oxygen atom, etc.). The above-mentioned ring may be an alicyclic ring or an aromatic ring, but an aromatic ring (preferably an aromatic hydrocarbon ring, more preferably a benzene ring or a naphthalene ring) is preferable.

In formula (C2), R ^c1 , R ^c2 , R ^c3 , and Ar ^c3 have the same meanings as R ^c1 , R ^c2 , R ^c3 , and Ar ^c1 in formula (C1), and preferred embodiments are also the same. be.
In formula (C2), Ar ^c2 represents an alicyclic group or an aromatic ring group.
The number of ring members of the alicyclic group represented by Ar ^c2 is, for example, 3 to 20, preferably 4 to 15, and more preferably 6 to 15. Further, the alicyclic group may contain an oxygen atom, a nitrogen atom, a sulfur atom, a ketone group, an ether bond, an ester bond, or an amide bond. Specific examples of the alicyclic group represented by Ar ^c1 and Ar ^c2 include, for example, a cycloalkyl group having 6 to 15 carbon atoms. Note that the alicyclic group may have a structure in which aromatic rings are condensed.
The aromatic ring constituting the aromatic ring group represented by Ar ^c2 may be either monocyclic or polycyclic, but polycyclic is preferable.
The polycyclic aromatic ring may be either an aromatic hydrocarbon ring or an aromatic heterocycle, and may be selected from the group consisting of a 6-membered aromatic hydrocarbon ring and a 5- or 6-membered aromatic heterocycle. The ring is preferably a ring formed by condensing two or more (preferably 2 to 5, more preferably 2 to 3) rings. Note that examples of the 5-membered aromatic heterocycle include a thiophene ring and a furan ring.
The polycyclic aromatic ring is preferably a fluorene ring.
The aromatic ring constituting the aromatic ring group represented by Ar ^c2 may further have a substituent. Examples of the substituent include the same substituents as the substituent that the aromatic ring represented by W ^c1 may have.

[Composition of aspect X3]
In the composition of embodiment X3, resin XA and onium salt XB are bonded via a covalent bond. That is, the composition of aspect X3 includes a resin (hereinafter also referred to as "resin XAX3") in which resin XA and onium salt XB are linked via a covalent bond.
Note that the resin XAX3 may or may not have an interactive group that can interact with the onium salt XB. In order to achieve better effects of the present invention, the resin XAX3 preferably has an interactive group.
Note that the composition of Embodiment X3 is the same as the composition of Embodiment X1, and the preferred embodiments are also the same, except that the composition includes resin XAX3 instead of containing resin XA and onium salt XB individually.

<Resin XAX3>
The resin XAX3 will be explained below.
Resin XAX3 is a resin in which resin XA and onium salt XB are linked via a covalent bond. Resin XAX3 may or may not have an interactive group that interacts with onium salt XB. Resin XAX3 preferably has an interactive group in that the effects of the present invention are more excellent. Note that the interactive group is as described above.

The resin XAX3 may contain a repeating unit having an acid-decomposable group. However, when resin XAX3 contains a repeating unit having an acid-decomposable group, its content is 20 mol% or less, preferably 15 mol% or less, and 10 mol% or less, based on the total repeating units of resin XAX3. The following is more preferable, 5 mol% or less is still more preferable, and 3 mol% or less is particularly preferable. Note that the lower limit is 0 mol% or more. Note that the acid-decomposable group is as described above.

Preferably, resin XAX3 contains a repeating unit having a group to which onium salt XB is covalently linked.
Examples of the group to which the onium salt XB is linked via a covalent bond include a group represented by -L ^r -O ^r . L ^r represents a single bond or a divalent linking group. ^Or represents a group formed by removing one hydrogen atom from the onium salt XB already described in the composition of aspect The following groups are mentioned.

The divalent linking group represented by L ^r is not particularly limited, but includes, for example, -CO-, -O-, -SO-, -SO ₂ -, -NR ^A -, alkylene group (preferably one having 1 carbon number) ～6. Can be linear or branched), cycloalkylene group (preferably has 3 to 15 carbon atoms), divalent aromatic hydrocarbon ring group (preferably 6 to 10-membered ring, more preferably 6-membered ring) ), and a divalent linking group that is a combination of a plurality of these. Further, the alkylene group, the cycloalkylene group, and the divalent aromatic hydrocarbon ring group may have a substituent. Examples of the substituent include an alkyl group, a halogen atom, and a hydroxyl group. Examples of R ^A include a hydrogen atom or an alkyl group having 1 to 6 carbon atoms.
A preferred embodiment of the divalent linking group represented by L ^r is an embodiment in which the position bonded to the main chain side of the divalent linking group represented by L ^r is -COO-.

*-X _A ^n- nM _A ⁺ formula (O1)
*-M _B ⁺ X _B ^-Formula (O2)

In formula (O1), X _A ^n- represents a monovalent anionic group with an n-valent charge. M _A ⁺ represents an organic cation. n represents 1 or 2.
In formula (O2), M _B ⁺ represents a monovalent organic cationic group.
Note that the organic anions represented by X _A ^n- and X _B ^- are preferably non-nucleophilic anions (anions with extremely low ability to cause a nucleophilic reaction).

Hereinafter, the group represented by the following formula (O1) and the group represented by the following formula (O2) will be explained in detail.

In formula (O1), X _A ^n- represents a monovalent anionic group having an n-valent charge (n is 1 or 2).
The monovalent ^anionic group _represented by Preferably, it is a group selected from the group consisting of the groups represented. The groups represented by the following formulas (B-1) to (B-12) correspond to monovalent anionic groups with a monovalent charge, and the groups represented by the following formula (B-13) corresponds to a monovalent anionic group with a divalent charge.

In formulas (B-1) to (B-12), * represents the bonding position.
In formulas (B-1) to (B-5) and formula (B-11), R ^X1 each independently represents a monovalent organic group.
In formulas (B-6) and (B-10), R ^X2 each independently represents a hydrogen atom or a substituent other than a fluorine atom and a perfluoroalkyl group. Two R ^X2 's in formula (B-6) may be the same or different.
In formula (B-7), R ^XF1 represents a hydrogen atom, a fluorine atom, or a perfluoroalkyl group. However, at least one of the two R ^XF1 represents a fluorine atom or a perfluoroalkyl group. Two R ^XF1 's in formula (B-7) may be the same or different.
In formula (B-8), R ^X3 represents a hydrogen atom, a halogen atom, or a monovalent organic group. n1 represents an integer from 0 to 4. When n1 represents an integer of 2 to 4, a plurality of R ^X3 may be the same or different.
In formula (B-9), R ^XF2 represents a fluorine atom or a perfluoroalkyl group.

In formulas (B-1) to (B-5) and formula (B-11), R ^X1 each independently represents a monovalent organic group.
R ^X1 is an alkyl group (which may be linear or branched, preferably having 1 to 15 carbon atoms), or a cycloalkyl group (which may be monocyclic or polycyclic, preferably having 3 to 20 carbon atoms). ), or an aryl group (which may be monocyclic or polycyclic. The number of carbon atoms is preferably 6 to 20). Further, the above group represented by R ^X1 may have a substituent.
In addition, in formula (B-5), it is also preferable that the atom directly bonded to N ^- in R ^X1 is neither the carbon atom in -CO- nor the sulfur atom in -SO ₂ -.

The cycloalkyl group in R ^X1 may be monocyclic or polycyclic.
Examples of the cycloalkyl group for R ^X1 include a norbornyl group and an adamantyl group.

The substituent that the cycloalkyl group in ^R One or more of the carbon atoms that are ring member atoms of the cycloalkyl group in R ^X1 may be replaced with a carbonyl carbon atom. The number of carbon atoms in the alkyl group in R ^X1 is preferably 1 to 10, more preferably 1 to 5.

The substituent that the alkyl group in R ^X1 may have is not particularly limited, but is preferably a cycloalkyl group, a fluorine atom, or a cyano group.
Examples of the cycloalkyl group as the above-mentioned substituent include the cycloalkyl group described in the case where R ^X1 is a cycloalkyl group.
When the alkyl group in R ^X1 has a fluorine atom as the substituent, the alkyl group may be a perfluoroalkyl group.
Furthermore, in the alkyl group in R ^X1 , one or more -CH ₂ - may be substituted with a carbonyl group.

The aryl group for R ^X1 is preferably a benzene ring group.
The substituent that the aryl group in R ^X1 may have is not particularly limited, but is preferably an alkyl group, a fluorine atom, or a cyano group. Examples of the alkyl group as the above-mentioned substituent include the alkyl groups explained in the case where R ^X1 is an alkyl group.

In formulas (B-6) and (B-10), R ^X2 each independently represents a hydrogen atom or a substituent other than a fluorine atom and a perfluoroalkyl group. Two R ^X2 's in formula (B-6) may be the same or different.
The substituent other than the fluorine atom and the perfluoroalkyl group represented by R ^X2 is preferably an alkyl group other than the perfluoroalkyl group or a cycloalkyl group.
Examples of the alkyl group include an alkyl group obtained by removing a perfluoroalkyl group from the alkyl group described in the case where R ^X1 is an alkyl group. Moreover, it is preferable that the alkyl group does not have a fluorine atom.
Examples of the cycloalkyl group include the cycloalkyl groups described in the case where R ^X1 is a cycloalkyl group. Further, it is preferable that the cycloalkyl group does not have a fluorine atom.

In formula (B-7), R ^XF1 represents a hydrogen atom, a fluorine atom, or a perfluoroalkyl group. However, at least one of the plurality of R ^XF1 represents a fluorine atom or a perfluoroalkyl group. Two R ^XF1 's in formula (B-7) may be the same or different. The number of carbon atoms in the perfluoroalkyl group represented by R ^XF1 is preferably 1 to 15, more preferably 1 to 10, and even more preferably 1 to 6.

In formula (B-8), R ^X3 represents a hydrogen atom, a halogen atom, or a monovalent organic group. Examples of the halogen atom as R ^X3 include a fluorine atom, a chlorine atom, a bromine atom, and an iodine atom, of which a fluorine atom is preferred.
The monovalent organic group as R ^X3 is the same as the monovalent organic group described as R ^X1 .
n1 represents an integer from 0 to 4.
n1 is preferably an integer of 0 to 2, and preferably 0 or 1. When n1 represents an integer of 2 to 4, a plurality of R ^X3 may be the same or different.

In formula (B-9), R ^XF2 represents a fluorine atom or a perfluoroalkyl group.
The number of carbon atoms in the perfluoroalkyl group represented by R ^XF2 is preferably 1 to 15, more preferably 1 to 10, and even more preferably 1 to 6.

*-B _M1 -L _M -B _M2 formula (B-13)
In formula (B-13), B _M1 represents a divalent anionic group represented by any of the following formulas (BB-1) to (BB-4). _LM represents a single bond or a divalent linking group. B _M2 represents any group selected from the group consisting of formulas (B-1) to (B-12) described above.

The divalent linking group represented by L _M is not particularly limited and includes -CO-, -NR-, -O-, -S-, -SO-, -SO ₂ -, alkylene group (preferably carbon Numbers 1 to 6, which may be linear or branched), cycloalkylene groups (preferably having 3 to 15 carbon atoms), alkenylene groups (preferably having 2 to 6 carbon atoms), divalent aliphatic heterocyclic groups ( A 5- to 10-membered ring having at least one N atom, O atom, S atom, or Se atom in the ring structure is preferred, a 5- to 7-membered ring is more preferred, and a 5- to 6-membered ring is even more preferred), 2 valent aromatic heterocyclic group (preferably a 5- to 10-membered ring having at least one N atom, O atom, S atom, or Se atom in the ring structure, more preferably a 5- to 7-membered ring, and a 5- to 6-membered ring) (more preferably a ring), a divalent aromatic hydrocarbon ring group (preferably a 6- to 10-membered ring, more preferably a 6-membered ring), and a divalent linking group that is a combination of a plurality of these. Examples of the above R include a hydrogen atom or a monovalent organic group. The monovalent organic group is not particularly limited, but is preferably an alkyl group (preferably having 1 to 6 carbon atoms).
The alkylene group, the cycloalkylene group, the alkenylene group, the divalent aliphatic heterocyclic group, the divalent aromatic heterocyclic group, and the divalent aromatic hydrocarbon ring group have a substituent. You may do so. Examples of the substituent include a halogen atom (preferably a fluorine atom).
The divalent linking group represented by _LM is preferably an alkylene group. The alkylene group is preferably substituted with a fluorine atom, and may be a perfluoro group.

The organic cation represented by M _A ⁺ in formula (O1) is an organic cation (cation (ZaI)) represented by the formula (ZaI) described above or an organic cation represented by the formula (ZaII) described above. Cations (cations (ZaII)) are preferred.

As the monovalent organic cationic group represented by M _B ⁺ in formula (O2), among others, an organic cationic group represented by the following formula (ZBI) or an organic group represented by the following formula (ZBII) Cationic groups are preferred.

In the above formula (ZBI), R ³⁰¹ and R ³⁰² each independently represent an organic group. The number of carbon atoms in the organic group as R ³⁰¹ and R ³⁰² is preferably 1 to 30, more preferably 1 to 20. R ³⁰³ represents a divalent linking group.
Further, two of R ³⁰¹ to R ³⁰³ may be combined to form a ring structure, and the ring may contain an oxygen atom, a sulfur atom, an ester group, an amide group, or a carbonyl group. Examples of the group formed by combining two of R ³⁰¹ to R ³⁰³ include an alkylene group (for example, a butylene group and a pentylene group), and -CH ₂ -CH ₂ -O-CH ₂ -CH ₂ -. Can be mentioned.

The organic groups as R ³⁰¹ and R ³⁰² are not particularly limited, but are preferably an alkyl group, a cycloalkyl group, or an aryl group.
As the aryl group, a phenyl group or a naphthyl group is preferable, and a phenyl group is more preferable. The aryl group may be an aryl group having a heterocyclic structure having an oxygen atom, a nitrogen atom, a sulfur atom, or the like. Examples of the heterocyclic structure include pyrrole residue, furan residue, thiophene residue, indole residue, benzofuran residue, and benzothiophene residue.
The alkyl group or cycloalkyl group is preferably a linear alkyl group having 1 to 15 carbon atoms, a branched alkyl group having 3 to 15 carbon atoms, or a cycloalkyl group having 3 to 15 carbon atoms, such as a methyl group, Examples include ethyl group, propyl group, n-butyl group, sec-butyl group, t-butyl group, cyclopropyl group, cyclobutyl group, and cyclohexyl group.

The substituents that the aryl group, alkyl group, and cycloalkyl group of R ³⁰¹ to R ³⁰² may each independently include an alkyl group (for example, carbon number 1 to 15), a cycloalkyl group (for example, carbon number 3 to 15), aryl groups (for example, carbon atoms 6 to 14), alkoxy groups (for example, carbon atoms 1 to 15), cycloalkylalkoxy groups (for example, carbon atoms 1 to 15), halogen atoms, hydroxyl groups, and phenylthio groups. It will be done.

The divalent linking group as R ³⁰³ is not particularly limited, but preferably represents an alkylene group, a cycloalkylene group, an aromatic group, or a group formed by combining two or more of these.
The alkylene group may be linear or branched and preferably has 1 to 20 carbon atoms, more preferably 1 to 10 carbon atoms.
The cycloalkylene group may be monocyclic or polycyclic, and preferably has 3 to 20 carbon atoms, more preferably 3 to 10 carbon atoms.
The aromatic group is a divalent aromatic group, preferably an aromatic group having 6 to 20 carbon atoms, and more preferably an aromatic group having 6 to 15 carbon atoms.
The aromatic ring constituting the aromatic group is not particularly limited, but includes, for example, an aromatic ring having 6 to 20 carbon atoms, and specific examples include a benzene ring, a naphthalene ring, an anthracene ring, a thiophene ring, and the like. A benzene ring or a naphthalene ring is preferred, and a benzene ring is more preferred.

The alkylene group, cycloalkylene group, and aromatic group may further have a substituent.

In the above formula (ZBII), R ³⁰⁴ represents an aryl group, an alkyl group, or a cycloalkyl group. R ³⁰⁵ represents a divalent linking group.
The aryl group for R ³⁰⁴ is preferably a phenyl group or a naphthyl group, and more preferably a phenyl group. The aryl group of R ³⁰⁴ may be an aryl group having a heterocycle having an oxygen atom, a nitrogen atom, a sulfur atom, or the like. Examples of the skeleton of the aryl group having a heterocycle include pyrrole, furan, thiophene, indole, benzofuran, and benzothiophene.
The alkyl group and cycloalkyl group of R ³⁰⁴ include a linear alkyl group having 1 to 10 carbon atoms or a branched alkyl group having 3 to 10 carbon atoms (for example, a methyl group, an ethyl group, a propyl group, a butyl group, or pentyl group), or a cycloalkyl group having 3 to 10 carbon atoms (eg, cyclopentyl group, cyclohexyl group, or norbornyl group).

The aryl group, alkyl group, and cycloalkyl group of R ³⁰⁴ may each independently have a substituent. Examples of substituents that the aryl group, alkyl group, and cycloalkyl group of R ³⁰⁴ may have include an alkyl group (for example, having 1 to 15 carbon atoms), a cycloalkyl group (for example, having 3 to 15 carbon atoms), Examples include aryl groups (eg, carbon atoms 6 to 15), alkoxy groups (eg, carbon atoms 1 to 15), halogen atoms, hydroxyl groups, and phenylthio groups.

The divalent linking group as R ³⁰⁵ is not particularly limited, but preferably represents an alkylene group, a cycloalkylene group, an aromatic group, or a group formed by combining two or more of these.
The alkylene group may be linear or branched and preferably has 1 to 20 carbon atoms, more preferably 1 to 10 carbon atoms.
The cycloalkylene group may be monocyclic or polycyclic, and preferably has 3 to 20 carbon atoms, more preferably 3 to 10 carbon atoms.
The aromatic group is a divalent aromatic group, preferably an aromatic group having 6 to 20 carbon atoms, and more preferably an aromatic group having 6 to 15 carbon atoms.
The aromatic ring constituting the aromatic group is not particularly limited, but examples include aromatic rings having 6 to 20 carbon atoms, and specific examples include benzene ring, naphthalene ring, anthracene ring, and thiophene ring. . The aromatic ring constituting the aromatic group is preferably a benzene ring or a naphthalene ring, and more preferably a benzene ring.

The organic anion represented by X _B ^- in formula (O2) is preferably a non-nucleophilic anion (an anion with extremely low ability to cause a nucleophilic reaction).
Examples of the organic anion represented by X _B ^- include those similar to the organic anions exemplified as the organic acid generated from the onium salt XB upon irradiation with light in Embodiment X1.

Specific examples of the repeating unit having a group to which the onium salt XB is covalently linked include a repeating unit represented by the following formula (XR).

In the formula, L ^r represents a single bond or a divalent linking group. In addition, as the divalent linking group represented by ^Lr , the same groups as those mentioned above as the divalent linking group represented by ^Lr can ^be mentioned. O1) or a group represented by formula (O2).
^Xr represents a hydrogen atom, a halogen atom, or an alkyl group that may have a substituent.
The halogen atom represented by X ^r is preferably a fluorine atom or a chlorine atom, and more preferably a chlorine atom.
The alkyl group represented by ^Xr may be linear, branched, or cyclic. The number of carbon atoms in the alkyl group is preferably 1 to 12, more preferably 1 to 6, and even more preferably 1 to 3.
Further, the substituent that the alkyl group represented by ^Xr may have is not particularly limited, and examples thereof include a halogen atom and a hydroxyl group.

In resin XAX3, the content of the repeating unit represented by the above formula (XR) is preferably 1 mol% or more, more preferably 3 mol% or more, based on all repeating units. In addition, as an upper limit, 15 mol% or less is preferable, and 10 mol% or less is more preferable. In the resin XAX3, only one kind of repeating unit represented by the above formula (XR) may be contained, or two or more kinds thereof may be contained. When a plurality of repeating units represented by the above formula (XR) are included, the above content is preferably the total content.

(Preferred embodiment of resin XAX3)
The resin XAX3 is preferably a resin whose main chain is cut by the action of exposure, acid, base, or heating and whose molecular weight decreases (main chain cleavage type resin), since the effects of the present invention are more excellent. .
Resin XAX3, which is a main chain cleavage type resin, contains a repeating unit represented by the above formula (XR), a repeating unit represented by formula (XP) in resin XA explained in the composition of aspect X1, and a repeating unit represented by formula ( A resin containing at least one repeating unit represented by XQ) is preferable. From the viewpoint of main chain scission property, among others, a resin containing a repeating unit represented by the formula (XR) in which X ^r represents a halogen atom and a repeating unit represented by the formula (XQ), or a resin in which X ^r is substituted It is preferable that the resin contains a repeating unit represented by the formula (XR) representing an alkyl group which may have a group and a repeating unit represented by the formula (XP).

Resin XAX3 has a repeating unit represented by the above formula (XR) and a repeating unit represented by formula (XP) or a repeating unit represented by formula (XQ) in resin XA explained in the composition of aspect X1. If the resin contains at least one type, the total content of the repeating unit represented by formula (XR), the repeating unit represented by formula (XP), and the repeating unit represented by the above formula (XQ) is preferably 90 mol% or more, more preferably 95 mol% or more, based on all repeating units. In addition, as an upper limit, 100 mol% or less is preferable.
In addition, in resin XAX3, the repeating unit selected from the group consisting of the repeating unit represented by formula (XR), the repeating unit represented by formula (XP), and the repeating unit represented by the above formula (XQ) is: It may be in any form such as a random copolymer, a block copolymer, or an alternating copolymer (ABAB...), but among these, an alternating copolymer is preferable.
A preferred embodiment of the resin XAX3 is an embodiment in which the proportion of the alternating copolymer in the resin XAX3 is 90% by mass or more (preferably 100% by mass or more) based on the total mass of the resin XAX3. It will be done.

Resin XAX3 can be synthesized according to conventional methods (eg, radical polymerization).
The weight average molecular weight (Mw) of the resin XAX3 is preferably 15,000 or more, more preferably 20,000 or more, even more preferably 30,000 or more, and particularly preferably 40,000 or more. The upper limit is, for example, preferably 200,000 or less, more preferably 150,000 or less, and even more preferably 100,000 or less.

The polydispersity (Mw/Mn) of the resin XAX3 is not particularly limited, but is preferably 2.5 or less, more preferably 2.0 or less, and even more preferably 1.7 or less. The lower limit value is not particularly limited, and may be 1.0 or more.

In the composition of aspect X3, the lower limit of the content of resin XAX3 is preferably 30.0% by mass or more, more preferably 45.0% by mass or more, and 65.0% by mass based on the total solid content of the composition. % or more is more preferable. In addition, as an upper limit, 99.9 mass % or less is preferable, for example. Further, resin XAX3 may be used alone or in combination. When two or more types are used, it is preferable that the total content is within the above-mentioned preferred content range.

[Composition of aspect X4]
Hereinafter, various components included in aspect X4 will be explained.
In the composition of aspect X4, the onium salt XB in the resin in which the resin XA and the onium salt XB are linked via a covalent bond acts on the sensitizer precursor XC to generate an acid capable of producing a sensitizer. The composition, rather than the compound, separately contains a photoacid generator XD as an acid source that generates an acid that can act on the sensitizer precursor XC to produce a sensitizer, or the sensitizer precursor The composition is the same as the composition of Embodiment X3 above, except that XC itself generates an acid capable of producing a sensitizer upon irradiation with light, and the preferred embodiments are also the same.

The resin (XAX4) in which resin XA and onium salt XB are linked via a covalent bond, which is contained in the composition of aspect It is the same as the resin XAX3 contained in the composition of Embodiment X3, except that it is not a compound that generates an acid capable of producing a sensitizer.
In other words, resin XAX4 in the composition of aspect is more than 2.0 (preferably more than 2.1, more preferably more than 2.5)) are linked via covalent bonds.
Examples of such onium salts XB include onium salts having weak acids such as carboxylic acids and phenolic acids as generated acids (that is, onium salts having carboxylic acid anions and phenolic acid anions).
In addition, as a specific example of the above-mentioned resin, a resin in which the anion of onium salt XB in resin XAX3 in aspect X3 is changed to a carboxylic acid anion and a phenolic acid anion can be mentioned. Examples of the carboxylic acid anion and phenolic acid anion include those described as the generated acid of the onium salt XB that can be used in the composition of embodiment X2.

In the composition of aspect Upon irradiation, it generates an acid that can produce a sensitizer.
The photoacid generator XD and the sensitizer precursor XC that generates an acid capable of producing a sensitizer upon irradiation with light and their contents include the photoacid generator XD and the sensitizer precursor XC in the composition of Embodiment X2 above. The same applies to the sensitizer precursor XC which generates an acid capable of producing a sensitizer, and the content thereof.

[Modifications of each composition of embodiments X1 to X4]
In each of the compositions of embodiments X1 to X4, the sensitizer precursor XC may be bonded to the resin XA via a covalent bond.
The resin in which the resin XA and the sensitizer precursor XC are linked via a covalent bond preferably contains a repeating unit having a group to which the sensitizer precursor XC is linked via a covalent bond. Such a repeating unit is a repeating unit represented by the formula ( ^XR ) described in the composition of aspect Repeating units representing groups to be formed are mentioned.
In the resin in which the resin XA and the sensitizer precursor XC are linked via a covalent bond, the content of repeating units having a group to which the sensitizer precursor XC is linked by a covalent bond is as follows: The content is preferably 1 mol% or more, more preferably 3 mol% or more. In addition, as an upper limit, 15 mol% or less is preferable, and 10 mol% or less is more preferable. The resin in which the resin XA and the sensitizer precursor XC are linked via a covalent bond may contain only one type of repeating unit or two or more types of repeating units. When a plurality of the repeating units are included, the content is preferably the total content.

In each of the compositions of embodiments X2 and X4, photoacid generator XD may be bonded to resin XA via a covalent bond.
The resin in which the resin XA and the photoacid generator XD are linked via a covalent bond preferably contains a repeating unit having a group to which the photoacid generator XD is linked via a covalent bond. Such a repeating unit is a repeating unit represented by the formula (XR) described in the composition of aspect X3, in which "O ^r " is formed by removing one hydrogen atom from the photoacid generator XD. Examples include repeating units representing groups.
In the resin in which the resin XA and the photoacid generator XD are linked via a covalent bond, the content of repeating units having a group to which the photoacid generator XD is linked via a covalent bond is 1 mol based on all repeating units. % or more is preferable, and 3 mol% or more is more preferable. In addition, as an upper limit, 15 mol% or less is preferable, and 10 mol% or less is more preferable. In the resin in which the resin XA and the photoacid generator XD are linked via a covalent bond, the repeating unit may contain only one type or two or more types. When a plurality of the repeating units are included, the content is preferably the total content.

[Composition of requirement 2]
An example of an embodiment of a composition meeting requirement 2 will be shown below.
・Aspect Y1
A composition comprising resin YA and compound YB,
The resin YA has an interactive group that interacts with the compound YB,
The onium salt structure in compound YB is a structure that generates an acid capable of producing a sensitizer,
The content of the repeating unit having a group that decomposes to produce a polar group by the action of an acid in the resin YA is 0 to 20 mol % based on the total repeating units of the resin YA.
・Aspect Y2
A composition comprising resin YA and compound YB,
The resin YA has an interactive group that interacts with the compound YB,
The onium salt structure in compound YB is not a structure that generates an acid capable of producing a sensitizer, and the composition further contains a photoacid generator YC,
The content of the repeating unit having a group that decomposes to produce a polar group by the action of an acid in the resin YA is 0 to 20 mol % based on the total repeating units of the resin YA.
・Aspect Y3
A composition comprising resin YA and compound YB,
The resin YA and the compound YB are bonded via a covalent bond,
The onium salt structure in compound YB is a structure that generates an acid capable of producing a sensitizer,
The content of the repeating unit having a group that decomposes to produce a polar group by the action of an acid in the resin YA is 0 to 20 mol % based on the total repeating units of the resin YA.
・Aspect Y4
A composition comprising resin YA and compound YB,
The resin YA and the compound YB are bonded via a covalent bond,
The onium salt structure in compound YB is not a structure that generates an acid capable of producing a sensitizer, and the composition further contains a photoacid generator YC,
The content of the repeating unit having a group that decomposes to produce a polar group by the action of an acid in the resin YA is 0 to 20 mol % based on the total repeating units of the resin YA.

Note that in embodiments Y1 to Y4, the photoacid generator YC may be bonded to the resin YA via a covalent bond.

In addition, when the compound YB is bonded to the resin YA via a covalent bond, the composition includes a resin in which the resin YA and the compound YB are bonded via a covalent bond.
In addition, when the photoacid generator YC is bonded to the resin YA via a covalent bond, the composition includes a resin in which the resin YA and the photoacid generator YC are bonded via a covalent bond.

[Composition of aspect Y1]
Hereinafter, various components included in aspect Y1 will be explained.

<Resin YA>
(interactive group)
Resin YA has an interactive group that interacts (for example, electrostatic interaction) with compound YB, which will be described later. Note that the interactive group is as described above.

(Repeating unit with acid-decomposable group)
The resin YA may include a repeating unit having a group (acid-decomposable group) that is decomposed by the action of an acid to produce a polar group. However, when resin YA contains a repeating unit having an acid-decomposable group, its content is 20 mol% or less, preferably 15 mol% or less, and 10 mol% or less, based on the total repeating units of resin YA. The following is more preferable, 5 mol% or less is still more preferable, and 3 mol% or less is particularly preferable. Note that the lower limit is 0 mol% or more. Note that the acid-decomposable group is as described above.

(Preferred embodiment of resin YA)
As the resin YA, it is preferable to use a resin whose main chain is cut by the action of exposure, acid, base, or heating and whose molecular weight decreases (main chain cut resin), since the effects of the present invention are more excellent. . Examples of the resin YA, which is a main chain cleavage type resin, include resin YA-1.

《Resin YA-1》
Resin YA-1 contains an interactive group, and includes a repeating unit represented by the following formula (YP) and a repeating unit represented by the following formula (YQ). However, if the resin YA-1 contains a repeating unit having an acid-decomposable group, its content is 20 mol% or less based on all repeating units.
Note that in resin YA-1, the interactive group may be contained in any position. In resin YA-1, the interactive group may be contained in the repeating unit represented by formula (YP) and/or the repeating unit represented by formula (YQ), or may be contained in the repeating unit represented by formula (YP). and the repeating unit represented by formula (YQ), and the other repeating unit may be included in the interactive group.

In formula (YP), X ^Yp represents a halogen atom. L ^Yp represents a single bond or a divalent linking group. R ^Yp represents a substituent.

In formula (YQ), R ^Yq1 represents an alkyl group that may have a substituent. L ^Yq represents a single bond or a divalent linking group. R ^Yq2 represents a substituent.

In the resin YA-1, at least one of the substituent represented by R ^Yp in formula (YP) and the substituent represented by R ^Yq2 in formula (YQ) has an interactive group, Alternatively, it is preferable that the repeating unit represented by the formula (YP) and the repeating unit other than the repeating unit represented by the formula (YQ) are included, and the other repeating unit has an interactive group.

In resin YA-1, the total content of the repeating units represented by the above formula (YP) and the repeating units represented by the above formula (YQ) is 90 mol% or more based on all repeating units. The content is preferably 95 mol% or more, and more preferably 95 mol% or more. In addition, as an upper limit, 100 mol% or less is preferable.

In addition, in resin YA-1, the repeating unit represented by the above formula (YP) and the repeating unit represented by the above formula (YQ) are a random copolymer, a block copolymer, and an alternating copolymer ( It may be in any form such as ABAB...), but among these, an alternating copolymer is preferred.
A preferred embodiment of the resin YA-1 is an embodiment in which the proportion of the alternating copolymer in the resin X is 90% by mass or more (preferably 100% by mass or more) based on the total mass of the resin YA-1. Certain embodiments may also be mentioned.

In resin YA-1, the content of the repeating unit represented by the above formula (YP) is preferably 10 to 90 mol%, and preferably 30 to 70 mol%, based on the total repeating units. More preferred. In resin YA-1, the repeating unit represented by the above formula (YQ) preferably accounts for 10 to 90 mol%, more preferably 30 to 70 mol%, based on the total repeating units. .

In the above formula (YP), the halogen atom represented by X ^Yp is preferably a fluorine atom or a chlorine atom, and more preferably a chlorine atom, since the effects of the present invention are more excellent.
In the above formula (YP), the divalent linking group represented by L ^Yp is not particularly limited, but includes, for example, -CO-, -O-, -SO-, -SO ₂ -, -NR ^A -, alkylene group (preferably 1 to 6 carbon atoms, may be linear or branched), cycloalkylene group (preferably 3 to 15 carbon atoms), divalent aromatic hydrocarbon ring group (6 to 10 membered ring (6-membered rings are preferred, and 6-membered rings are more preferred), and divalent linking groups that are a combination of a plurality of these. Further, the alkylene group, the cycloalkylene group, and the divalent aromatic hydrocarbon ring group may have a substituent. Examples of the substituent include an alkyl group, a halogen atom, and a hydroxyl group. Examples of R ^A include a hydrogen atom or an alkyl group having 1 to 6 carbon atoms.
A preferred embodiment of the divalent linking group represented by L ^Yp includes an embodiment in which the position bonded to the main chain side of the divalent linking group represented by L ^Yp is -COO-.

In the above formula (YP), the substituent represented by ^R groups, halogen atoms, ester groups (-OCOR'' or -COOR'': R'' represents an alkyl group or a fluorinated alkyl group), lactone groups, alcoholic hydroxyl groups, interactive groups, etc. It will be done.
Note that the alcoholic hydroxyl group is to be distinguished from the phenolic hydroxyl group, and in this specification, a hydroxyl group that is substituted for an aliphatic hydrocarbon group is intended.

The repeating unit represented by the formula (YP) is preferably a repeating unit represented by the following formula (YP1).

In formula (YP1), X ^Yp1 has the same meaning as X ^Yp in formula (YP) above, and preferred embodiments are also the same.

Y ^Yp1 represents a single bond or -COO-.

L ^Yp1 represents a single bond or a divalent linking group.
The divalent linking group represented by L ^Yp1 is not particularly limited, but includes, for example, -CO-, -O-, -SO-, -SO ₂ -, -NR ^A -, alkylene group (preferably one carbon number to 6) (which may be linear or branched), and divalent linking groups that are a combination of two or more of these. Further, the alkylene group may have a substituent. Examples of the substituent include a halogen atom and a hydroxyl group. Examples of R ^A include a hydrogen atom or an alkyl group having 1 to 6 carbon atoms.

Ar ^Yp1 represents a (Yp2+1)-valent aromatic ring group or alicyclic group.
Examples of the divalent aromatic ring group when Yp2 is 1 include arylene groups having 6 to 18 carbon atoms such as phenylene group, tolylene group, naphthylene group, and anthracenylene group, or thiophene ring, furan ring, and pyrrole ring. , a benzothiophene ring, a benzofuran ring, a benzopyrrole ring, a triazine ring, an imidazole ring, a benzimidazole ring, a triazole ring, a thiadiazole ring, and a divalent aromatic ring group containing a heterocycle such as a thiazole ring. Among these, an arylene group is preferred, a phenylene group, a naphthalene group, or an anthracenylene group is more preferred, and a phenylene group or a naphthalene group is even more preferred.

As a specific example of a (Yp2+1)-valent aromatic ring group when Yp2 is an integer of 2 or more, (Yp2-1) arbitrary hydrogen atoms are removed from the above-mentioned specific example of a divalent aromatic ring group. The following groups are mentioned.

The (Yp2+1)-valent alicyclic group represented by Ar ^Yp1 may contain a heteroatom such as an oxygen atom or a carbonyl carbon. The (Yp2+1)-valent alicyclic group represented by Ar ^Yp1 includes, for example, polycyclic cycloalkanes such as norbornene, tetracyclodecane, tetracyclododecane, and adamantane from which (Yp2+1) arbitrary hydrogen atoms have been removed. The following groups are mentioned. Further, the (Yp2+1)-valent alicyclic group represented by Ar ^Yp1 includes a group obtained by removing (Yp2+1) arbitrary hydrogen atoms from a lactone ring or a sultone ring. The lactone ring and sultone ring are preferably 5- to 7-membered lactone rings and sultone rings, and other ring structures are fused to the 5- to 7-membered lactone ring and sultone ring to form a bicyclo structure or a spiro structure. A ring is more preferable.

The (Yp2+1)-valent aromatic ring group and alicyclic group may have a substituent other than R ^Yp1 .

Yp1 represents 0 or 1.
When Yp1 is 0, Yp2 represents 1. When Yp1 is 1, Yp2 represents an integer from 0 to 4.

R ^Yp1 represents a substituent. Examples of the substituent represented by R ^Yp1 include those similar to R ^Yp in the above formula (YP), and among them, an alkyl group or an interactive group which may have a substituent is preferable. As the substituent, a halogen atom is preferred.

In formula (YQ), the alkyl group represented by R ^Yq1 may be linear, branched, or cyclic. The number of carbon atoms in the alkyl group is preferably 1 to 12, more preferably 1 to 6, and even more preferably 1 to 3.
Further, the alkyl group represented by R ^Yq1 may have a substituent. Substituents include, but are not particularly limited to, halogen atoms, hydroxyl groups, and the like.
In formula (YQ), the divalent linking group represented by L ^Yq includes the same divalent linking group as the divalent linking group represented by L ^Yp in formula (YP) above.
Examples of the substituent represented by R ^q2 in formula (YQ) include the same substituents as the substituent represented by R ^Yp in the above formula (YP).

The repeating unit represented by formula (YQ) is preferably a repeating unit represented by formula (YQ1) below.

In formula (YQ1), R ^Yq11 has the same meaning as R ^Yq1 in formula (YQ) above, and preferred embodiments are also the same.

Y ^Yq1 represents a single bond or -COO-.

L ^Yq1 represents a single bond or a divalent linking group.
The divalent linking group represented by L ^Yq1 is not particularly limited, but includes, for example, -CO-, -O-, -SO-, -SO ₂ -, -NR ^A -, alkylene group (preferably one carbon number to 6) (which may be linear or branched), and divalent linking groups that are a combination of two or more of these. Further, the alkylene group may have a substituent. Examples of the substituent include a halogen atom and a hydroxyl group. Examples of R ^A include a hydrogen atom or an alkyl group having 1 to 6 carbon atoms.

Ar ^Yq1 represents a (Yq2+1)-valent aromatic ring group or alicyclic group.
Examples of the divalent aromatic ring group when Yq2 is 1 include arylene groups having 6 to 18 carbon atoms such as phenylene group, tolylene group, naphthylene group, and anthracenylene group, or thiophene ring, furan ring, and pyrrole ring. , a benzothiophene ring, a benzofuran ring, a benzopyrrole ring, a triazine ring, an imidazole ring, a benzimidazole ring, a triazole ring, a thiadiazole ring, and a divalent aromatic ring group containing a heterocycle such as a thiazole ring. Among these, an arylene group is preferred, and a phenylene group or a naphthalene group is more preferred.

Specific examples of (Yq2+1)-valent aromatic ring groups when Yq2 is an integer of 2 or more include (Yq2-1) arbitrary hydrogen atoms removed from the above-mentioned specific examples of divalent aromatic ring groups. The following groups are mentioned.

The (Yq2+1)-valent alicyclic group represented by Ar ^Yq1 may contain a hetero atom such as an oxygen atom or a carbonyl carbon. The (Yq2+1)-valent alicyclic group represented by Ar ^Yq1 includes, for example, polycyclic cycloalkanes such as norbornene, tetracyclodecane, tetracyclododecane, and adamantane from which (Yq2+1) arbitrary hydrogen atoms have been removed. The following groups are mentioned. Further, the (Yq2+1)-valent alicyclic group represented by Ar ^Yq1 includes a group obtained by removing (Yq2+1) arbitrary hydrogen atoms from a lactone ring or a sultone ring. The lactone ring and sultone ring are preferably 5- to 7-membered lactone rings and sultone rings, and other ring structures are fused to the 5- to 7-membered lactone ring and sultone ring to form a bicyclo structure or a spiro structure. A ring is more preferable.

The (Yq2+1)-valent aromatic ring group and alicyclic group may have a substituent other than R ^Yq12 .

Yq1 represents 0 or 1.
When Yq1 is 0, Yq2 represents 1. When Yq1 is 1, Yq2 represents an integer from 0 to 4.

R ^Yq12 represents a substituent. Examples of the substituent represented by R ^Yq12 include those similar to R ^Yp in the above formula (YP), and among them, an alkyl group or an interactive group which may have a substituent is preferable. As the substituent, a halogen atom is preferred.

The above-mentioned resin YA-1 may contain repeating units other than the above-mentioned repeating units as long as the effects of the present invention are not impaired.

Resin YA can be synthesized according to conventional methods (eg, radical polymerization).
The weight average molecular weight (Mw) of the resin YA is preferably 15,000 or more, more preferably 20,000 or more, and even more preferably 30,000 or more. The upper limit is, for example, preferably 200,000 or less, more preferably 150,000 or less, and even more preferably 100,000 or less.

The polydispersity (Mw/Mn) of the resin YA is not particularly limited, but is preferably 2.5 or less, more preferably 2.0 or less, and even more preferably 1.7 or less. The lower limit value is not particularly limited, and may be 1.0 or more.

In the composition of aspect Y1, the lower limit of the content of resin YA is preferably 30.0% by mass or more, more preferably 45.0% by mass or more, and 65.0% by mass based on the total solid content of the composition. % or more is more preferable. In addition, as an upper limit, 99.9 mass % or less is preferable, for example. Further, resin YA may be used alone or in combination. When two or more types are used, it is preferable that the total content is within the above-mentioned preferred content range.

<Compound YB>
The composition of embodiment Y1 comprises compound YB. Compound YB is a compound having an onium salt structure that generates an acid upon irradiation with light, and generates a sensitizer under the action of the acid.

The sensitizer produced from compound YB is preferably a sensitizer (photosensitizer) that absorbs light with a wavelength of more than 200 nm (preferably 250 nm or more). When the sensitizer produced from compound YB has the above wavelength characteristics, in step 3 (flood exposure step) of the pattern forming method described below, the absorption wavelength of compound YB itself and the absorption wavelength of the sensitizer produced from compound YB are (In other words, the absorption wavelength shifts significantly before and after the structural change from compound YB to a sensitizer), and unnecessary photosensitivity of compound YB can be suppressed. As a result, the sensitizer can be selectively exposed in step 3 (flood exposure step), and the resolution of the formed pattern is better.

The sensitizer produced from compound YB is preferably a compound that contains a carbonyl group and absorbs light on the long wavelength side of wavelengths exceeding 200 nm.
When the sensitizer produced from compound YB is a compound containing a carbonyl group, examples thereof include benzophenone derivatives, xanthone derivatives, thioxanthone derivatives, coumarin derivatives, acridone derivatives, naphthalene derivatives, anthracene derivatives, and acridone derivatives.

Compound YB has an onium salt structure that generates an acid upon irradiation with light.
The above-mentioned onium salt structure is intended to be a salt structure consisting of an anion site and a cation site, which is easily decomposed by exposure to light and has excellent acid production. It is preferable that the organic anion moiety has a very low ability to cause a nucleophilic reaction.
The number of onium salt structures in compound YB is not particularly limited, but is preferably 1 to 10, more preferably 1 to 6, and even more preferably 1 to 3.

Examples of organic acids generated from compound YB upon irradiation with light include sulfonic acids (aliphatic sulfonic acids, aromatic sulfonic acids, camphor sulfonic acids, etc.), carbonylsulfonylimidic acids, bis(alkylsulfonyl)imide acids, and , tris(alkylsulfonyl)methide acid, and the like.
Specific examples of the organic acid generated from compound YB upon irradiation with light include the organic acids exemplified as the generated acid of the onium salt in the composition of Embodiment X1.

If the sensitizer formation site of compound YB is a site that is deprotected by the action of an acid, such as a ketal structure or an acetal structure as described below, in order to generate a carbonyl compound by the deprotection reaction, the generation generated from compound YB is The pKa of the acid is preferably 2.0 or less, more preferably 1.0 or less, and even more preferably 0.0 or less. Note that the lower limit is preferably −15.0 or more.

Compound YB is preferably a compound having an onium salt structural part and a sensitizer forming part, and a structural part having a cation part and a sensitizer forming part, and a counter anion of the cation part of the above structural part. More preferably, it is a compound having In the above compound, the cation moiety and the counter anion form an onium salt structure site.
The onium salt structure is preferably a sulfonium salt structure or an iodonium salt structure.
The sensitizer forming site is preferably a site that has a ketal or acetal structure in which a carbonyl group is protected with an alcohol, and that can undergo a deprotection reaction to the carbonyl group by the action of an acid.

Examples of the compound YB include compounds represented by the following formula (Y1) or formula (Y2).

In formula (Y1), R ^Y1 and R ^Y2 each independently represent an organic group. The number of carbon atoms in the organic groups as R ^Y1 and R ^Y2 is preferably 1 to 30, more preferably 1 to 20. L ^Y1 represents a divalent linking group.
Furthermore, two of R ^Y1 , R ^Y2 , and L ^Y1 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. good. Examples of the group formed by combining two of R ^Y1 , R ^Y2 , and L ^Y1 include an alkylene group (e.g., butylene group and pentylene group), and -CH ₂ -CH ₂ -O-CH ₂ - CH ₂ - is mentioned.

The organic groups as R ^Y1 and R ^Y2 are not particularly limited, but are preferably an alkyl group, a cycloalkyl group, or an aryl group.
As the aryl group, a phenyl group or a naphthyl group is preferable, and a phenyl group is more preferable. The aryl group may be an aryl group having a heterocyclic structure having an oxygen atom, a nitrogen atom, a sulfur atom, or the like. Examples of the heterocyclic structure include pyrrole residue, furan residue, thiophene residue, indole residue, benzofuran residue, and benzothiophene residue.
The alkyl group or cycloalkyl group is preferably a linear alkyl group having 1 to 15 carbon atoms, a branched alkyl group having 3 to 15 carbon atoms, or a cycloalkyl group having 3 to 15 carbon atoms, such as a methyl group, Examples include ethyl group, propyl group, n-butyl group, sec-butyl group, t-butyl group, cyclopropyl group, cyclobutyl group, and cyclohexyl group.

The substituents that the aryl group, alkyl group, and cycloalkyl group of R ^Y1 and R ^Y2 may each independently include an alkyl group (for example, carbon number 1 to 15), a cycloalkyl group (for example, carbon number 3 to 15), aryl groups (for example, carbon atoms 6 to 14), alkoxy groups (for example, carbon atoms 1 to 15), cycloalkylalkoxy groups (for example, carbon atoms 1 to 15), halogen atoms, hydroxyl groups, and phenylthio groups. It will be done.

In formula (Y1), the divalent linking group as L ^Y1 is not particularly limited, but preferably represents an alkylene group, a cycloalkylene group, an aromatic group, or a group formed by combining two or more of these.
The alkylene group may be linear or branched and preferably has 1 to 20 carbon atoms, more preferably 1 to 10 carbon atoms.
The cycloalkylene group may be monocyclic or polycyclic, and preferably has 3 to 20 carbon atoms, more preferably 3 to 10 carbon atoms.
The aromatic group is a divalent aromatic group, preferably an aromatic group having 6 to 20 carbon atoms, and more preferably an aromatic group having 6 to 15 carbon atoms.
The aromatic ring constituting the aromatic group is not particularly limited, but includes, for example, an aromatic ring having 6 to 20 carbon atoms, and specific examples include a benzene ring, a naphthalene ring, an anthracene ring, a thiophene ring, and the like. A benzene ring or a naphthalene ring is preferred, and a benzene ring is more preferred.

In formula (Y1), R ^Y3 , R ^Y4 , and R ^Y5 have the same meanings as R ²³ , R ²⁴ , and R ⁹ in formula (XXXVI) above. Note that R ^Y3 and R ^Y4 may be connected to each other to form a ring structure. Examples of the group to which R ^Y3 and R ^Y4 are connected to each other include those mentioned above, and among them, an alkylene group having 1 to 10 carbon atoms is preferable.
Further, R ^Y5 is also preferably a polycyclic aromatic ring such as a carbazole group or a fluorene group. The polycyclic aromatic ring may further have a substituent. Examples of the substituent include a halogen atom, an alkyl group, an aryl group, a heteroaryl group, an alkyloxy group, an aryloxy group, an alkylthio group, an arylthio group, an alkyloxycarbonyl group, an aryloxycarbonyl group, and an aminocarbonyl group. Can be mentioned.

In formula (Y1), A _Y1 ^- represents an organic acid anion.
The organic acid anion represented by A _Y1 ^- has a proton adduct (A _Y1 ^- H) having a pKa of 2.0 or less (preferably 1.0 or less, more preferably 0.0 or less). Note that the lower limit value is preferably -15.0 or more.
Examples of the organic acid anion represented by A _Y1 ^- include those already mentioned as organic acids generated from compound YB upon irradiation with light.

In formula (Y2), R ^Y6 represents an aryl group, an alkyl group, or a cycloalkyl group.
Examples of the aryl group, alkyl group, and cycloalkyl group represented by ^RY6 include those similar to the aryl group, alkyl group, and cycloalkyl group represented by ^RY1 above, and preferred embodiments are also the same. be.
In formula (Y2), R ^Y3 , R ^Y4 , R ^Y5 , L ^Y1 , and A _Y1 ^- have the same meaning as R ^Y3 , R ^Y4 , R ^Y5 , L ^Y1 , and A _Y1 ^- in formula (Y1) above. The preferred embodiments are also the same.

Examples of compound YB include compounds represented by the following formulas (I) to (IV).

In the above formulas (I) to (III), R ¹ , R ² , R ^1' , R ^2' , R ^1'' , R ^2'' , R ³ , and R ⁴ are each independently a hydrogen atom; Phenyl group; naphthyl group; anthracenyl group; phenoxy group; naphthoxy group; anthracenoxy group; amino group; amide group; halogen atom; linear, branched or branched having 1 to 30 carbon atoms (preferably 1 to 5 carbon atoms) Cyclic saturated or unsaturated hydrocarbon group (preferably an alkyl group); a phenoxy group substituted with an alkoxy group having 1 to 5 carbon atoms, a hydroxy group, an amino group, an amide group, or an alkyl group having 1 to 5 carbon atoms; A linear, branched or cyclic saturated or unsaturated hydrocarbon group (preferably an alkyl group) having 1 to 30 carbon atoms (preferably 1 to 5 carbon atoms), an alkoxy group having 1 to 5 carbon atoms, an amino group , an amide group, or a phenyl group substituted with a hydroxy group; an alkoxy group having 1 to 5 carbon atoms, an alkyl group having 1 to 5 carbon atoms, a naphthoxy group substituted with an amino group, an amide group, or a hydroxy group; carbon number anthracenoxy group substituted with an alkoxy group having 1 to 5 carbon atoms, an alkyl group having 1 to 5 carbon atoms, an amino group, an amide group, or a hydroxy group; an alkoxy group having 1 to 5 carbon atoms, a phenoxy group, a naphthoxy group, an anthracenoxy group; A linear, branched or cyclic saturated or unsaturated hydrocarbon group (preferably an alkyl group); or represents a carbonyl group to which an alkyl group having 1 to 12 carbon atoms is bonded.
In the above formulas (I) to (III), the hydrogen atom of the hydroxy group is a phenyl group; a halogen atom; a linear, branched, or cyclic saturated or an unsaturated hydrocarbon group (preferably an alkyl group); or a linear, branched or cyclic saturated or unsaturated hydrocarbon group having 1 to 30 carbon atoms (preferably 1 to 5 carbon atoms); (alkyl group), an alkoxy group having 1 to 5 carbon atoms, or a phenyl group substituted with a hydroxy group. When the hydrogen atom of the hydroxy group is substituted, the sulfonium salt compound will contain a ketal compound group or an acetal compound group. In formulas (I) to (III), any two or more groups among R ¹ , R ² , R ^1' , R ^2' , R ^1'' , R ^2'' , R ³ , and R ⁴ are , by a single bond or a double bond, or -CH ₂ -, -O-, -S-, -SO ₂ -, -SO ₂ NH-, -CO-, -COO-, -NHCO-, -NHCO- They may be bonded to each other to form a ring structure via a bond containing NH-, -CHR ^e -, -CR ^e ₂ -, -NH- or -NR ^e -. R ^e represents a phenyl group; a phenoxy group; a halogen atom; a linear, branched or cyclic saturated or unsaturated hydrocarbon group having 1 to 30 carbon atoms (preferably 1 to 5 carbon atoms) (preferably an alkyl group); ); a phenoxy group substituted with an alkoxy group having 1 to 5 carbon atoms, a hydroxy group, or an alkyl group having 1 to 5 carbon atoms; or a straight chain having 1 to 30 carbon atoms (preferably 1 to 5 carbon atoms); , a branched or cyclic saturated or unsaturated hydrocarbon group (preferably an alkyl group), an alkoxy group having 1 to 5 carbon atoms, or a phenyl group substituted with a hydroxy group. R ¹ , R ² , R ^1' , R ^2' , R ^1'' , R ^2'' , R ³ and R ⁴ each independently represent a phenyl group; a phenoxy group; an alkyl group having 1 to 5 carbon atoms; It preferably represents a substituted phenoxy group; or a phenyl group substituted with an alkoxy group having 1 to 5 carbon atoms, or a hydroxy group.

In formulas (I) to (III), X ⁻ represents an organic acid anion.
As for the ^organic acid anion represented by The value is preferably −15.0 or higher.).

In the above formulas (I) to (III), -C(-OH)R ¹ R ² , -C(-OH)R ^1' R ^2' , and -C(-OH)R ^1'' R ^2'' Specific examples of the group represented by the above include groups represented by the following formulas. Note that * in the formula represents a bonding moiety with a sulfur ion in the above formulas (I) to (III). In the groups represented by -C(-OH)R ¹ R ² , -C(-OH)R ^1' R ^2' , and -C(-OH)R ^1'' R ^2'' , a hydroxy group and this The carbon atom to which the hydroxy group is bonded becomes a carbonyl group in step 2 (pattern exposure step) described below. In this way, in the compounds represented by formulas (I) to (III) above, -C(-OH)R ¹ R ² , -C(-OH)R ^1' R ^2' , and -C(- The group represented by OH)R ^1'' R ^2'' separates after step 2 (pattern exposure step) to generate a sensitizer.

In the above formulas (IV) to (V), R ⁵ , R ⁶ , R ^5' , R ^6' and R ⁷ each independently represent a hydrogen atom; a phenyl group; a naphthyl group; an anthracenyl group; a phenoxy group; group; anthracenoxy group; amino group; amide group; halogen atom; linear, branched or cyclic saturated or unsaturated hydrocarbon group having 1 to 30 carbon atoms (preferably 1 to 5 carbon atoms) (preferably alkyl group); a phenoxy group substituted with an alkoxy group having 1 to 5 carbon atoms, a hydroxy group, an amino group, an amide group, or an alkyl group having 1 to 5 carbon atoms; a phenoxy group having 1 to 30 carbon atoms (preferably 1 to 5 carbon atoms) ), a phenyl group substituted with a linear, branched or cyclic saturated or unsaturated hydrocarbon group (preferably an alkyl group), an alkoxy group having 1 to 5 carbon atoms, an amino group, an amide group, or a hydroxy group. ; C1-5 alkoxy group, C1-5 alkyl group, amino group, amido group, or naphthoxy group substituted with a hydroxy group; C1-5 alkoxy group, C1-5 alkoxy group; Anthracenoxy group substituted with an alkyl group, amino group, amide group, or hydroxy group; substituted with an alkoxy group having 1 to 5 carbon atoms, phenoxy group, naphthoxy group, anthracenoxy group, amino group, amide group, or hydroxy group , a linear, branched or cyclic saturated or unsaturated hydrocarbon group (preferably an alkyl group) having 1 to 30 carbon atoms (preferably 1 to 5 carbon atoms); or an alkyl group having 1 to 12 carbon atoms represents a bonded carbonyl group. In the above formulas (IV) to (V), the hydrogen atom of the hydroxy group is a phenyl group; a halogen atom; a linear, branched, or cyclic saturated or an unsaturated hydrocarbon group (preferably an alkyl group); or a linear, branched or cyclic saturated or unsaturated hydrocarbon group having 1 to 30 carbon atoms (preferably 1 to 5 carbon atoms); (alkyl group), an alkoxy group having 1 to 5 carbon atoms, or a phenyl group substituted with a hydroxy group. When the hydrogen atom of the hydroxy group is substituted, the iodonium salt compound will contain a ketal compound group or an acetal compound group. In formulas (IV) to (V), any two or more groups among R ⁵ , R ⁶ , R ^5' , R ^6' , and R ⁷ may be bonded by a single bond or double bond, or -CH ₂ -, -O-, -S-, -SO ₂ -, -SO ₂ NH-, -CO-, -COO-, -NHCO-, -NHCO-NH-, -CHR ^f -, -CR ^f ₂ - , -NH- or -NR ^f - may form a ring structure. R ^f is a phenyl group; a phenoxy group; a halogen atom; a linear, branched or cyclic saturated or unsaturated hydrocarbon group having 1 to 30 carbon atoms (preferably 1 to 5 carbon atoms) (preferably an alkyl group); ); a phenoxy group substituted with an alkoxy group having 1 to 5 carbon atoms, a hydroxy group, or an alkyl group having 1 to 5 carbon atoms; or a straight chain having 1 to 30 carbon atoms (preferably 1 to 5 carbon atoms); , a branched or cyclic saturated or unsaturated hydrocarbon group (preferably an alkyl group), an alkoxy group having 1 to 5 carbon atoms, or a phenyl group substituted with a hydroxy group. R ⁵ , R ⁶ , R ^5' , R ^6' and R ⁷ each independently represent a phenyl group; a phenoxy group; an alkoxy group having 1 to 5 carbon atoms, a hydroxy group, or an alkyl group having 1 to 5 carbon atoms; or a phenyl group substituted with an alkoxy group having 1 to 5 carbon atoms or a hydroxy group.

In formulas (IV) to (V), Y ⁻ represents an organic acid anion.
As for the organic acid anion represented by Y ^- , the pKa of its proton adduct (YH) is 2.0 or less (preferably 1.0 or less, more preferably 0.0 or less. Note that the lower limit The value is preferably −15.0 or higher.).

In the above formulas (IV) to (V), the groups represented by -C(-OH)R ⁵ R ⁶ and -C(-OH)R ^5' R ^6' are specifically the groups represented by the above formula ( -C(-OH)R ¹ R ² , -C(-OH)R ^1' R ^2' , and -C(-OH)R ^1'' R ^2'' etc. exemplified in I) to (III) Groups similar to those represented may be mentioned.

Specific examples of the organic acid anions represented by X ^- and Y ^- mentioned above include those already described as organic acids generated from compound YB upon irradiation with light.

In step 3 (flood exposure step), which will be described later, the sensitizer generated from compound YB is more likely to undergo energy transfer from the sensitizer generated from compound YB to compound YB, and the decomposition of compound YB is better. It is desirable that the energy level of the LUMO of compound YB is higher than that of the LUMO of compound YB.

In the composition of aspect Y1, the content of compound YB is not particularly limited, but is preferably 1.0% by mass or more, more preferably 2.0% by mass or more, and 3.0% by mass or more based on the total solid content of the composition. More preferably, the amount is % by mass or more. Further, the content is preferably 30.0% by mass or less, more preferably 25.0% by mass or less. Compound YB may be used alone or in combination of two or more. When two or more types are used, it is preferable that the total content is within the above-mentioned preferred content range.

<Other ingredients>
The composition of aspect Y1 may further contain other components than the above-mentioned components.
Other components include the surfactant, basic compound (quencher), solvent, and other additives described in the composition of aspect X1. Further, the contents of other components are also the same as those explained for the composition of aspect X1.

[Composition of aspect Y2]
Hereinafter, various components included in aspect Y2 will be explained.
In the composition of aspect Y2, the onium salt structure in compound YB is not a structure that generates an acid that can generate a sensitizer, and the composition separately contains a photoacid generator YC as a source of the acid. Other than this point, it is the same as the composition of the above-mentioned embodiment Y1, and the preferred embodiments are also the same.

In the composition of aspect Y2, when compound YB is a compound having a site that can be deprotected by the action of an acid, such as the above-mentioned ketal structure or acetal structure, in producing a carbonyl compound by the deprotection reaction, compound YB As mentioned above, the pKa of the generated acid is preferably about -15.0 to 2.0. The composition of embodiment Y2 is a compound in which the onium salt structure in compound YB is not a structure that generates an acid capable of producing a sensitizer (for example, the pKa of the generated acid is more than 2.0 (preferably 2.0). (more than 1, more preferably more than 2.5)). Note that specific examples of compound YB that can be used in the composition of aspect Y2 include compounds in which the anion of compound YB in aspect Y1 is changed to a carboxylic acid anion and a phenolic acid anion. Examples of the carboxylic acid anion and phenolic acid anion include those described as the generated acid of the onium salt XB that can be used in the composition of embodiment X2.
The composition of embodiment Y2 includes a photoacid generator YC as a compound that acts on compound YB to generate an acid capable of producing a sensitizer.

Examples of the photoacid generator YC include those similar to the photoacid generator XD included in the composition of Aspect 3 described above, and the content in the composition can also be in the same numerical range.

[Composition of aspect Y3]
Hereinafter, various components included in aspect Y3 will be explained.
In the composition of aspect Y3, resin YA and compound YB are bonded via a covalent bond. That is, the composition of aspect Y3 includes a resin (hereinafter also referred to as "resin YAY3") in which resin YA and compound YB are linked via a covalent bond.
Note that the resin YAY3 may or may not have an interactive group that can interact with the onium salt structure in compound YB. It is preferable that the resin YAY3 has an interactive group so that the effects of the present invention are more excellent.
The composition of Embodiment Y3 is the same as the composition of Embodiment Y1, and the preferred embodiments are also the same, except that the composition includes resin YAY3 instead of containing resin YA and compound YB individually.

<Resin YAY3>
The resin YAY3 will be explained below.
Resin YAY3 is a resin in which resin YA and compound YB are linked via a covalent bond. Resin YAY3 may or may not have an interactive group that interacts with the onium salt structure in compound YB. It is preferable that the resin YAY3 has an interactive group since the effects of the present invention are more excellent. Note that the interactive group is as described above.

The resin YAY3 may contain a repeating unit having an acid-decomposable group. However, when resin YAY3 contains a repeating unit having an acid-decomposable group, its content is 20 mol% or less, preferably 15 mol% or less, and 10 mol% or less, based on the total repeating units of resin YAY3. The following is more preferable, 5 mol% or less is still more preferable, and 3 mol% or less is particularly preferable. Note that the lower limit is 0 mol% or more. Note that the acid-decomposable group is as described above.

Preferably, the resin YAY3 contains a repeating unit in which the compound YB has a group connected by a covalent bond.
Examples of the group to which compound YB is linked via a covalent bond include a group represented by -L ^yr -O ^yr . L ^yr represents a single bond or a divalent linking group, and O ^yr represents a group formed by removing one hydrogen atom from the compound YB already described in the composition of embodiment Y1. Among these, O ^yr preferably represents a group formed by removing one hydrogen atom from the anion site of the compound YB described above. Specific examples of O ^yr include groups represented by the following formula (O3) or formula (O4), which will be described later.

The divalent linking group represented by L ^yr is not particularly limited, but includes, for example, -CO-, -O-, -SO-, -SO ₂ -, -NR ^A -, and an alkylene group (preferably one having 1 carbon number). ～6. Can be linear or branched), cycloalkylene group (preferably has 3 to 15 carbon atoms), divalent aromatic hydrocarbon ring group (preferably 6 to 10-membered ring, more preferably 6-membered ring) ), and a divalent linking group that is a combination of a plurality of these. Further, the alkylene group, the cycloalkylene group, and the divalent aromatic hydrocarbon ring group may have a substituent. Examples of the substituent include an alkyl group, a halogen atom, and a hydroxyl group. Examples of R ^A include a hydrogen atom or an alkyl group having 1 to 6 carbon atoms.
A preferred embodiment of the divalent linking group represented by L ^yr is an embodiment in which the position bonded to the main chain side of the divalent linking group represented by L ^yr is -COO-.

*-Y _A ^- N _A ⁺ formula (O3)
*-N _B ⁺ Y _B ^-Formula (O4)

In formula (O3), Y _A ^- represents a monovalent anionic group. N _A ⁺ represents a group having a cation site serving as a counter cation of Y _A ^- and a sensitizer forming site. * represents the connection position.
*-Y _A ^- N _A ⁺ is specifically a group represented by formulas (I) to (V), formula (Y1), and formula (Y2) explained in the composition of aspect Y1. Examples include groups formed by removing one hydrogen atom from the anion moiety of the compound.

In formula (O4), N _B ⁺ represents a group having a cation site and a sensitizer forming site. Y _A ^- represents an organic anion serving as a counter anion to N _B ⁺ . * represents the connection position.
*-N _B ⁺ Y _B ^- is specifically a group represented by formulas (I) to (V), formula (Y1), and formula (Y2) explained in the composition of embodiment Y1. Examples include groups formed by removing one hydrogen atom from the non-anionic part (structural part having a cation part and a sensitizer forming part) of the compound.

Specific examples of the repeating unit in which compound YB has a group connected by a covalent bond include a repeating unit represented by (YR) below.

In the formula, L ^yr represents a single bond or a divalent linking group. Note that the divalent linking group represented by L ^yr includes the same groups as those mentioned above as the divalent linking group represented by L ^yr . Examples of O ^yr include a group represented by the above-mentioned formula (O3) or formula (O4).
X ^yr represents a hydrogen atom, a halogen atom, or an alkyl group which may have a substituent.
The halogen atom represented by X ^yr is preferably a fluorine atom or a chlorine atom, more preferably a chlorine atom.
The alkyl group represented by X ^yr may be linear, branched, or cyclic. The number of carbon atoms in the alkyl group is preferably 1 to 12, more preferably 1 to 6, and even more preferably 1 to 3.
Further, the substituent that the alkyl group represented by X ^yr may have is not particularly limited, and examples thereof include a halogen atom and a hydroxyl group.

In the resin YAY3, the content of the repeating unit represented by the above formula (YR) is preferably 30 mol% or more, more preferably 40 mol% or more, based on all repeating units. In addition, as an upper limit, 100 mol% or less is preferable, and 80 mol% or less is more preferable.

(Preferred embodiment of resin YAY3)
The resin YAY3 is preferably a resin whose main chain is cut by the action of exposure, acid, base, or heating and whose molecular weight decreases (main chain cleavage type resin), since the effects of the present invention are more excellent. .
The resin YAY3, which is a main chain cleavage type resin, contains a repeating unit represented by the above formula (YR), a repeating unit represented by the formula (YP) in the resin YA explained in the composition of aspect Y1, and a repeating unit represented by the formula (YP) and the formula ( It is preferable that the resin contains at least one type of repeating unit represented by YQ). From the viewpoint of main chain scission property, among others, a resin containing a repeating unit represented by the formula (YR) in which X ^r represents a halogen atom and a repeating unit represented by the formula (YQ), or a resin in which X ^r is substituted It is preferable that the resin contains a repeating unit represented by the formula (YR) representing an alkyl group which may have a group and a repeating unit represented by the formula (YP).

When the resin YAY3 is a resin containing a repeating unit represented by the above-mentioned formula (YR) and at least one repeating unit represented by the formula (YP) or a repeating unit represented by the formula (YQ), The total content of the repeating unit represented by the formula (YR), the repeating unit represented by the formula (YP), and the repeating unit represented by the above formula (YQ) is 90 mol based on all repeating units. % or more, more preferably 95 mol% or more. In addition, as an upper limit, 100 mol% or less is preferable.
In addition, in the resin YAY3, the repeating unit selected from the group consisting of the repeating unit represented by the formula (YR), the repeating unit represented by the formula (YP), and the repeating unit represented by the above formula (YQ) is: It may be in any form such as a random copolymer, a block copolymer, or an alternating copolymer (ABAB...), but among these, an alternating copolymer is preferable.
A preferred embodiment of the resin YAY3 includes an embodiment in which the proportion of the alternating copolymer in the resin YAY3 is 90% by mass or more (preferably 100% by mass or more) based on the total mass of the resin YAY3. It will be done.

Resin YAY3 can be synthesized according to conventional methods (eg, radical polymerization).
The weight average molecular weight (Mw) of the resin YAY3 is preferably 15,000 or more, more preferably 20,000 or more, even more preferably 30,000 or more, and particularly preferably 40,000 or more. The upper limit is, for example, preferably 200,000 or less, more preferably 150,000 or less, and even more preferably 100,000 or less.

The polydispersity (Mw/Mn) of the resin YAY3 is not particularly limited, but is preferably 2.5 or less, more preferably 2.0 or less, and even more preferably 1.7 or less. The lower limit value is not particularly limited, and may be 1.0 or more.

In the composition of aspect Y3, the lower limit of the content of resin YAY3 is preferably 30.0% by mass or more, more preferably 45.0% by mass or more, and 65.0% by mass based on the total solid content of the composition. % or more is more preferable. In addition, as an upper limit, 100 mass % or less is preferable, and 99.9 mass % or less is more preferable, for example. Furthermore, the resin YAY3 may be used alone or in combination. When two or more types are used, it is preferable that the total content is within the above-mentioned preferred content range.

[Composition of aspect Y4]
Hereinafter, various components included in aspect Y4 will be explained.
In the composition of aspect Y4, the onium salt structure of compound YB in the resin in which resin YA and compound YB are linked via a covalent bond is not a structure that generates an acid capable of producing a sensitizer, and the composition The composition is the same as the composition of Embodiment X3 above, except that it separately contains a photoacid generator YC as an acid source for producing a sensitizer by acting on compound YB, and the preferred embodiments are also the same.

In the resin (YAY4) in which resin YA and compound YB are linked via a covalent bond, which is included in the composition of aspect Y4, the onium salt structure of compound YB to which resin YA is covalently bonded can generate a sensitizer. It is the same as resin XAY3 contained in the composition of aspect Y3 except that it does not have a structure that generates acid.
That is, resin YAY4 in the composition of aspect Y4 is composed of resin XA and compound YB whose onium salt structure in the molecule is not a structure that generates an acid that can generate a sensitizer (for example, the pKa of the generated acid is 2.0 (preferably greater than 2.1, more preferably greater than 2.5) are linked via covalent bonds.
Examples of such onium salt structures include onium salt structures in which weak acids such as carboxylic acids and phenolic acids are used as generated acids.
A specific example of the above-mentioned resin includes a resin in which the anion in compound YB is changed to a carboxylic acid anion and a phenolic acid anion in resin YAY3 in aspect Y3. Examples of the carboxylic acid anion and phenolic acid anion include those described as the generated acid of the onium salt XB that can be used in the composition of embodiment X2.
The composition of embodiment Y4 contains a photoacid generator YC as a compound that generates an acid capable of producing a sensitizer by acting on compound YB.

The photoacid generator YC and its content are the same as the photoacid generator YC and its content in the composition of embodiment Y2 described above.

[Modifications of each composition of aspects Y2 and Y4]
In each of the compositions of aspects Y2 and Y4, the photoacid generator YC may be bonded to the resin YA via a covalent bond.
The resin in which the resin YA and the photoacid generator YC are linked via a covalent bond preferably contains a repeating unit having a group to which the photoacid generator YC is linked via a covalent bond. Such a repeating unit is a repeating unit represented by the formula (YR) described in the composition of aspect Y3, where "O ^yr " is formed by removing one hydrogen atom from the photoacid generator YC. Examples include repeating units representing groups.
In the resin in which the resin YA and the photoacid generator YC are linked via a covalent bond, the content of repeating units having a group to which the photoacid generator YC is linked via a covalent bond is 1 mol based on all repeating units. % or more is preferable, and 3 mol% or more is more preferable. In addition, as an upper limit, 15 mol% or less is preferable, and 10 mol% or less is more preferable. In the resin in which the resin YA and the photoacid generator YC are linked via a covalent bond, the repeating unit may contain only one type or two or more types. When a plurality of the repeating units are included, the content is preferably the total content.

[Resist film, pattern formation method]
The procedure of the pattern forming method using the above resist composition is not particularly limited, but preferably includes the following steps.
Step 1: Forming a resist film on a substrate using a resist composition Step 2: Exposing the resist film in a pattern with light having a wavelength of 200 nm or less to generate a sensitizer Step 3: Pattern Step 4: Flood exposure of the exposed resist film (resist film obtained in step 2) with light having a wavelength of more than 200 nm and sensitizing the sensitizer. A process of forming a pattern by performing a development process using a developer on the resist film obtained in

Further, after step 2, the following step 2-A may be included.
Step 2-A: Heating step of heating the pattern-exposed resist film (resist film obtained in Step 2)

Furthermore, after step 3, the following step 3-A may be included.
Step 3-A: Heating step of heating the flood exposed resist film (resist film obtained in step 3)

Furthermore, after step 4, step 4-A may be further included.
Step 4-A: A step of rinsing the developed resist film (resist film obtained in step 4) using a rinsing liquid

[Step 1: Resist film formation step]
Step 1 is a step of forming a resist film on a substrate using a resist composition.
The definition of the resist composition is as described above.

Examples of methods for forming a resist film on a substrate using a resist composition include a method of applying a resist composition onto a substrate.
Note that it is preferable to filter the resist composition as necessary before coating. 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 can be applied onto a substrate (eg, silicon, silicon dioxide coated), such as those used in the manufacture of integrated circuit devices, by any suitable application method, such as a spinner or coater. The coating method is preferably spin coating using a spinner. The rotation speed during spin coating using a spinner is preferably 1000 to 3000 rpm.
After applying the resist composition, the substrate may be dried to form a resist film. Note that, if necessary, various base films (inorganic film, organic film, antireflection film) may be formed under the resist film.

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

The thickness of the resist film is not particularly limited, but is preferably 10 to 120 nm from the standpoint of forming fine patterns with higher precision. Among these, when EUV exposure and EB exposure are used in the pattern exposure step of Step 2, the thickness of the resist film is more preferably 10 to 65 nm, and even more preferably 15 to 50 nm.

Note that a top coat may be formed on the upper layer of the resist film using a top coat composition.
Preferably, the top coat composition does not mix with the resist film and can be uniformly applied to the upper layer of the resist film. The top coat is not particularly limited, and a conventionally known top coat can be formed by a conventionally known method. Can be formed.
For example, it is preferable to form a top coat containing a basic compound as described in JP-A-2013-061648 on the resist film. Specific examples of basic compounds that may be included in the top coat include basic compounds that may be included in the resist composition.
It is also preferable that the top coat contains a compound containing at least one group or bond selected from the group consisting of an ether bond, a thioether bond, a hydroxyl group, a thiol group, a carbonyl bond, and an ester bond.

[Process 2: Pattern exposure process]
Step 2 is a step of exposing the resist film in a pattern.
Examples of the exposure method include a method of irradiating the formed resist film with actinic light or radiation of a predetermined wavelength through a predetermined mask.
The exposure light is preferably deep ultraviolet light with a wavelength of 200 nm or less, and specific examples include ArF excimer laser (193 nm), F ₂ excimer laser (157 nm), EUV (13 nm), X-rays, and electron beams.
Among these, EUV or electron beams are preferred as actinic rays or radiation.

When the composition used in Step 1 is a composition that satisfies Requirement 1, in Step 2, the resist film is pattern-exposed to light with a wavelength of 200 nm or less, so that the onium salt XB and the photoacid generator are removed in the exposed area. XD or the sensitizer precursor XC is decomposed to generate an acid, and a sensitizer can be produced from the sensitizer precursor XC by the action of this acid.
When the composition used in Step 1 is a composition that satisfies Requirement 2, in Step 2, the resist film is pattern-exposed to light with a wavelength of 200 nm or less, so that the onium salt structure or light in compound YB is removed in the exposed region. Acid generator YC decomposes to generate acid, and a sensitizer can be produced from compound YB by the action of this acid.
In the pattern exposure in step X2, only a part of the acid generating components such as the onium salt XB, the photoacid generator XD, the sensitizer precursor XC, the onium salt structure in compound YB, and the photoacid generator YC are cleaved. It is preferable to adjust the exposure amount accordingly.

[Step 3: Flood exposure]
Step 4 is a step of flood exposure with light having a wavelength of over 200 nm and sensitizing the sensitizer. In step 3 (flood exposure step), the sensitizer in the exposed area in step 2 (pattern exposure step) selectively absorbs light and is excited, causing energy transfer to components such as onium salt XB and compound YB. cleavage of the onium salt or onium salt structure may occur. As a result, when the resin contains an interactive group, the association structure due to electrostatic interaction between the interactive group contained in the resin and the onium salt or the onium salt structure contained in the predetermined compound can be released. In addition, in systems in which a resin and an onium salt or a specified compound containing an onium salt structure in the molecule are bonded together via a covalent bond and exist as one body, the molecular weight of the resin is lowered by cleavage of the onium salt or onium salt structure. and polarity changes may occur. On the other hand, the reaction in the unexposed region in step 2 (pattern exposure step) is suppressed due to the absence of the sensitizer. As a result, in step 4 (developing step), a pattern can be formed by the dissolution contrast in the exposed and unexposed regions.
In addition, in step 3 (flood exposure), in order to suppress the cleavage of the onium salt or onium salt structure in the unexposed region in step 2 (pattern exposure step), the wavelength of the exposure light in step 3 is set to The wavelength is preferably longer than the wavelength that can be absorbed by acid-generating components such as sensitizer precursor XC, photoacid generator XD, compound YB, and photoacid generator XC.
Specifically, the wavelength of the exposure light is preferably 280 nm or more, more preferably 320 nm or more, and may be 350 nm or more. The upper limit is not particularly limited, but is often 500 nm or less.

Examples of the exposure light include infrared light, visible light, and near-ultraviolet light, with near-ultraviolet light being preferred.
Step 2 (pattern exposure step) and Step 3 (flood exposure step) are preferably carried out under the atmosphere, under a reduced pressure atmosphere, under an inert atmosphere, or the like. Among these, it is more preferable to carry out under a reduced pressure atmosphere or an inert atmosphere containing nitrogen or argon.

[Step 2-A, Step 3-A: Heating step]
It is preferable to perform a heating step after step 2 and before performing step 3 (flood exposure step). By performing the heating step of Step 2-A, the reaction in the exposed region of Step 2 can be promoted.
Moreover, after step 3 and before implementing step 4 (developing step), it is preferable to perform a heating step. By performing the heating step of Step 3-A, the reaction in the exposed region of Step 2 is promoted, and the sensitivity and pattern shape are improved.

The heating temperature in Step 2-A and Step 3-A is preferably 30 to 150°C, more preferably 60 to 140°C, and even more preferably 60 to 120°C.
The heating time in Step 2-A and Step 3-A is preferably 5 to 1000 seconds, more preferably 10 to 180 seconds, and even more preferably 10 to 120 seconds.
The heating in Step 2-A and Step 3-A can be carried out by means provided in a normal exposure machine and/or developing machine, or may be carried out using a hot plate or the like.
Note that it is also preferable that the heating step is carried out in a humidity-controlled environment.

[Step 4: Development step]
Step 4 is a step in which the exposed resist film is developed using a developer.
The developer may be an alkaline aqueous solution or a developer containing an organic solvent (hereinafter also referred to as an organic solvent developer), but is preferably an organic solvent developer. In addition, in the case of a resist film containing the main chain-cleaved resin described above, by developing it using an organic solvent-based developer, the exposed region of the exposed resist film is removed and a pattern is formed. Note that the developer will be described later.

Development methods include, for example, a method in which the substrate is immersed in a tank filled with a developer for a certain period of time (dip method), a method in which the developer is raised on the surface of the substrate by surface tension and the substrate is left still for a certain period of time for development (paddle 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 rotating substrate (dynamic dispensing method). can be mentioned.
Furthermore, after the step of developing, a step of stopping the development may be carried out while substituting another solvent.
The development time is not particularly limited as long as the resin in the unexposed 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.

[Step 4-A (rinsing step)]
Step 4-A is a step of cleaning the pattern obtained in step 3 (developing step) using a rinsing liquid. Note that the rinsing liquid will be described later.

Examples of the rinsing method include methods similar to the developing method in step 3 (developing step) described above (dip method, paddle method, spray method, and dynamic dispense method).
The treatment time is preferably 10 to 300 seconds, more preferably 10 to 120 seconds, even more preferably 10 to 100 seconds, and particularly preferably 10 to 60 seconds.
The temperature of the rinse liquid is preferably 0 to 50°C, more preferably 15 to 35°C.

<Developer and rinse solution>
The developer and rinse solution may be an alkaline aqueous solution or a developer containing an organic solvent (organic solvent developer), but an organic solvent developer is preferable.
Hereinafter, chemical solutions that are preferably used as a developer and a rinse solution will be described.
Note that at least one of the developing solution and the rinsing solution is preferably a chemical solution containing two or more types of organic solvents, which will be described later.

(chemical solution)
The content of the organic solvent in the chemical solution is preferably 50% by mass or more, more preferably 80% by mass or more, even more preferably 90% by mass or more, and particularly preferably 95% by mass or more, based on the total amount of the chemical solution. In addition, as an upper limit, 99.9 mass % or less is preferable, 99.5 mass % or less is more preferable, 99.0 mass % or less is more preferable, and 98.0 mass % or less is still more preferable.
The organic solvent contained in the chemical solution may be one type alone or two or more types.
In addition, when a chemical|medical solution contains two or more types of organic solvents, it is preferable that the above-mentioned content is a total content of two or more types of organic solvents.
Moreover, the chemical solution may contain water. The water content relative to the total mass of the chemical solution 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.

As the organic solvent contained in the chemical solution, organic solvents known as developing solutions and rinsing solutions can be used.
Preferably, the chemical solution contains at least one organic solvent selected from the group consisting of ester solvents, hydrocarbon solvents, alcohol solvents, ether solvents, ketone solvents, and amide solvents. The organic solvent contained in the chemical solution is preferably an organic solvent selected from the group consisting of ester solvents, hydrocarbon solvents, alcohol solvents, ether solvents, ketone solvents, and amide solvents.
Furthermore, at least one of the organic solvents contained in the chemical solution is preferably an ester solvent or a hydrocarbon solvent, and the organic solvent contained in the chemical solution preferably contains both an ester solvent and a hydrocarbon solvent. More preferred.

<Specific examples of ester solvents, hydrocarbon solvents, alcohol solvents, ether solvents, and ketone solvents>
Hereinafter, specific examples of ester solvents, hydrocarbon solvents, alcohol solvents, ether solvents, ketone solvents, and amide solvents that can be suitably used as organic solvents included in the chemical solution will be described.

(ester solvent)
The ester solvent is not particularly limited, but it preferably has 3 to 12 carbon atoms, more preferably 5 to 10 carbon atoms, in order to achieve better effects of the present invention.

Ester solvents have heteroatoms. Examples of the above-mentioned heteroatoms include oxygen atoms, and it is preferable that the heteroatoms include only oxygen atoms.
The number of heteroatoms that the ester solvent has is preferably 2 to 6, more preferably 2 to 3, and even more preferably 2. Further, the ester solvent may have one or more -COO-, and preferably has only one -COO-.

The boiling point of the ester solvent is preferably 100 to 200°C, more preferably 120 to 200°C, even more preferably 120 to 180°C.
The ClogP of the ester solvent is preferably 0.50 to 4.00, more preferably 1.00 to 4.00, even more preferably 1.20 to 3.50, particularly preferably 1.50 to 3.00. .

Examples of ester solvents include methyl acetate, butyl acetate, ethyl acetate, propyl acetate, isopropyl acetate, pentyl acetate, isopentyl acetate, hexyl acetate, propylene glycol monomethyl ether acetate (PGMEA), ethylene glycol monoethyl ether acetate, diethylene glycol mono Butyl ether acetate, diethylene glycol monoethyl ether acetate, ethyl-3-ethoxypropionate, 3-methoxybutyl acetate, 3-methyl-3-methoxybutyl acetate, methyl formate, ethyl formate, butyl formate, propyl formate, ethyl lactate, lactic acid Examples include butyl, propyl lactate, butyl butanoate, methyl 2-hydroxyisobutyrate, isoamyl butyrate, isobutyl isobutyrate, ethyl propionate, propyl propionate, and butyl propionate.
As the ester solvent, propyl acetate, butyl acetate, hexyl acetate, PGMEA, ethyl lactate, isoamyl butyrate, ethyl propionate, or propyl propionate is preferred, and propyl acetate, butyl acetate, hexyl acetate, ethyl lactate, isoamyl butyrate, propion Ethyl acid or propyl propionate is more preferred.

The ester solvents may be used alone or in combination of two or more.
When the chemical solution contains an ester solvent, the lower limit of the content of the ester solvent is preferably 30% by mass or more, more preferably 40% by mass or more, and still more preferably 50% by mass or more, based on the total mass of the chemical solution. It is preferably 60% by mass or more, particularly preferably 60% by mass or more. Further, the upper limit is preferably 100% by mass or less, more preferably 95% by mass or less, and even more preferably 90% by mass or less.

(hydrocarbon solvent)
Examples of the hydrocarbon solvent include aliphatic hydrocarbon solvents and aromatic hydrocarbon solvents. The aliphatic hydrocarbon solvent may be a saturated aliphatic hydrocarbon solvent or an unsaturated aliphatic hydrocarbon solvent, with a saturated aliphatic hydrocarbon solvent being preferred.

The hydrocarbon solvent preferably has 3 to 20 carbon atoms, more preferably 8 to 12 carbon atoms, and still more preferably 9 to 11 carbon atoms.
The aliphatic hydrocarbon solvent may be linear, branched or cyclic, preferably linear. The aromatic hydrocarbon solvent may be monocyclic or polycyclic.

Examples of hydrocarbon solvents include saturated aliphatic hydrocarbons such as pentane, hexane, octane, nonane, decane, undecane, dodecane, hexadecane, 2,2,4-trimethylpentane, and 2,2,3-trimethylhexane. System solvents: Mesitylene, cumene, pseudocumene, 1,2,4,5-tetramethylbenzene, p-cymene, toluene, xylene, ethylbenzene, propylbenzene, 1-methylpropylbenzene, 2-methylpropylbenzene, dimethylbenzene, diethylbenzene , ethylmethylbenzene, trimethylbenzene, ethyldimethylbenzene, and dipropylbenzene.
The hydrocarbon solvent is preferably a saturated aliphatic hydrocarbon solvent, more preferably at least one selected from the group consisting of octane, nonane, decane, undecane, and dodecane, and more preferably at least one selected from the group consisting of nonane, decane, and undecane. More preferably, at least one selected from the following is preferred.

The boiling point of the hydrocarbon solvent is preferably 100 to 260°C, more preferably 120 to 240°C, even more preferably 125 to 220°C, and particularly preferably 140 to 220°C.
The ClogP of the hydrocarbon solvent is preferably 3.00 to 10.0, more preferably 4.00 to 9.00, even more preferably 4.50 to 8.00.

The hydrocarbon solvents may be used alone or in combination of two or more.
When the chemical solution contains a hydrocarbon solvent, the content of the hydrocarbon solvent is preferably 5 to 30% by mass, more preferably 10 to 25% by mass, and 10 to 20% by mass based on the total mass of the chemical solution. is more preferred, and 15 to 20% by mass is particularly preferred.

(ketone solvent)
The ketone solvent preferably has 3 to 20 carbon atoms, more preferably 3 to 15 carbon atoms, and still more preferably 3 to 12 carbon atoms.

Examples of ketone solvents include 1-octanone, 2-octanone, 1-nonanone, 2-nonanone, acetone, 2-heptanone, 4-heptanone, 1-hexanone, 2-hexanone, diisobutylketone, cyclohexanone, methylcyclohexanone, Examples include phenylacetone, methyl ethyl ketone, methyl isobutyl ketone, acetylacetone, acetonylacetone, ionone, diacetonyl alcohol, acetyl carbinol, acetophenone, methyl naphthyl ketone, isophorone, and propylene carbonate.
As the ketone solvent, cyclohexanone, 2-heptanone, or diisobutyl ketone is preferable.
The boiling point of the ketone solvent is preferably 100 to 200°C, more preferably 120 to 180°C, even more preferably 150 to 180°C.
The ClogP of the ketone solvent is preferably 1.00 to 4.00, more preferably 1.20 to 3.50, even more preferably 1.50 to 3.00.

The ketone solvents may be used alone or in combination of two or more.
When the chemical solution contains a ketone solvent, the lower limit of the content of the ketone solvent is, for example, preferably 20% by mass or more, more preferably 30% by mass or more, based on the total mass of the chemical solution. The upper limit is, for example, preferably 90% by mass or less, more preferably 80% by mass or less, and even more preferably 70% by mass or less.

(alcohol solvent)
Examples of alcoholic solvents include methyl alcohol, ethyl alcohol, n-propyl alcohol, isopropyl alcohol, n-butyl alcohol, sec-butyl alcohol, tert-butyl alcohol, isobutyl alcohol, n-hexyl alcohol, n-heptyl alcohol, n-octyl alcohol, n-decanol, ethylene glycol, diethylene glycol, triethylene glycol, ethylene glycol monomethyl ether, propylene glycol monomethyl ether, ethylene glycol monoethyl ether, propylene glycol monoethyl ether, diethylene glycol monomethyl ether, triethylene glycol monoethyl ether , and methoxymethylbutanol.

The boiling point of the alcoholic solvent is preferably 80 to 180°C, more preferably 80 to 160°C, even more preferably 80 to 150°C.
The ClogP of the alcohol solvent is preferably 0.00 to 3.00, more preferably 0.20 to 2.50, and even more preferably 0.50 to 2.00.

The alcoholic solvents may be used alone or in combination of two or more.
When the chemical solution contains an alcoholic solvent, the lower limit of the content of the alcoholic solvent is, for example, preferably 20% by mass or more, more preferably 30% by mass or more, based on the total mass of the chemical solution. The upper limit is, for example, preferably 90% by mass or less, more preferably 80% by mass or less, and even more preferably 70% by mass or less.

(Ether solvent)
Examples of the ether solvent include dioxane, tetrahydrofuran, and diisobutyl ether.

The boiling point of the ether solvent is preferably 100 to 180°C, more preferably 100 to 160°C, even more preferably 100 to 140°C.
The ClogP of the ether solvent is preferably 1.00 to 4.00, more preferably 1.20 to 3.50, even more preferably 1.50 to 3.00.

The ether solvents may be used alone or in combination of two or more.
When the chemical solution contains an ether solvent, the lower limit of the content of the ether solvent is, for example, preferably 20% by mass or more, more preferably 30% by mass or more, based on the total mass of the chemical solution. The upper limit is, for example, preferably 90% by mass or less, more preferably 80% by mass or less, and even more preferably 70% by mass or less.

(amide solvent)
Examples of amide solvents include N-methyl-2-pyrrolidone, N,N-dimethylacetamide, N,N-dimethylformamide, hexamethylphosphoric triamide, and 1,3-dimethyl-2-imidazolidinone. can be mentioned.

The boiling point of the amide solvent is preferably 140 to 250°C, more preferably 150 to 230°C.
The ClogP of the amide solvent is preferably -2.00 to 1.00, more preferably -1.80 to 0.50, even more preferably -1.50 to 0.00.

The amide solvents may be used alone or in combination of two or more.
When the chemical solution contains an amide solvent, the lower limit of the content of the amide solvent is, for example, preferably 20% by mass or more, more preferably 30% by mass or more, based on the total mass of the chemical solution. The upper limit is, for example, preferably 90% by mass or less, more preferably 80% by mass or less, and even more preferably 70% by mass or less.

It is preferable that the chemical solution contains two or more types of organic solvents in order to improve the effects of the present invention.
The chemical solution preferably contains two or more kinds of organic solvents and at least an organic solvent having a boiling point of 100° C. or higher, since the effects of the present invention are more excellent. In other words, it is preferable that the chemical solution contains two or more types of organic solvents, and at least one of the organic solvents included in the chemical solution is an organic solvent having a boiling point of 100° C. or higher.
A preferred embodiment of the chemical solution includes an embodiment in which at least one of the organic solvents contained in the chemical solution has a boiling point of 120° C. or higher.
Another preferable embodiment of the chemical solution is an embodiment in which all organic solvents contained in the chemical solution are organic solvents having a boiling point of 100° C. or higher. Further, in the above embodiment, it is preferable that at least one of the organic solvents contained in the chemical solution is an organic solvent with a boiling point of 120°C or higher, and all organic solvents contained in the chemical liquid are organic solvents with a boiling point of 120°C or higher. is more preferable.
Note that the upper limit of the boiling point of the organic solvent having a boiling point of 100°C or higher is not particularly limited, and is often 260°C or lower, and more often 220°C or lower.

The chemical solution preferably contains a first organic solvent and a second organic solvent, since the effects of the present invention are more excellent. The boiling point of the first organic solvent is higher than the boiling point of the second organic solvent, and the ClogP value of the first organic solvent is higher than the ClogP value of the second organic solvent. That is, at least two of the organic solvents contained in the chemical solution preferably satisfy a relationship such that the boiling point and CloP of one organic solvent are larger than the boiling point and CloP of the other organic solvent.
As a chemical solution, the effect of the present invention is superior in that the relationship between the boiling point and ClogP of two arbitrarily selected organic solvents is such that the boiling point of one organic solvent and ClogP are the same as the boiling point of the other organic solvent. It is more preferable that the value is larger than ClogP and ClogP.

(Example of preferred embodiment of organic solvent composition)
An example of a preferred embodiment of the composition of the organic solvent in the chemical solution will be given below.

<Aspect 1> The chemical solution includes at least a first organic solvent and a second organic solvent,
at least one of the first organic solvent and the second organic solvent has a boiling point of 100°C or higher,
the first organic solvent is an ester solvent,
The second organic solvent is an organic solvent selected from the group consisting of hydrocarbon solvents, ester solvents, alcohol solvents, ether solvents, and ketone solvents (however, the ester solvent in the second organic solvent is It is a different type of organic solvent from ester solvents),
The content of the first organic solvent is 40% by mass or more (preferably 50% by mass or more, more preferably 60% by mass or more) with respect to the total content of the first organic solvent and the second organic solvent. Note that the upper limit is not particularly limited, and is preferably 95% by mass or less, more preferably 90% by mass or less.

<<Aspect 2>> The chemical solution includes at least a first organic solvent and a second organic solvent,
at least one of the first organic solvent and the second organic solvent has a boiling point of 100°C or higher,
the first organic solvent is a hydrocarbon solvent,
The second organic solvent is an organic solvent selected from the group consisting of ester solvents, hydrocarbon solvents, alcohol solvents, ether solvents, and ketone solvents (however, the hydrocarbon solvent in the second organic solvent is 1 is a different type of organic solvent from hydrocarbon solvents),
The content of the first organic solvent is 30% by mass or less (preferably 20% by mass or less) with respect to the total content of the first organic solvent and the second organic solvent. Note that the lower limit is not particularly limited, and is preferably 10% by mass or more, more preferably 15% by mass or more.

<Aspect 3> The chemical solution includes at least a first organic solvent and a second organic solvent,
at least one of the first organic solvent and the second organic solvent has a boiling point of 100°C or higher,
the first organic solvent is a ketone solvent,
The second organic solvent is an organic solvent selected from the group consisting of alcohol-based solvents and ketone-based solvents (however, the ketone-based solvent in the second organic solvent is of a different type from the ketone-based solvent in the first organic solvent). can be,
The content of the first organic solvent is 20 to 80% by mass (preferably 30 to 70% by mass) with respect to the total content of the first organic solvent and the second organic solvent.

<Aspect 4> The chemical solution includes at least a first organic solvent and a second organic solvent,
at least one of the first organic solvent and the second organic solvent has a boiling point of 100°C or higher,
the first organic solvent is an ester solvent,
the second organic solvent is a hydrocarbon solvent,
The mass ratio of the content of the first organic solvent to the content of the second organic solvent (content of the first organic solvent/content of the second organic solvent) is 1 to 50 (preferably 3 to 20, more preferably 6 to 15).

<Aspect 5> The chemical solution includes at least a first organic solvent and a second organic solvent,
at least one of the first organic solvent and the second organic solvent has a boiling point of 100°C or higher,
The first organic solvent is an organic solvent with a ClogP value of 3.00 or more (preferably 3.50 or more, more preferably 5.00 or more, preferably 10.0 or less),
The second organic solvent is an organic solvent different from the first organic solvent, and is a ketone solvent or an ester solvent.

Further, in the above-mentioned aspects 1 to 5, the total content of the first organic solvent and the second organic solvent is preferably 80 to 100% by mass, and 90% by mass, based on the total content of organic solvents in the chemical solution. It is more preferably 100% by mass, and even more preferably 95% to 100% by mass. Note that when the chemical solution contains an organic solvent other than the first organic solvent and the second organic solvent, examples of the other organic solvent include known organic solvents other than those mentioned above.

In addition, in the above-mentioned aspects 1 to 4, the relationship between the boiling point and ClogP value of the first organic solvent and the second organic solvent is that one of the first organic solvent and the second organic solvent is higher than the other organic solvent. , it is preferable that the boiling point is high and the ClogP value is large. It is more preferable that the lower the content of the first organic solvent and the second organic solvent, the higher the boiling point and the larger the ClogP value.

Furthermore, in the above-mentioned embodiments 1 to 5, the boiling points of the first organic solvent and the second organic solvent are both preferably 100°C or higher, more preferably 120°C or higher.

In addition, the chemical solution preferably does not substantially contain an organic solvent containing 50% by mass or more of fluorine atoms, in order to improve the effects of the present invention. "Substantially free of" means that the content of organic solvents containing 50% or more of fluorine atoms is 5% by mass or less, preferably 3% by mass or less, based on the total mass of the chemical solution. , more preferably 1% by mass or less, and even more preferably the chemical solution does not contain an organic solvent containing 50% by mass or more of fluorine atoms.

[Other processes]
The pattern forming method may further include other steps (other steps) than the above-described steps 1 to 4, step 2-A, step 3-A, and step 4-A.

<Post bake (PB) process>
The pattern forming method may include a step of heating the pattern (post-bake step) after step 4-A (rinsing step). By the post-baking process, the developer and rinse solution remaining between patterns and inside the patterns can be removed, and surface roughness of the patterns can be improved.
The heating temperature in the post-bake step is preferably 40 to 250°C, more preferably 80 to 200°C.
The heating time in the post-bake step is preferably 10 to 180 seconds, more preferably 30 to 120 seconds.

<Etching process>
The pattern forming method may include an etching step of etching the substrate using the formed pattern as a mask.
Examples of the etching method include known etching methods. Specifically, the Proceedings of the International Society of Optical Engineering (Proc. of SPIE) Vol. 6924, 692420 (2008), "Chapter 4 Etching" of "Semiconductor Process Textbook 4th Edition Published in 2007, Publisher: SEMI Japan", and the method described in JP-A No. 2009-267112.

<Refining process>
The pattern forming method includes a resist composition, a developer, a rinsing liquid, and/or other various components (for example, an antireflection film forming composition and a top coat forming composition) used in the pattern forming method. It may also include a purification step.

As the purification method, for example, a known purification method can be mentioned, and a method of filtration using a filter or a purification method using an adsorbent is preferable.
The pore diameter of the filter is preferably less than 100 nm, more preferably 10 nm or less, and even more preferably 5 nm or less. The lower limit is often 0.01 nm or more.
The material of the filter is preferably polytetrafluoroethylene, polyethylene or nylon. The filter may be made of a composite material that is a combination of the above filter materials and ion exchange media. A filter that has been previously washed with an organic solvent may be used.

In the method of filtering using a filter, multiple types of filters may be connected in series or in parallel. When using multiple types of filters, filters with different pore sizes and/or materials may be used in combination. Further, the product to be purified may be filtered once or twice or more. If the method involves filtering twice or more, the filter may be filtered while circulating.

In the method using an adsorbent, the adsorbent alone may be used, or the above-mentioned filter and adsorbent may be used in combination.
Examples of the adsorbent include known adsorbents, and specifically, inorganic adsorbents such as silica gel and zeolite, and organic adsorbents such as activated carbon.

In the production of a resist composition, for example, it is preferable to dissolve each component such as a resin that may be included in the resist composition in an organic solvent, and then filter the solution while circulating it using a plurality of filters made of different materials. Specifically, it is preferable to connect a polyethylene filter with a pore diameter of 50 nm, a nylon filter with a pore diameter of 10 nm, and a polyethylene filter with a pore diameter of 3 nm in series, and perform circulation filtration 10 times or more.
It is preferable that the pressure difference between each filter is small. Specifically, the pressure difference between each filter is preferably 0.1 MPa or less, more preferably 0.05 MPa or less, and even more preferably 0.01 MPa or less. The lower limit is often over 0 MPa.
It is also preferable that the pressure difference between the filter and the filling nozzle is small. Specifically, it is preferably 0.5 MPa or less, more preferably 0.2 MPa or less, and even more preferably 0.1 MPa or less. The lower limit is often over 0 MPa.

It is preferable that the resist composition is filtered using a filter and then filled into a clean container. From the viewpoint of suppressing deterioration over time, it is further preferable that the resist composition filled in the container be stored under refrigeration. The time from when the resist composition is completely filled into the container until the start of refrigerated storage is preferably short. Specifically, it is preferably within 24 hours, more preferably within 16 hours, even more preferably within 12 hours, and particularly preferably within 10 hours.
The refrigerated storage temperature is preferably 0 to 15°C, more preferably 0 to 10°C, and even more preferably 0 to 5°C.

It is preferable that the resist composition, developer, and other various components do not contain impurities.
Examples of impurities include metal impurities. Specifically, Na, K, Ca, Fe, Cu, Mg, Al, Li, Cr, Ni, Sn, Ag, As, Au, Ba, Cd, Co, Pb, Ti, V, W, and Zn Can be mentioned.
The content of impurities in the resist composition is based on the total mass of the resist composition, the content of impurities in the developer is based on the total mass of the developer, or the content of impurities in each of the other various components is based on the total mass of the resist composition. Relative to the total mass of impurities in each of the other various components (for example, the content of impurities in the rinse solution is based on the total mass of the rinse solution, etc.), preferably 1 mass ppm or less, more preferably 10 mass ppb or less. , more preferably 100 mass ppt or less, particularly preferably 10 mass ppt or less, and most preferably 1 mass ppt or less. The lower limit is often 0 mass ppt or more.
Examples of methods for measuring impurities include known measuring methods such as ICP-MS (ICP mass spectrometry).
Methods for reducing the content of the impurities include, for example, filtration using the filter, selecting raw materials with a low content of impurities as raw materials constituting various materials, and using Teflon (registered trademark) in the equipment. An example is a method of distilling under conditions in which contamination is suppressed as much as possible by lining the product with water or the like.

Liquids containing organic solvents, such as developing solutions and rinsing solutions, must be conductive to prevent damage to chemical piping and various parts (e.g., filters, O-rings, tubes, etc.) due to static electricity charging and discharge. It may also contain a compound.
Examples of the conductive compound include methanol. From the viewpoint of maintaining development performance or rinsing performance, the content of conductive compounds in the developer is determined based on the total mass of the developer, or the content of conductive compounds in the rinse solution is determined based on the total mass of the rinse solution. , is preferably 10% by mass or less, more preferably 5% by mass or less. The lower limit is often 0.01% by mass or more.
Examples of the chemical liquid piping include various materials coated with SUS (stainless steel), antistatically treated polyethylene, polypropylene, or fluororesin (eg, polytetrafluoroethylene, perfluoroalkoxy resin, etc.).
Examples of the filter and O-ring include various materials coated with antistatically treated polyethylene, polypropylene, or fluororesin (eg, polytetrafluoroethylene, perfluoroalkoxy resin, etc.).

[Manufacturing method of electronic device]
The present invention also relates to a method of manufacturing an electronic device, including the above-described pattern forming method.
The above electronic device is suitably installed in electrical and electronic equipment (home appliances, office automation (OA), media-related equipment, optical equipment, communication equipment, etc.).

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

[Various components of actinic ray-sensitive or radiation-sensitive resin composition]
Below, various components used in the preparation of the actinic ray-sensitive or radiation-sensitive resin composition or materials used in the evaluation are shown.
〔resin〕
The structures of repeating units derived from the monomers used in the synthesis of resins P-1 to P-16 shown in Table 3 are shown below.
Note that M-3 corresponds to a repeating unit having a sensitizer precursor XC. That is, the resin having the repeating unit represented by M-3 corresponds to a structure in which the sensitizer precursor XC is bonded via a covalent bond.
Furthermore, M-7 and M-13 correspond to repeating units containing the compound YB. That is, the resin having repeating units represented by M-7 and M-13 corresponds to a structure in which compound YB is bonded via a covalent bond. The onium salt structure in the site corresponding to compound YB in M-13 (hereinafter referred to as "compound YB site") corresponds to an onium salt structure that does not generate an acid that can generate a sensitizer from the compound YB site (generated acid pKa is greater than 2.0). Furthermore, the onium salt structure at the compound YB site of M-7 can generate an acid that can generate a sensitizer from the compound YB site.
Furthermore, M-11 and M-12 correspond to repeating units having onium salt XB. In other words, the resin having repeating units represented by M-11 and M-12 corresponds to a structure in which onium salt XB is bonded via a covalent bond. Note that the onium salt structure of M-12 corresponds to an onium salt structure that does not generate an acid that can generate a sensitizer from the sensitizer precursor XC (the generated acid has a pKa of more than 2.0). Furthermore, the onium salt structure of M-11 can generate an acid capable of producing a sensitizer from the sensitizer precursor XC.
Furthermore, M-14 corresponds to a repeating unit having a sensitizer precursor XC. That is, the resin having the repeating unit represented by MM-14 corresponds to a structure in which the sensitizer precursor XC is bonded via a covalent bond. Furthermore, the sensitizer precursor XC in M-14 can generate an acid capable of producing a sensitizer upon irradiation with light.
Furthermore, M-15 corresponds to a repeating unit having a photoacid generator. In other words, a resin having a repeating unit represented by M-15 corresponds to a structure in which a photoacid generator is bound via a covalent bond.

Resins P-2 to P-16 were synthesized according to the synthesis method of resin P-1 (Synthesis Example 1) described below or a known method. Table 1 shows the composition ratio, weight average molecular weight (Mw), number average molecular weight (Mn), and polydispersity (Mw/Mn (PDI)) of each repeating unit in the resin.
The weight average molecular weight (Mw), number average molecular weight (Mn), and polydispersity (PDI) of resins P-1 to P-16 were measured using a GPC (Gel Permeation Chromatography) device (Tosoh HLC-8120GPC). GPC measurement (solvent: tetrahydrofuran, flow rate (sample injection amount): 10 μL, column: Tosoh TSK gel Multipore HXL-M, column temperature: 40°C, flow rate: 1.0 mL/min, detector: differential refractive index detector (Refractive Index Detector)) as a polystyrene equivalent value. Further, the composition ratios (mol% ratio) of the resins P-1 to P-16 were measured by ¹³ C-NMR (Nuclear Magnetic Resonance).

<Synthesis Example 1: Synthesis of Resin P-1>
70.0 g of cyclohexanone was placed in a three-necked flask under a nitrogen stream, and the flask was heated to 85°C. To this, 15.0 g, 40.0 g, 44.0 g of monomers corresponding to each repeating unit of the above-mentioned resin P-1 were added in order from the left in Table 1, and polymerization initiator V-601 (Fujifilm Wako Pure Chemical Industries, Ltd. A solution of 70.0 g of cyclohexanone dissolved in 70.0 g of cyclohexanone was added dropwise over 6 hours. After the dropwise addition was completed, the reaction was further carried out at 85° C. for 2 hours. After the reaction solution was allowed to cool, it was added dropwise to a methanol:water mixture over 20 minutes. Next, the powder precipitated by the dropping was collected by filtration and dried to obtain resin P-1 (73.6 g). The composition ratio (molar ratio) of the repeating units determined by NMR (nuclear magnetic resonance) method was 20/30/50. The weight average molecular weight of the obtained resin P-1 was 40,000 in terms of standard polystyrene, and the polydispersity index (PDI) was 1.6.

[Onium salt compound]
The structures of the onium salts (B-1 to B-4) shown in Table 3 are shown below.
B-1 and B-3 correspond to onium salt XB. Note that the onium salt B-3 corresponds to an onium salt that does not generate an acid capable of producing a sensitizer from the sensitizer precursor XC (the generated acid has a pKa of more than 2.0). Further, the onium salt of B-1 can generate an acid that can generate a sensitizer from the sensitizer precursor XC.
Furthermore, B-2 and B-4 correspond to compound YB. Note that the onium salt structure in B-4 corresponds to an onium salt that does not generate an acid that can generate a sensitizer from compound YB (the generated acid has a pKa of more than 2.0). Further, the onium salt structure in B-2 can generate an acid that can generate a sensitizer from compound YB.

[Nonionic photoacid generator]
The structure of the nonionic photoacid generator (nonionic PAG) C-1 shown in Table 3 is shown below.
Note that C-1 corresponds to photoacid generator XD or photoacid generator YC.

[Quencher]
The structure of the quencher (D-1) shown in Table 3 is shown below.

[Sensitizer precursor component]
The structures of the sensitizer precursor components (E-1 to E-3) shown in Table 3 are shown below.
Note that E-1 to E-3 all correspond to the sensitizer precursor XC. Among them, E-2 is a sensitizer precursor XC, and is a compound that itself can generate an acid capable of producing a sensitizer upon irradiation with light.

〔solvent〕
The solvents shown in Table 3 are shown below.
SL-1: Propylene glycol monomethyl ether acetate (PGMEA)
SL-2: Propylene glycol monomethyl ether (PGME)
SL-3: Cyclohexanone SL-4: γ-butyrolactone SL-5: Ethyl lactate SL-6: Diacetone alcohol

[Solvent used in developer and rinse solution]
The solvents used in the developer and rinse solutions shown in Table 4 are shown below.
D-1: Propyl acetate D-2: Butyl acetate D-3: Propyl propionate D-4: Hexyl acetate D-5: n-octane D-6: n-undecane D-7: Diisobutyl ether D-8: 2 -Heptanone D-9: Diisobutyl ketone D-10: Propylene glycol monomethyl ether acetate (PGMEA)
D-11: 2.38% by mass tetramethylammonium hydroxide aqueous solution D-12: Pure water Table 2 shows the physical properties of the organic solvents used as the developer and rinse solution. In addition, "boiling point" in Table 2 means the boiling point under 1 atmosphere (760 mmHg).

Various components shown in Table 3 below were mixed. Next, the obtained mixed solution was filtered through a polyethylene filter having a pore size of 0.03 μm to prepare a resin composition (resist composition). In Table 3, "resin (X)" refers to a resin whose main chain is cleaved by the action of exposure, acid, base, or heating and whose molecular weight decreases, and "resin (Y)" refers to "resin (X)". )" refers to resins other than ". "Onium salt (B)" refers to the above onium salt compound. "Nonionic PAG (C)" refers to the above nonionic photoacid generator. "Quencher (D)" refers to the above quencher. "Sensitizer precursors (E)" refers to the above-mentioned sensitizer precursor components.
The solid content concentration of each resist composition was adjusted as appropriate so that the resist composition could be coated with a film thickness shown in Table 4 below. Solid content means all components other than the solvent. The obtained resist compositions were used in Examples and Comparative Examples.
In addition, "content (mass %)" in Table 3 represents the content (mass %) of each component with respect to the total solid content in the resist composition.

[Pattern formation and evaluation]
[Pattern formation by EUV exposure]
A lower layer film forming composition SHB-A940 (manufactured by Shin-Etsu Chemical Co., Ltd.) was applied onto a silicon wafer with a diameter of 300 mm, and baked at 205° C. for 60 seconds to form a lower layer film with a thickness of 20 nm. A resist composition shown in Table 3 was applied thereon to form a resist film under the conditions (film thickness and PreBake) shown in Table 4. As a result, a silicon wafer having a resist film was formed.
A silicon wafer having a resist film obtained by the above procedure was subjected to pattern irradiation while changing the exposure amount using an EUV scanner NXE3400 (NA 0.33) manufactured by ASML. As the reticle, a hexagonal array contact hole mask with a pitch of 38 nm and an opening size of 22 nm was used. Thereafter, only if there is a description, baking (Post Exposure Bake; PEB) was performed under the conditions shown in Table 4 below. Thereafter, the substrate was flood exposed (full surface exposure) using a UV exposure device (355 nm to 410 nm) at an exposure dose of 2000 J/cm ² , and then developed by puddle for 30 seconds with the developer shown in Table 4 below. In some cases, the wafer can be rinsed with a pitch of 38 nm by running the rinsing liquid shown in Table 4 for 10 seconds while rotating the wafer at a rotation speed of 1000 rpm, and then rotating the wafer for 30 seconds at a rotation speed of 4000 rpm. A contact hole pattern was obtained.

[Limit resolution evaluation]
Using a length-measuring scanning electron microscope (SEM: CG6300, manufactured by Hitachi High-Technologies), we observed 2,000 arbitrary holes at each exposure level and evaluated the average hole diameter and hole quality. did. The average hole diameter at the minimum exposure amount that satisfies the condition that no unresolved holes occur among the 2,000 observed holes was defined as the critical resolution. The smaller this value is, the better the resolution is and the better the performance is.

[result]
Table 4 shows the above evaluation results.

From the results in Table 4, it was confirmed that the resist composition of the present invention exhibited the desired effects. Note that R-14 is a positive resist whose dissolution rate in a developer increases as the interaction between the resin and the onium salt is canceled by exposure.
Note that R-1 to R-13 and R-15 to R-18 are positive resists that show an effect of increasing the rate of dissolution in the developer by cutting the main chain of the resin and lowering the molecular weight by exposure.

A comparison between Example 14 and Example 16 shows that when the resist composition of the present invention contains a base resin whose main chain is cleaved by the action of exposure and whose molecular weight decreases, the limit resolution is better. I understand.

A comparison between Example 1 and Example 15 shows that when the polydispersity (PDI) of the resin (X) is 1.7 or less, the critical resolution is better.

A comparison between Example 15 and Example 16 shows that when the weight average molecular weight (Mw) of the resin (X) is 40,000 or more, the limit resolution is better.

From the comparison between Example 1 and Example 19, it was found that when the resist film was further brought into contact with the rinsing liquid and the rinsing step (Step 4-A) was carried out after the development step (Step 4), the critical resolution was higher. I know it's excellent.

A comparison between Example 1 and Example 20 shows that the marginal resolution is better when the heating step (Step 2-A) is further performed after the pattern exposure step (Step 2).

From a comparison between Example 1 and Example 21, in a chemical solution consisting of two or more organic solvents used as a developer and/or a rinse agent, the relationship between the boiling point of any two organic solvents and the ClogP value is as follows. It can be seen that when one has a higher boiling point and a larger ClogP value than the other, the marginal resolution is better.

From a comparison between Example 21 and Example 22, it was found that the chemical solution used as the developer and/or the rinse solution contains two or more organic solvents, and the chemical solution containing the two or more organic solvents has a boiling point. It can be seen that when an organic solvent of 120° C. or higher is included, the limiting resolution is better.

From the comparison of Example 1 and Example 23 and Example 4 and Example 24, it is found that when the chemical solution used as the developer and/or the rinse solution contains two or more types of organic solvents, the marginal resolution is better. I understand that.

Example 24 A comparison with Example 25 shows that the limiting resolution is better when the chemical solution used as the developer and/or the rinse solution contains an organic solvent.

Claims

An actinic ray- or radiation-sensitive resin composition that satisfies Requirement 1 or Requirement 2.
Requirement 1: The composition includes a resin XA, an onium salt XB that generates an acid upon irradiation with light, and a sensitizer precursor XC that generates a sensitizer by the action of the acid,
The resin XA has an interactive group that interacts with the onium salt XB, or the resin XA and the onium salt XB are bonded via a covalent bond,
The onium salt XB is a compound that acts on the sensitizer precursor XC to generate an acid capable of producing a sensitizer, or
When the onium salt XB is a compound that does not generate an acid that can act on the sensitizer precursor XC to produce a sensitizer, the composition further acts on the sensitizer precursor XC. contains a photoacid generator XD capable of generating an acid capable of producing a sensitizer, or the sensitizer precursor XC generates an acid capable of producing the sensitizer upon irradiation with light;
The content of the repeating unit having a group that decomposes to produce a polar group by the action of an acid in the resin XA is 0 to 20 mol % based on the total repeating units of the resin XA.
Note that the sensitizer precursor XC may be bonded to the resin XA via a covalent bond. Furthermore, the photoacid generator XD may be bonded to the resin XA via a covalent bond.
Requirement 2: Contains resin YA and compound YB, which has an onium salt structure that generates an acid when irradiated with light and generates a sensitizer by the action of the acid,
The resin YA has an interactive group that interacts with the compound YB, or the resin YA and the compound YB are bonded via a covalent bond,
The onium salt structure is a structure that generates the acid that can generate the sensitizer, or
When the onium salt structure is not a structure that generates the acid that can generate the sensitizer, the composition further includes a photoacid generator YC that can generate an acid that can generate the sensitizer,
The content of the repeating unit having a group that decomposes to produce a polar group by the action of an acid in the resin YA is 0 to 20 mol % based on the total repeating units of the resin YA.
Note that the photoacid generator YC may be bonded to the resin YA via a covalent bond.
The actinic ray- or radiation-sensitive resin composition according to claim 1, wherein the resin XA and the resin YA are resins whose main chains are cleaved by the action of exposure, acid, base, or heating, resulting in a decrease in molecular weight. thing.
The actinic ray- or radiation-sensitive resin composition according to claim 1 or 2, wherein the resin XA and the resin YA have a weight average molecular weight of 40,000 or more.
The actinic ray- or radiation-sensitive resin composition according to claim 1 or 2, wherein the polydispersity of the resin XA and the resin YA is 1.7 or less.
A resist film formed using the actinic ray- or radiation-sensitive resin composition according to claim 1 or 2.
Step 1 of forming a resist film using the actinic ray- or radiation-sensitive resin composition according to claim 1 or 2;
Step 2 of exposing the resist film to a pattern of light with a wavelength of 200 nm or less to generate a sensitizer;
Step 3 of flood-exposing the resist film obtained in Step 2 with light having a wavelength of more than 200 nm and sensitizing the sensitizer;
A pattern forming method comprising a step 4 of performing a development process using a developer on the resist film obtained in step 3 to form a pattern,
When the composition used in step 1 satisfies requirement 1, in step 2, the resist film is pattern-exposed to light with a wavelength of 200 nm or less to remove the onium salt XB, the A step of decomposing the photoacid generator XD or the sensitizer precursor XC to generate an acid, and generating a sensitizer from the sensitizer precursor XC by the action of the acid,
When the composition used in step 1 satisfies requirement 2, in step 2, the resist film is pattern-exposed to light with a wavelength of 200 nm or less to form an onium salt structure in compound YB. Or a pattern forming method, which is a step of decomposing the photoacid generator YC to generate an acid and generating a sensitizer from the compound YB by the action of the acid.
After the step 2, further includes a heating step 2-A of heating the resist film obtained in step 2, or
After the step 3, the method further includes a heating step 3-A of heating the resist film obtained in the step 3, or
The pattern forming method according to claim 6, comprising both the step 2-A and the step 3-A.
7. The pattern forming method according to claim 6, further comprising, after the step 4, a step 4-A of rinsing the resist film obtained in the step 4 using a rinsing liquid.
The developing solution is a chemical solution containing an organic solvent, or
After the step 4, the method further includes a step 4-A of rinsing the resist film obtained in the step 4 using a rinsing liquid, and the rinsing liquid contains an organic solvent. The pattern forming method according to claim 6, wherein the pattern forming method is a chemical liquid.
The pattern forming method according to claim 9, wherein the chemical solution containing an organic solvent is a chemical solution containing two or more types of organic solvents.
The pattern forming method according to claim 10, wherein the chemical solution containing two or more organic solvents contains an organic solvent with a boiling point of 120°C or higher.
The chemical solution containing two or more organic solvents contains organic solvent A and organic solvent B,
The boiling point of the organic solvent A is higher than the boiling point of the organic solvent B,
The pattern forming method according to claim 10, wherein the ClogP value of the organic solvent A is larger than the ClogP value of the organic solvent B.
A method for manufacturing an electronic device, comprising the pattern forming method according to claim 6.