JP6997803B2 - Sensitive ray-sensitive or radiation-sensitive resin composition, resist film, pattern forming method, electronic device manufacturing method, compound - Google Patents

Description

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

Conventionally, in the manufacturing process of semiconductor devices such as ICs (Integrated Circuits) and LSIs (Large Scale Integrated Circuits), fine processing by lithography using a chemically amplified resist composition is performed. There is.

For example, in Patent Document 1, as a pattern forming method using a chemically amplified resist composition, "(a) a film is formed by a sensitive light-sensitive or radiation-sensitive resin composition containing the following (A) to (C). The process of forming,
(A) A resin whose polarity is increased by the action of an acid and its solubility in a developing solution containing an organic solvent is reduced.
(B) A compound that generates an acid by irradiation with active light or radiation, and (C) a cation moiety and an anion moiety are contained in the same molecule, and the cation moiety and the anion moiety are linked by a covalent bond. Compound (a) A pattern forming method comprising a step of exposing the above-mentioned film and (c) a step of developing the above-mentioned exposed film with a developing solution containing an organic solvent to form a negative pattern. Is disclosed. Further, Patent Document 1 discloses the following two types of betaine-type compounds as the component (C).

The component (B) is a so-called acid generator, and generates an acid by being irradiated with active light or radiation during the exposure step (step (a)). This generated acid mainly contributes to the deprotection reaction of the acid-decomposable resin (component (A) above).

Japanese Unexamined Patent Publication No. 2014-170205

With reference to Patent Document 1, the present inventors usually use acid generation to cause a deprotection reaction of a resin component (a deprotection reaction of an acid-degradable resin) or to cause a cross-linking reaction of a resin component. When an active light-sensitive or radiation-sensitive resin composition containing an agent (hereinafter referred to as "acid generator X") and the betaine-type compound was prepared and examined, the betaine-type compound was found to be active light or radiation. When irradiated with, an acid diffusion control agent (neutralization) that generates an acid that is relatively weaker than the acid generated from the acid generator X and controls the diffusion of the acid generated from the acid generator X to the unexposed portion. It is known that it functions as an agent).
On the other hand, the present inventors tend to form aggregates (for example, dimers) in the sensitive light-sensitive or radiation-sensitive resin composition, and the betaine-type compound is difficult to be uniformly dispersed in the system. Was clarified. As a result, the film of the sensitive light-sensitive or radiation-sensitive resin composition containing the acid generator X and the betaine-type compound (hereinafter, "the film of the sensitive light-sensitive or radiation-sensitive resin composition" is referred to as "resist film". In), the non-uniform presence of the betaine-type compound prevents the diffusion (neutralization) of the acid generated from the acid generator X by the betaine-type compound during the exposure step. It was clarified that the pattern that did not proceed uniformly and was formed did not necessarily have sufficient pattern line width fluctuation (LWR (line width roughness)) and in-plane uniformity (CDU (critical dimension uniformity)).

Therefore, it is an object of the present invention to provide a sensitive light-sensitive or radiation-sensitive resin composition capable of forming a pattern excellent in fluctuation of pattern line width (LWR) and in-plane uniformity (CDU).
Another object of the present invention is to provide a resist film, a pattern forming method, and a method for manufacturing an electronic device using the above-mentioned sensitive light-sensitive or radiation-sensitive resin composition.
Another object of the present invention is to provide a novel compound.

As a result of diligent studies to achieve the above problems, the present inventors have made a sensitive light-sensitive or radiation-sensitive resin containing an acid generator and a compound represented by the general formula (1) as an acid diffusion control agent. We have found that the above problems can be solved by the composition, and have completed the present invention.
That is, it was found that the above problem can be solved by the following configuration.

[1] Resin and
An acid generator that generates acid by irradiation with active light or radiation,
Contains acid diffusion regulators,
An actinic light-sensitive or radiation-sensitive resin composition in which the acid diffusion control agent contains at least a compound represented by the general formula (1).
[2] The actinic light-sensitive or radiation-sensitive resin composition according to [1], wherein the compound represented by the general formula (1) is a compound represented by the general formula (2).
[3] In the general formula (2), R ₁ to R ₄ are all hydrogen atoms, or at least one of Ar ₂ and Ar ₃ is an unsubstituted monocyclic aromatic hydrocarbon group [2]. The sensitive light-sensitive or radiation-sensitive resin composition according to.
[4] In the general formula (2), whether R ₁ to R ₄ are all hydrogen atoms and one of Ar ₂ and Ar ₃ is an unsubstituted monocyclic aromatic hydrocarbon group.
Both Ar ₂ and Ar ₃ are unsubstituted monocyclic aromatic hydrocarbon groups, or
The sensitive light-sensitive or radiation-sensitive resin composition according to [2], wherein R ₁ to R ₄ are all hydrogen atoms and Ar ₂ and Ar ₃ are both unsubstituted monocyclic aromatic hydrocarbon groups. ..
[5] In the general formula (1) or the general formula (2), A ₁ is -L ₁ -CO _2- or -L ₃ ^- X ₁ -N --Y ₁ ^[ 1] to [4]. ] The sensitive light-sensitive or radiation-sensitive resin composition according to any one of.
[6] The actinic or radiation-sensitive resin composition according to [5], wherein L ₁ and L ₃ are single bonds.
[7] A resist film formed by using the sensitive light-sensitive or radiation-sensitive resin composition according to any one of [1] to [6].
[8] A resist film forming step of forming a resist film using the sensitive light-sensitive or radiation-sensitive resin composition according to any one of [1] to [6].
The exposure process for exposing the resist film and
A pattern forming method comprising a developing step of developing the exposed resist film using a developing solution.
[9] A method for manufacturing an electronic device, which comprises the pattern forming method according to [8].
[10] A compound represented by the general formula (1).
[11] A compound represented by the general formula (2).
[12] In the general formula (2), R ₁ to R ₄ are all hydrogen atoms, or at least one of Ar ₂ and Ar ₃ is an unsubstituted monocyclic aromatic hydrocarbon group [11]. The compound described in.
[13] In the general formula (2), whether R ₁ to R ₄ are all hydrogen atoms and one of Ar ₂ and Ar ₃ is an unsubstituted monocyclic aromatic hydrocarbon group.
Both Ar ₂ and Ar ₃ are unsubstituted monocyclic aromatic hydrocarbon groups, or
The compound according to [11], wherein R ₁ to R ₄ are all hydrogen atoms and Ar ₂ and Ar ₃ are both unsubstituted monocyclic aromatic hydrocarbon groups.
[14] In the general formula (1) or the general formula (2), A ₁ is −L ₁ −CO ₂ ⁻ or −L ₃ −X ₁ −N ^－ −Y ₁ , [10] to [13]. ] The compound according to any one of.
[15] The compound according to [14], wherein L ₁ and L ₃ are single bonds.

According to the present invention, it is possible to provide a sensitive light-sensitive or radiation-sensitive resin composition capable of forming a pattern excellent in fluctuation of pattern line width (LWR) and in-plane uniformity (CDU).
Further, according to the present invention, it is possible to provide a resist film, a pattern forming method, and a method for manufacturing an electronic device using the above-mentioned sensitive light-sensitive or radiation-sensitive resin composition.
Further, according to the present invention, a novel compound can be provided.

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

As used herein, (meth) acrylate represents acrylate and methacrylate.
In the present specification, the weight average molecular weight (Mw), the number average molecular weight (Mn), and the degree of dispersion (also referred to as molecular weight distribution) (Mw / Mn) of the resin are referred to as GPC (Gel Permeation Chromatography) apparatus (HLC manufactured by Toso Co., Ltd.). GPC measurement by (-8120 GPC) (solvent: tetrahydrofuran, flow rate (sample injection amount): 10 μL, column: TSK gel Multipore HXL-M manufactured by Toso Co., Ltd., column temperature: 40 ° C., flow velocity: 1.0 mL / min, detector: differential It is defined as a polystyrene-equivalent value by a refractive index detector.

Regarding the notation of a group (atomic group) in the present specification, the notation not describing substitution and non-substitution includes a group having a substituent as well as a group having no substituent. For example, the "alkyl group" includes not only an alkyl group having no substituent (unsubstituted alkyl group) but also an alkyl group having a substituent (substituted alkyl group).

Further, in the present specification, the type of the substituent, the position of the substituent, and the number of the substituents when "may have a substituent" are not particularly limited. The number of substituents may be, for example, one, two, three, or more. As an example of the substituent, a monovalent non-metal atomic group excluding a hydrogen atom can be mentioned, and for example, it can be selected from the following substituent group T.
(Substituent T)
The substituent T includes a halogen atom such as a fluorine atom, a chlorine atom, a bromine atom and an iodine atom; an alkoxy group such as a methoxy group, an ethoxy group and a tert-butoxy group; an aryloxy group such as a phenoxy group and a p-tolyloxy group; Alkoxycarbonyl groups such as methoxycarbonyl group, butoxycarbonyl group and phenoxycarbonyl group; acyloxy groups such as acetoxy group, propionyloxy group and benzoyloxy group; acetyl group, benzoyl group, isobutyryl group, acryloyl group, methacryloyl group and metoxalyl group and the like. Acrylic groups of: alkylsulfanyl groups such as methylsulfanyl group and tert-butylsulfanyl group; arylsulfanyl groups such as phenylsulfanyl group and p-tolylsulfonyl group; alkyl groups; cycloalkyl groups; aryl groups; heteroaryl groups; hydroxyl groups; Carboxy group; formyl group; sulfo group; cyano group; alkylaminocarbonyl group; arylaminocarbonyl group; sulfonamide group; silyl group; amino group; monoalkylamino group; dialkylamino group; arylamino group; Can be mentioned.

[Actinic cheilitis or radiation-sensitive resin composition]
The sensitive light-sensitive or radiation-sensitive resin composition of the present invention (hereinafter, also referred to as “composition of the present invention”) is a resin and an acid generator that generates an acid by irradiation with active light or radiation (hereinafter, also referred to as “composition”). It also includes an "acid generator X") and an acid diffusion control agent, and the acid diffusion control agent contains at least a compound represented by the general formula (1) described later.

A feature of the present invention is that the compound represented by the general formula (1) is contained as an acid diffusion control agent.
Hereinafter, the mechanism of action of the compound represented by the general formula (1) as an acid diffusion control agent will be described, and then the structural characteristics of the compound represented by the general formula (1) will be described.

<Mechanism of action of the compound represented by the general formula (1) as an acid diffusion control agent>
The compound represented by the general formula (1) generates an acid by being irradiated with active light or radiation. The acid generated from the compound represented by the general formula (1) is usually used to cause a deprotection reaction of the resin component (deprotection reaction of the acid-degradable resin) or to cause a cross-linking reaction of the resin component. The acid is relatively weak with respect to the acid generator (acid generator X). Therefore, in the resist film system during and / or after exposure, the apparent proton exchange between the acid generated by the acid generator X and the acid anion generated from the compound represented by the general formula (1). A reaction occurs. As a result, the acid generated by the acid generator X is neutralized, and the diffusion of the acid generated from the acid generator X to the unexposed portion is suppressed.

<Structural characteristics of the compound represented by the general formula (1)>
As a structural feature of the compound represented by the general formula (1), the anionic group represented by A ₁ is bonded to S ⁺ on Ar ₁ (aromatic hydrocarbon group) bonded to the sulfonium cation. The point is that the carbon atom is substituted with the ortho position.
The present inventors tend to aggregate the betaine-type compound described in Patent Document 1 in the sensitive light-sensitive or radiation-sensitive resin composition (prone to form a multimer such as a dimer). It is speculated that it is due to the intramolecular polarization of the type compound. More specifically, in the betaine-type compound, it is considered that the positive charge and the negative charge in the molecule are too far apart and aggregate with other molecules to neutralize the charge.
On the other hand, the compound represented by the general formula ( ₁ ) is structurally close to the anionic group represented by A1 and the cation site of the sulfur atom represented by S ⁺ , so that it is sensitive to radiation or Hard to aggregate in the radiation sensitive resin composition. Therefore, the compound represented by the general formula (1) is uniformly dispersed even in the resist membrane system. As a result, in the resist film system during and / or after exposure, diffusion suppression (neutralization) of the acid generated from the acid generator X by the acid generated from the compound represented by the general formula (1) is achieved. It is estimated that it will proceed uniformly.
By the above mechanism of action, the pattern formed by the composition of the present invention is excellent in LWR performance and CDU performance.
The acid generated from the compound represented by the general formula (1) is one or more of the acid represented by the following general formula (1X) and the acid represented by the following general formula (1Y). I'm guessing. That is, depending on the structure, the acid represented by the following general formula (1X) is generated alone, the acid represented by the following general formula (1Y) is generated alone, or the following general formula ( It is presumed that both the acid represented by 1X) and the acid represented by the following general formula (1Y) are generated.
In the following general formula (1X) and the following general formula (1Y), Ar ₁ , Ar ₂ , Ar ₃ , and A 1 are Ar ₁ , Ar ₂ , Ar ₃ , and A ₁ in the general formula ( ₁ ). Is synonymous with.
General formula (1X): Ar ₁ -A ₁ -H
General formula (1Y): Ar ₂ -S-Ar ₃ -Ar ₁ -A ₁ -H

In addition to the above points, it is presumed that the acid diffusion control agent having a betaine structure also contributes to the improvement of LWR performance and CDU performance. As an acid diffusion control agent having the same action mechanism of acid diffusion control as the compound represented by the general formula (1) (action mechanism of neutralization of the acid generator X), for example, a triphenylsulfonium salt and the like are known. However, the resist film is less likely to be plasticized when the betaine-structured acid diffusion control agent is used, as compared with the case where these acid diffusion control agents are used. Therefore, it is considered that the resist film after exposure is less likely to melt unevenly during development, and as a result, contributes to the improvement of LWR performance and CDU performance.

Hereinafter, the components contained in the composition of the present invention will be described in detail. The composition of the present invention is a so-called resist composition, and may be a positive type resist composition or a negative type resist composition. Further, it may be a resist composition for alkaline development or a resist composition for organic solvent development.
The composition of the present invention is typically a chemically amplified resist composition.

<Resin (A)>
The composition of the present invention contains a resin (hereinafter, also referred to as "resin (A)").
As the resin (A), for example, a resin (AX1), a resin (AX2), and the like can be used, and among them, the resin (AX1) is preferable.

(Resin (AX1))
The resin (AX1) is a resin (hereinafter, also referred to as “acid-decomposable resin”) having a group (hereinafter, also referred to as “acid-decomposable group”) which is decomposed by the action of an acid and whose polarity is increased (hereinafter, also referred to as “acid-decomposable group”).
When the composition of the present invention contains a resin (AX1), the pattern formed is usually a positive pattern when an alkaline developer is used as the developer, and when an organic developer is used as the developer. Is a negative pattern.

The resin (AX1) preferably has a repeating unit having an acid-degradable group.

As the resin (AX1), a known resin can be appropriately used. For example, paragraphs <0055> to <0191> of U.S. Patent Application Publication No. 2016/0274458A1, paragraphs <0035> to <0087> of U.S. Patent Application Publication No. 2015/0004544A1, and U.S. Patent Application Publication No. 2016/0147150A1. The known resin disclosed in paragraphs <0045> to <0090> of the specification can be suitably used as the resin (AX1).

The acid-degradable group preferably has a structure in which the polar group is protected by a group (leaving group) that is decomposed and desorbed by the action of an acid.
The polar group includes a carboxy group, a phenolic hydroxyl group, a fluorinated alcohol group, a sulfonic acid group, a sulfonamide group, a sulfonylimide group, a (alkylsulfonyl) (alkylcarbonyl) methylene group, and a (alkylsulfonyl) (alkylcarbonyl) imide group. , Bis (alkylcarbonyl) methylene group, bis (alkylcarbonyl) imide group, bis (alkylsulfonyl) methylene group, bis (alkylsulfonyl) imide group, tris (alkylcarbonyl) methylene group, tris (alkylsulfonyl) methylene group, etc. Examples thereof include an acidic group (a group that dissociates in a 2.38 mass% tetramethylammonium hydroxide aqueous solution) and an alcoholic hydroxyl group.

The alcoholic hydroxyl group is a hydroxyl group bonded to a hydrocarbon group and refers to a hydroxyl group other than the hydroxyl group directly bonded on the aromatic ring (phenolic hydroxyl group), and the α-position of the hydroxyl group is electron attraction such as a fluorine atom. Excludes aliphatic alcohols substituted with sex groups (eg, hexafluoroisopropanol groups, etc.). The alcoholic hydroxyl group is preferably a hydroxyl group having a pKa (acid dissociation constant) of 12 or more and 20 or less.

Preferred polar groups include a carboxy group, a phenolic hydroxyl group, a fluorinated alcohol group (preferably a hexafluoroisopropanol group), and a sulfonic acid group.

A preferable group as an acid-degradable group is a group in which the hydrogen atom of these groups is replaced with a group (leaving group) that is eliminated by the action of an acid.
Examples of the group desorbed by the action of an acid (leaving group) include -C (R ₃₆ ) (R ₃₇ ) (R ₃₈ ), -C (R ₃₆ ) (R ₃₇ ) (OR ₃₉ ), and-. Examples thereof include C (R ₀₁ ) (R ₀₂ ) (OR ₃₉ ).
In the formula, R ₃₆ to R ₃₉ each independently represent an alkyl group, a cycloalkyl group, an aryl group, an aralkyl group, or an alkenyl group. R ₃₆ and R ₃₇ may be coupled to each other to form a ring.
R ₀₁ and R ₀₂ each independently represent a hydrogen atom, an alkyl group, a cycloalkyl group, an aryl group, an aralkyl group, or an alkenyl group.

As the alkyl group represented by R ₃₆ to R ₃₉ , R ₀₁ , and R ₀₂ , an alkyl group having 1 to 8 carbon atoms is preferable, and for example, a methyl group, an ethyl group, a propyl group, an n-butyl group, or sec- Examples thereof include a butyl group, a hexyl group, and an octyl group.
The cycloalkyl group represented by R ₃₆ to R ₃₉ , R ₀₁ and R ₀₂ may be monocyclic or polycyclic. The monocyclic cycloalkyl group is preferably a cycloalkyl group having 3 to 8 carbon atoms, and examples thereof include a cyclopropyl group, a cyclobutyl group, a cyclopentyl group, a cyclohexyl group, and a cyclooctyl group. The polycyclic cycloalkyl group is preferably a cycloalkyl group having 6 to 20 carbon atoms, for example, an adamantyl group, a norbornyl group, an isobornyl group, a camphanyl group, a dicyclopentyl group, an α-pinel group, a tricyclodecanyl group, Examples thereof include a tetracyclododecyl group and an androstanyl group. In addition, at least one carbon atom in the cycloalkyl group may be substituted with a heteroatom such as an oxygen atom.
As the aryl group represented by R ₃₆ to R ₃₉ , R ₀₁ and R ₀₂ , an aryl group having 6 to 10 carbon atoms is preferable, and examples thereof include a phenyl group, a naphthyl group, and an anthryl group.
The aralkyl group represented by R ₃₆ to R ₃₉ , R ₀₁ and R ₀₂ is preferably an aralkyl group having 7 to 12 carbon atoms, and examples thereof include a benzyl group, a phenethyl group and a naphthylmethyl group.
The alkenyl group represented by R ₃₆ to R ₃₉ , R ₀₁ and R ₀₂ is preferably an alkenyl group having 2 to 8 carbon atoms, and examples thereof include a vinyl group, an allyl group, a butenyl group, and a cyclohexenyl group. ..
The ring formed by bonding R ₃₆ and R ₃₇ to each other is preferably a cycloalkyl group (monocyclic or polycyclic). As the cycloalkyl group, a monocyclic cycloalkyl group such as a cyclopentyl group and a cyclohexyl group, or a polycyclic cycloalkyl group such as a norbornyl group, a tetracyclodecanyl group, a tetracyclododecanyl group, and an adamantyl group is preferable. ..

As the acid-degradable group, a cumyl ester group, an enol ester group, an acetal ester group, a tertiary alkyl ester group and the like are preferable, and an acetal group or a tertiary alkyl ester group is more preferable.

The resin (AX1) preferably has a repeating unit represented by the following general formula (AI) as a repeating unit having an acid-degradable group.

In the general formula (AI)
Xa ₁ represents a hydrogen atom, a halogen atom, or a monovalent organic group.
T represents a single bond or a divalent linking group.
Rx ₁ to Rx ₃ independently represent an alkyl group or a cycloalkyl group, respectively.
Any two of Rx ₁ to Rx ₃ may or may not be combined to form a ring structure.

Examples of the divalent linking group represented by T include an alkylene group, an arylene group, -COO-Rt-, and -O-Rt-. In the formula, Rt represents an alkylene group, a cycloalkylene group, or an arylene group.
T is preferably a single bond or -COO-Rt-. As Rt, a chain alkylene group having 1 to 5 carbon atoms is preferable, and −CH _2- , − (CH ₂ ) ₂ −, or − (CH ₂ ) ₃ − is more preferable.
The T is more preferably a single bond.

Xa ₁ is preferably a hydrogen atom or an alkyl group.
The alkyl group represented by Xa ₁ may have a substituent, and examples of the substituent include a hydroxyl group and a halogen atom (preferably a fluorine atom).
The alkyl group represented by Xa ₁ preferably has 1 to 4 carbon atoms, and examples thereof include a methyl group, an ethyl group, a propyl group, a hydroxymethyl group, and a trifluoromethyl group. The alkyl group of Xa ₁ is preferably a methyl group.

The alkyl group represented by Rx ₁ , Rx ₂ and Rx ₃ may be linear or branched, and may be a methyl group, an ethyl group, an n-propyl group, an isopropyl group, or n-. A butyl group, an isobutyl group, a t-butyl group and the like are preferable. The number of carbon atoms of the alkyl group is preferably 1 to 10, more preferably 1 to 5, and even more preferably 1 to 3. The alkyl group represented by Rx ₁ , Rx ₂ , and Rx ₃ may have a part of the carbon-carbon bond as a double bond.
Examples of the cycloalkyl group represented by Rx ₁ , Rx ₂ and Rx ₃ include a monocyclic cycloalkyl group such as a cyclopentyl group and a cyclohexyl group, or a norbornyl group, a tetracyclodecanyl group, a tetracyclododecanyl group, and a tetracyclododecanyl group. Polycyclic cycloalkyl groups such as adamantyl groups are preferred.

The ring structure formed by combining Rx ₁ , Rx ₂ and Rx ₃ is a monocyclic cycloalkane ring such as a cyclopentyl ring, a cyclohexyl ring, a cycloheptyl ring, and a cyclooctane ring, or a norbornane ring or a tetracyclo. Polycyclic cycloalkyl rings such as decane rings, tetracyclododecane rings, and adamantane rings are preferred. Of these, a cyclopentyl ring, a cyclohexyl ring, or an adamantane ring is more preferable. As the ring structure formed by combining Rx ₁ , Rx ₂ and Rx ₃ , the structure shown below is also preferable.

Specific examples of the monomer corresponding to the repeating unit represented by the general formula (AI) will be given below, but the present invention is not limited to these specific examples. The following specific examples correspond to the case where Xa ₁ in the general formula (AI) is a methyl group, but Xa ₁ can be arbitrarily substituted with a hydrogen atom, a halogen atom, or a monovalent organic group.

It is also preferable that the resin (AX1) has the repeating unit described in paragraphs <0336> to <0369> of US Patent Application Publication No. 2016/0070167A1 as the repeating unit having an acid-degradable group.

Further, the resin (AX1) is decomposed by the action of the acid described in paragraphs <0363> to <0364> of US Patent Application Publication No. 2016/0070167A1 as a repeating unit having an acid-degradable group and is alcoholic. It may have a repeating unit containing a group that produces a hydroxyl group.

The resin (AX1) may contain a repeating unit having an acid-decomposable group alone or in combination of two or more.

The content of the repeating unit having an acid-degradable group contained in the resin (AX1) (the total of multiple repeating units having an acid-degradable group) is determined with respect to all the repeating units of the resin (AX1). It is preferably 10 to 90 mol%, more preferably 20 to 80 mol%, still more preferably 30 to 70 mol%.

The resin (AX1) preferably has a repeating unit having at least one selected from the group consisting of a lactone structure, a sultone structure, and a carbonate structure.

The lactone structure or sultone structure may have a lactone structure or a sultone structure, and a 5- to 7-membered ring lactone structure or a 5- to 7-membered ring sultone structure is preferable. Among them, a 5- to 7-membered ring lactone structure in which another ring structure is condensed in a form forming a bicyclo structure or a spiro structure, or a 5- to 7-membered ring in the form of forming a bicyclo structure or a spiro structure. A sultone structure in which another ring structure is fused is more preferable.
The resin (AX1) has a lactone structure represented by any of the following general formulas (LC1-1) to (LC1-21), or any of the following general formulas (SL1-1) to (SL1-3). It is more preferred to have a repeating unit with the represented sultone structure. Further, the lactone structure or the sultone structure may be directly bonded to the main chain. Preferred structures include general formula (LC1-1), general formula (LC1-4), general formula (LC1-5), general formula (LC1-8), general formula (LC1-16), or general formula (LC1). Examples thereof include a lactone structure represented by -21) and a sultone structure represented by the general formula (SL1-1).

The lactone-structured portion or the sultone-structured portion may or may not have a substituent (Rb ₂ ). Preferred substituents (Rb ₂ ) include an alkyl group having 1 to 8 carbon atoms, a cycloalkyl group having 4 to 7 carbon atoms, an alkoxy group having 1 to 8 carbon atoms, an alkoxycarbonyl group having 2 to 8 carbon atoms, and a carboxy group. , Halogen atom, hydroxyl group, cyano group, acid-degradable group and the like, and an alkyl group having 1 to 4 carbon atoms, a cyano group, or an acid-degradable group is preferable. n ₂ represents an integer from 0 to 4. When n ₂ is 2 or more, the plurality of substituents (Rb ₂ ) may be the same or different. Further, a plurality of existing substituents (Rb ₂ ) may be bonded to each other to form a ring.

As the repeating unit having a lactone structure or a sultone structure, a repeating unit represented by the following general formula (III) is preferable.

In the above general formula (III),
A represents an ester bond (a group represented by -COO-) or an amide bond (a group represented by -CONH-).
n is the number of repetitions of the structure represented by −R ₀ −Z—, represents an integer of 0 to 5, is preferably 0 or 1, and more preferably 0. When n is 0, -R ₀ -Z- does not exist and a single bond is formed.
_R0 represents an alkylene group, a cycloalkylene group, or a combination thereof. When there are a plurality of R _0s , each R ₀ independently represents an alkylene group, a cycloalkylene group, or a combination thereof.
Z represents a single bond, an ether bond, an ester bond, an amide bond, a urethane bond or a urea bond. When there are a plurality of Z's, Z independently represents a single bond, an ether bond, an ester bond, an amide bond, a urethane bond or a urea bond.
R ₈ represents a monovalent organic group having a lactone structure or a sultone structure.
R ₇ represents a hydrogen atom, a halogen atom or a monovalent organic group (preferably a methyl group).

The alkylene group or cycloalkylene group of _R0 may have a substituent.
As Z, an ether bond or an ester bond is preferable, and an ester bond is more preferable.

The resin (AX1) may have a repeating unit having a carbonate structure. The carbonate structure is preferably a cyclic carbonate ester structure.
The repeating unit having a cyclic carbonate structure is preferably a repeating unit represented by the following general formula (A-1).

In the general formula (A-1), _RA ¹ represents a hydrogen atom, a halogen atom or a monovalent organic group (preferably a methyl group).
n represents an integer of 0 or more.
_RA ² represents a substituent. When n is 2 or more, _RA ² independently represents a substituent.
A represents a single bond or a divalent linking group.
Z represents an atomic group forming a monocyclic structure or a polycyclic structure together with the group represented by —O—C (= O) —O— in the formula.

The resin (AX1) is a repeating unit having at least one selected from the group consisting of a lactone structure, a sultone structure, and a carbonate structure, as paragraphs <0370> to <0414> of US Patent Application Publication No. 2016/0070167A1. It is also preferable to have the repeating unit described in 1.

The resin (AX1) may have a repeating unit having at least one selected from the group consisting of a lactone structure, a sultone structure, and a carbonate structure, and may have two or more kinds in combination. May be.

Hereinafter, specific examples of the monomer corresponding to the repeating unit represented by the general formula (III) and the specific example of the monomer corresponding to the repeating unit represented by the general formula (A-1) will be given. It is not limited to these specific examples. The following specific examples correspond to the case where R ₇ in the general formula (III) and RA 1 in the general formula ( _A - ¹ ) are methyl groups, but R ₇ and _RA ¹ are hydrogen atoms and halogen atoms. , Or can be optionally replaced with a monovalent organic group.

In addition to the above-mentioned monomers, the monomers shown below are also suitably used as raw materials for the resin (AX1).

The content of the repeating unit having at least one selected from the group consisting of a lactone structure, a sultone structure, and a carbonate structure contained in the resin (AX1) (selected from the group consisting of a lactone structure, a sultone structure, and a carbonate structure). If there are a plurality of repeating units having at least one kind, the total) is preferably 5 to 70 mol%, more preferably 10 to 65 mol%, and 20 to 20 to all the repeating units in the resin (AX1). 60 mol% is more preferred.

The resin (AX1) preferably has a repeating unit having a polar group.
Examples of the polar group include a hydroxyl group, a cyano group, a carboxy group, a fluorinated alcohol group and the like.
As the repeating unit having a polar group, a repeating unit having an alicyclic hydrocarbon structure substituted with a polar group is preferable. Moreover, it is preferable that the repeating unit having a polar group does not have an acid-decomposable group. In the alicyclic hydrocarbon structure substituted with the polar group, the adamantane group or the norbornane group is preferable as the alicyclic hydrocarbon structure.

Specific examples of the monomer corresponding to the repeating unit having a polar group will be given below, but the present invention is not limited to these specific examples.

In addition, specific examples of the repeating unit having a polar group include the repeating unit disclosed in paragraphs <0415> to <0433> of US Patent Application Publication No. 2016/0070167A1.
The resin (AX1) may have one type of repeating unit having a polar group alone, or may have two or more types in combination.
The content of the repeating unit having a polar group is preferably 5 to 50 mol%, more preferably 5 to 48 mol%, still more preferably 10 to 25 mol%, based on all the repeating units in the resin (AX1).

The resin (AX1) may further have a repeating unit that has neither an acid-degradable group nor a polar group. The repeating unit having neither an acid-degradable group nor a polar group preferably has an alicyclic hydrocarbon structure. Examples of the repeating unit having neither an acid-degradable group nor a polar group include the repeating units described in paragraphs <0236> to <0237> of US Patent Application Publication No. 2016/0026083A1. Preferred examples of monomers corresponding to repeating units having neither an acid-degradable group nor a polar group are shown below.

In addition, specific examples of the repeating unit having neither an acid-degradable group nor a polar group include the repeating unit disclosed in paragraph <0433> of US Patent Application Publication No. 2016/0070167A1. ..
The resin (AX1) may have one type of repeating unit having neither an acid-decomposable group nor a polar group, or may have two or more types in combination.
The content of the repeating unit having neither an acid-degradable group nor a polar group is preferably 5 to 40 mol%, more preferably 5 to 30 mol%, based on all the repeating units in the resin (AX1). 5 to 25 mol% is more preferred.

In addition to the above-mentioned repeating structural units, the resin (AX1) has dry etching resistance, standard developer suitability, substrate adhesion, resist profile, or resolution, heat resistance, and heat resistance, which are generally required properties of resist. It may have various repeating structural units for the purpose of adjusting sensitivity and the like.
Examples of such a repeating structural unit include, but are not limited to, a repeating structural unit corresponding to a predetermined monomer.

The predetermined monomer has one addition-polymerizable unsaturated bond selected from, for example, acrylic acid esters, methacrylic acid esters, acrylamides, methacrylamides, allyl compounds, vinyl ethers, vinyl esters and the like. Examples include compounds.
In addition, an addition-polymerizable unsaturated compound that can be copolymerized with the monomers corresponding to the above-mentioned various repeating structural units may be used.
In the resin (AX1), the molar ratio of each repeating structural unit is appropriately set in order to adjust various performances.

When the composition of the present invention is for ArF exposure, it is preferable that the resin (AX1) has substantially no aromatic group from the viewpoint of the transparency of ArF light. More specifically, the repeating unit having an aromatic group is preferably 5 mol% or less, more preferably 3 mol% or less, and ideally, with respect to all the repeating units in the resin (AX1). Is more preferably 0 mol%, i.e. not having a repeating unit with an aromatic group. Further, the resin (AX1) preferably has a monocyclic or polycyclic alicyclic hydrocarbon structure.

It is preferable that all of the repeating units of the resin (AX1) are composed of (meth) acrylate-based repeating units. In this case, all of the repeating units are methacrylate-based repeating units, all of the repeating units are acrylate-based repeating units, and all of the repeating units are either methacrylate-based repeating units or acrylate-based repeating units. Although it can be used, it is preferable that the acrylate-based repeating unit is 50 mol% or less with respect to all the repeating units of the resin (AX1).

When the composition of the present invention is for KrF exposure, EB exposure or EUV exposure, the resin (AX1) preferably has a repeating unit having an aromatic hydrocarbon ring group. It is more preferable that the resin (AX1) has a repeating unit containing a phenolic hydroxyl group. Examples of the repeating unit containing a phenolic hydroxyl group include a hydroxystyrene repeating unit or a hydroxystyrene (meth) acrylate repeating unit.
When the composition of the present invention is for KrF exposure, EB exposure or EUV exposure, the resin (AX1) is a group in which the hydrogen atom of the phenolic hydroxyl group is decomposed and desorbed by the action of an acid (leaving group). It is preferable to have a structure protected by.
The content of the repeating unit having an aromatic hydrocarbon ring group contained in the resin (AX1) is preferably 30 to 100 mol%, more preferably 40 to 100 mol%, based on all the repeating units in the resin (AX1). It is preferable, 50 to 100 mol% is more preferable.

The weight average molecular weight of the resin (AX1) is preferably 1,000 to 200,000, more preferably 2,000 to 20,000, and even more preferably 3,000 to 20,000. The degree of dispersion (Mw / Mn) is usually 1.0 to 3.0, preferably 1.0 to 2.6, more preferably 1.0 to 2.0, and further preferably 1.1 to 2.0. preferable.

The resin (AX1) may be used alone or in combination of two or more.
In the composition of the present invention, the content of the resin (AX1) is generally 20.0% by mass or more, preferably 40.0% by mass or more, preferably 60.0% by mass, based on the total solid content. By mass or more is more preferable, and 80.0% by mass or more is further preferable. The upper limit is not particularly limited, but 99.5% by mass or less is preferable, 99.0% by mass or less is more preferable, and 97.0% by mass or less is further preferable.

(Resin (AX2))
The resin (AX2) is an alkali-soluble resin having a phenolic hydroxyl group.
When the composition of the present invention contains a resin (AX2), the composition of the present invention contains a cross-linking agent (G) described later together with the resin (AX2). The cross-linking agent (G) may be supported on the resin (AX2).
When the composition of the present invention contains a resin (AX2), the pattern formed is usually a negative pattern.
The resin (AX2) preferably has a repeating unit having a phenolic hydroxyl group. Further, the resin (AX2) may have the above-mentioned acid-decomposable group.

As the repeating unit having the phenolic hydroxyl group of the resin (AX2), the repeating unit represented by the following general formula (II) is preferable.

In general formula (II),
R ₂ represents a hydrogen atom, an alkyl group (preferably a methyl group), or a halogen atom (preferably a fluorine atom).
B'represents a single bond or a divalent linking group.
Ar'represents an aromatic ring group.
m represents an integer of 1 or more.

The divalent linking group represented by B'is synonymous with T in the general formula (AI), and the preferred embodiment is also the same.
As the aromatic ring group represented by Ar', a benzene ring is preferable.
m is not particularly limited as long as it is an integer of 1 or more, but for example, 1 to 4 is preferable, 1 to 3 is more preferable, and 1 or 2 is further preferable.

The resin (AX2) may be used alone or in combination of two or more.
The content of the resin (AX2) in the total solid content of the composition of the present invention is generally 30% by mass or more, preferably 40% by mass or more, and more preferably 50% by mass or more. The upper limit is not particularly limited, but is preferably 99% by mass or less, more preferably 90% by mass or less, and further preferably 85% by mass or less.
Preferred examples of the resin (AX2) include the resins disclosed in paragraphs <0142> to <0347> of US Patent Application Publication No. 2016/0282720A1.

The composition of the present invention may contain both a resin (AX1) and a resin (AX2).

<Acid generator (B)>
The composition of the present invention contains a compound that generates an acid by irradiation with active light or radiation (hereinafter, also referred to as "acid generator (B)").
The acid generator (B) referred to here is an acid generator usually used to cause a deprotection reaction of a resin component (a deprotection reaction of an acid-degradable resin) or to cause a cross-linking reaction of a resin component. (The above-mentioned acid generator X) corresponds to this, and the acid generator (B) does not include the compound represented by the above-mentioned general formula (1).
As the acid generator (B), a compound that generates an organic acid by irradiation with active light or radiation is preferable. For example, a sulfonium salt compound, an iodonium salt compound, a diazonium salt compound, a phosphonium salt compound, an imide sulfonate compound, an oxime sulfonate compound, a diazodisulfone compound, a disulfone compound, and an o-nitrobenzylsulfonate compound can be mentioned.

As the acid generator (B), a known compound that generates an acid by irradiation with active light or radiation can be appropriately selected and used alone or as a mixture thereof. For example, paragraphs <0125> to <0319> of U.S. Patent Application Publication No. 2016/0070167A1, paragraphs <0086> to <0094> of U.S. Patent Application Publication No. 2015/0004544A1, and U.S. Patent Application Publication 2016 / The known compounds disclosed in paragraphs <0323> to <0402> of 0237190A1 can be suitably used as the acid generator (B).

As the acid generator (B), for example, a compound represented by the following general formula (ZI), general formula (ZII), or general formula (ZIII) is preferable.

In the above general formula (ZI)
R ₂₀₁ , R ₂₀₂ and R ₂₀₃ each independently represent an organic group.
The number of carbon atoms of the organic group as R ₂₀₁ , R ₂₀₂ and R ₂₀₃ is generally 1 to 30, preferably 1 to 20.
Further, two of R ₂₀₁ to R ₂₀₃ may be bonded to form a ring structure, and the ring may contain an oxygen atom, a sulfur atom, an ester bond, an amide bond, or a carbonyl group. Examples of the group formed by bonding 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.
Z ^- represents an anion.

Preferable embodiments of the cation in the general formula (ZI) include the corresponding groups in compound (ZI-1), compound (ZI-2), compound (ZI-3), and compound (ZI-4) described below. Be done.
The acid generator (B) may be a compound having a plurality of structures represented by the general formula (ZI). For example, at least one of R ₂₀₁ to R ₂₀₃ of the compound represented by the general formula (ZI) and at least one of R ₂₀₁ to R ₂₀₃ of the other compound represented by the general formula (ZI) are single-bonded. Alternatively, it may be a compound having a structure bonded via a linking group.

First, the compound (ZI-1) will be described.
The compound (ZI-1) is an aryl sulfonium compound in which at least one of R ₂₀₁ to R ₂₀₃ of the above general formula (ZI) is an aryl group, that is, a compound having an aryl sulfonium as a cation.
In the aryl sulfonium compound, all of R ₂₀₁ to R ₂₀₃ may be an aryl group, or a part of R ₂₀₁ to R ₂₀₃ may be an aryl group and the rest may be an alkyl group or a cycloalkyl group.
Examples of the aryl sulfonium compound include a triaryl sulfonium compound, a diarylalkyl sulfonium compound, an aryl dialkyl sulfonium compound, a diaryl cycloalkyl sulfonium compound, and an aryl dicycloalkyl sulfonium compound.

As the aryl group contained in the aryl sulfonium compound, 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 and the like. Examples of the heterocyclic structure include pyrrole residues, furan residues, thiophene residues, indole residues, benzofuran residues, benzothiophene residues and the like. When the aryl sulfonium compound has two or more aryl groups, the two or more aryl groups may be the same or different.
The alkyl group or cycloalkyl group contained in the aryl sulfonium compound as required is a linear alkyl group having 1 to 15 carbon atoms, a branched chain alkyl group having 3 to 15 carbon atoms, or a branched alkyl group having 3 to 15 carbon atoms. Cycloalkyl group is preferable, and examples thereof include a methyl group, an ethyl group, a propyl group, an n-butyl group, a sec-butyl group, a t-butyl group, a cyclopropyl group, a cyclobutyl group, and a cyclohexyl group.

The aryl group, alkyl group, and cycloalkyl group represented by R ₂₀₁ to R ₂₀₃ are independently an alkyl group (for example, 1 to 15 carbon atoms), a cycloalkyl group (for example, 3 to 15 carbon atoms), and an aryl group. It may have (for example, 6 to 14 carbon atoms), an alkoxy group (for example, 1 to 15 carbon atoms), a halogen atom, a hydroxyl group, or a phenylthio group as a substituent.

Next, the compound (ZI-2) will be described.
The compound (ZI-2) is a compound in which R ₂₀₁ to R ₂₀₃ in the formula (ZI) each independently represent an organic group having no aromatic ring. Here, the aromatic ring also includes an aromatic ring containing a heteroatom.
The organic group having no aromatic ring as R ₂₀₁ to R ₂₀₃ generally has 1 to 30 carbon atoms, and preferably 1 to 20 carbon atoms.
Independently, each of R ₂₀₁ to R ₂₀₃ is preferably an alkyl group, a cycloalkyl group, an allyl group, or a vinyl group, and is 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 chain alkyl group having 3 to 10 carbon atoms (for example, a methyl group, an ethyl group, a propyl group, etc.). Butyl group and pentyl group) or cycloalkyl group having 3 to 10 carbon atoms (for example, cyclopentyl group, cyclohexyl group, and norbornyl group) are preferable.
R ₂₀₁ to R ₂₀₃ may be further substituted with a halogen atom, an alkoxy group (for example, 1 to 5 carbon atoms), a hydroxyl group, a cyano group, or a nitro group.

Next, the compound (ZI-3) will be described.
The compound (ZI-3) is represented by the following general formula (ZI-3) and has a phenacylsulfonium salt structure.

In the general formula (ZI-3),
R _1c to R _5c are independently hydrogen atom, alkyl group, cycloalkyl group, aryl group, alkoxy group, aryloxy group, alkoxycarbonyl group, alkylcarbonyloxy group, cycloalkylcarbonyloxy group, halogen atom, hydroxyl group. , Nitro group, alkylthio group or arylthio group.
R _6c and R _7c each independently represent a hydrogen atom, an alkyl group, a cycloalkyl group, a halogen atom, a cyano group or an aryl group.
R _x and R _y each independently represent an alkyl group, a cycloalkyl group, a 2-oxoalkyl group, a 2-oxocycloalkyl group, an alkoxycarbonylalkyl group, an allyl group or a vinyl group.

Even if any two or more of R _1c to R _5c , R _5c and R _6c , R _6c and R _7c , R _5c and R _x , and R _x and R _y are combined to form a ring structure, respectively. Often, this ring structure may independently contain an oxygen atom, a sulfur atom, a ketone group, an ester bond, or an amide bond.
Examples of the ring structure include aromatic or non-aromatic hydrocarbon rings, aromatic or non-aromatic heterocycles, and polycyclic fused rings in which two or more of these rings are combined. Examples of the ring structure 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 a butylene group and a pentylene group.
As the group formed by bonding R _5c and R _6c , and R _5c and R _x , a single bond or an alkylene group is preferable. Examples of the alkylene group include a methylene group and an ethylene group.
Zc ^- represents an anion.

Next, the compound (ZI-4) will be described.
The compound (ZI-4) is represented by the following general formula (ZI-4).

In the general formula (ZI-4),
l represents an integer of 0 to 2.
r represents an integer from 0 to 8.
R ₁₃ represents a hydrogen atom, a fluorine atom, a hydroxyl group, an alkyl group, a cycloalkyl group, an alkoxy group, an alkoxycarbonyl group, or a group having a cycloalkyl group. These groups may have substituents.
R ₁₄ represents a hydroxyl group, an alkyl group, a cycloalkyl group, an alkoxy group, an alkoxycarbonyl group, an alkylcarbonyl group, an alkylsulfonyl group, a cycloalkylsulfonyl group, or a group having a cycloalkyl group. These groups may have substituents. When a plurality of _R14 are present, each independently represents the above group such as a hydroxyl group.
R ₁₅ independently represents an alkyl group, a cycloalkyl group, or a naphthyl group. These groups may have substituents. The two _R15s may combine with each other to form a ring. When two _R15s 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, it is preferred that the two _R15s are alkylene groups and are bonded to each other to form a ring structure.
Z ^- represents an anion.

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

Next, the general formulas (ZII) and (ZIII) will be described.
In the general formulas (ZII) and (ZIII), R ₂₀₄ to R ₂₀₇ each independently represent an aryl group, an alkyl group or a cycloalkyl group.
As the aryl group represented by R ₂₀₄ to R ₂₀₇ , a phenyl group or a naphthyl group is preferable, and a phenyl group is more preferable. The aryl group represented by R ₂₀₄ to R ₂₀₇ may be an aryl group having a heterocyclic structure having an oxygen atom, a nitrogen atom, a sulfur atom and the like. Examples of the skeleton of the aryl group having a heterocyclic structure include pyrrole, furan, thiophene, indole, benzofuran, and benzothiophene.
Examples of the alkyl group and cycloalkyl group represented by R ₂₀₄ to R ₂₀₇ include a linear alkyl group having 1 to 10 carbon atoms and a branched chain alkyl group having 3 to 10 carbon atoms (for example, a methyl group and an ethyl group). A propyl group, a butyl group, a pentyl group, etc.) or a cycloalkyl group having 3 to 10 carbon atoms (for example, a cyclopentyl group, a cyclohexyl group, a norbornyl group, etc.) is preferable.

The aryl group, alkyl group, and cycloalkyl group represented by R ₂₀₄ to R ₂₀₇ may each independently have a substituent. Examples of the substituent which the aryl group represented by R ₂₀₄ to R ₂₀₇ , the alkyl group, and the cycloalkyl group may have include an alkyl group (for example, 1 to 15 carbon atoms) and a cycloalkyl group (for example, carbon). Numbers 3 to 15), aryl groups (for example, 6 to 15 carbon atoms), alkoxy groups (for example, 1 to 15 carbon atoms), halogen atoms, hydroxyl groups, phenylthio groups and the like can be mentioned.
Z ^- represents an anion.

The Z − in the general formula (ZI), the Z ⁻ in the general formula (ZII), the Zc ⁻ in the general formula (ZI-3), and the Z ⁻ in the general formula (ZI ^- 4) are as follows in the general formula (3). The represented anion is preferred.

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

Xf represents a fluorine atom or an alkyl group substituted with at least one fluorine atom. The number of carbon atoms of this alkyl group is preferably 1 to 10, and more preferably 1 to 4. Further, as the alkyl group substituted with at least one fluorine atom, a perfluoroalkyl group is preferable.
Xf is preferably a fluorine atom or a perfluoroalkyl group having 1 to 4 carbon atoms, and more preferably a fluorine atom or CF ₃ . In particular, it is more preferable that both Xf are fluorine atoms.

R ₄ and R ₅ each independently represent a hydrogen atom, a fluorine atom, an alkyl group, or an alkyl group substituted with at least one fluorine atom. When there are a plurality of R ₄ and R ₅ , R ₄ and R ₅ may be the same or different from each other.
The alkyl group represented by R ₄ and R ₅ may have a substituent, and preferably has 1 to 4 carbon atoms. R ₄ and R ₅ are preferably hydrogen atoms.
Specific examples and preferred embodiments of the alkyl group substituted with at least one fluorine atom are the same as the specific examples and preferred embodiments of Xf in the general formula (3).

L represents a divalent linking group. When there are a plurality of L's, the L's may be the same or different.
Examples of the divalent linking group include -COO- (-C (= O) -O-), -OCO-, -CONH-, -NHCO-, -CO-, -O-, -S-,-. SO-, -SO _2- , alkylene group (preferably 1 to 6 carbon atoms), cycloalkylene group (preferably 3 to 15 carbon atoms), alkenylene group (preferably 2 to 6 carbon atoms), and a plurality of these. Examples thereof include a combined divalent linking group. Among these, -COO-, -OCO-, -CONH-, -NHCO-, -CO-, -O-, -SO _2- , -COO-alkylene group-, -OCO-alkylene group-, -CONH- The alkylene group-or -NHCO-alkylene group-is preferred, and the -COO-, -OCO-, -CONH-, -SO _2- , -COO-alkylene group-, or -OCO-alkylene group-is more preferred.

W represents an organic group containing a cyclic structure. Among these, a cyclic organic group is preferable.
Examples of the cyclic organic group include an alicyclic group, an aryl group, and a heterocyclic group.
The alicyclic group may be a monocyclic type or a polycyclic type. Examples of the monocyclic alicyclic group include a monocyclic cycloalkyl group such as a cyclopentyl group, a cyclohexyl group, and a cyclooctyl group. Examples of the polycyclic alicyclic group include a polycyclic cycloalkyl group such as a norbornyl group, a tricyclodecanyl group, a tetracyclodecanyl group, a tetracyclododecanyl group, and an adamantyl group. Of these, alicyclic groups having a bulky structure having 7 or more carbon atoms, such as a norbornyl group, a tricyclodecanyl group, a tetracyclodecanyl group, a tetracyclododecanyl group, and an adamantyl group, are preferable.

The aryl group may be monocyclic or polycyclic. Examples of the aryl group include a phenyl group, a naphthyl group, a phenanthryl group, and an anthryl group.
The heterocyclic group may be monocyclic or polycyclic. The polycyclic method can suppress the diffusion of acid more. Further, the heterocyclic group may or may not have aromaticity. Examples of the heterocyclic ring having aromaticity include a furan ring, a thiophene ring, a benzofuran ring, a benzothiophene ring, a dibenzofuran ring, a dibenzothiophene ring, and a pyridine ring. Examples of the non-aromatic heterocycle include a tetrahydropyran ring, a lactone ring, a sultone ring, and a decahydroisoquinoline ring. Examples of the lactone ring and the sultone ring include the lactone structure and the sultone structure exemplified in the above-mentioned resin. As the heterocycle in the heterocyclic group, a furan ring, a thiophene ring, a pyridine ring, or a decahydroisoquinoline ring is particularly preferable.

The cyclic organic group may have a substituent. Examples of the substituent include an alkyl group (which may be linear or branched, preferably 1 to 12 carbon atoms) and a cycloalkyl group (single ring, polycyclic, and spiro ring). Any of them may be used, preferably 3 to 20 carbon atoms), an aryl group (preferably 6 to 14 carbon atoms), a hydroxyl group, an alkoxy group, an ester group, an amide group, a urethane group, a ureido group, a thioether group and a sulfonamide. Groups and sulfonic acid ester groups are mentioned. The carbon constituting the cyclic organic group (carbon contributing to ring formation) may be carbonyl carbon.

Examples of the anion represented by the general formula (3) include SO ₃ ^- CF ₂ -CH ₂ -OCO- (L) q'-W and SO ₃ ^- CF ₂ -CHF-CH ₂ -OCO- (L). q'-W, SO ₃ ^- CF ₂ -COO- (L) q'-W, SO ₃ ^- CF ₂ -CF ₂ -CH ₂ -CH _2- (L) q ^- W, or SO _3- -CF ₂ -CH (CF ₃ ) -OCO- (L) q'-W is preferable. Here, L, q, and W are the same as in the general formula (3). q'represents an integer from 0 to 10.

In one embodiment, Z − in the general formula (ZI), Z ⁻ in the general formula (ZII), Zc ⁻ in the general formula (ZI-3), and Z ⁻ in the general formula (ZI ^- 4) are as follows. An anion represented by the formula (4) is also preferable.

In general formula (4),
X ^B1 and X ^B2 each independently represent a monovalent organic group having no hydrogen atom or fluorine atom. It is preferable that X ^B1 and X ^B2 are hydrogen atoms.
X ^B3 and X ^B4 each independently represent a hydrogen atom or a monovalent organic group. It is preferable that at least one of X ^B3 and X ^B4 is a fluorine atom or a monovalent organic group having a fluorine atom, and both X ^B3 and X ^B4 are monovalent organic groups having a fluorine atom or a fluorine atom. Is more preferable. It is more preferred that both X ^B3 and X ^B4 are fluorine-substituted alkyl groups.
L, q and W are the same as those in the general formula (3).

The Z − in the general formula (ZI), the Z ⁻ in the general formula (ZII), the Zc ⁻ in the general formula (ZI-3), and the Z ⁻ in the general formula (ZI ^- 4) are as follows in the general formula (5). The represented anion is also preferred.

In the general formula (5), Xa independently represents an alkyl group substituted with a fluorine atom or at least one fluorine atom. Xb independently represents an organic group having no hydrogen atom or fluorine atom. The definitions and preferred embodiments of o, p, q, R ₄ , R ₅ , L, and W are the same as in the general formula (3).

Z-in the general formula (ZI), Z ^- in the general formula (ZII), Zc ^- in the general formula (ZI-3), and Z ^- in the general formula (ZI ^- 4) may be benzenesulfonic acid anions. Often, it is preferably a benzenesulfonic acid anion substituted with a branched chain alkyl group or a cycloalkyl group.

The following general formula (SA1) is used as ^Z- in the general formula (ZI), ^Z- in the general formula (ZII), Zc- in the general formula (ZI ^- 3), and ^Z- in the general formula (ZI-4). Aromatic sulfonic acid anions represented by are also preferred.

In formula (SA1),
Ar represents an aryl group and may further have a substituent other than the sulfonic acid anion and the- (DB) group. Further, examples of the substituent which may be possessed include a fluorine atom and a hydroxyl group.

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

D represents a single bond or a divalent linking group. Examples of the divalent linking group include an ether group, a thioether group, a carbonyl group, a sulfoxide group, a sulfone group, a sulfonic acid ester group, an ester group, and a group composed of a combination of two or more thereof.

B represents a hydrocarbon group.

It is preferable that D is a single bond and B is an aliphatic hydrocarbon structure. B is more preferably an isopropyl group or a cyclohexyl group.

Preferred examples of the sulfonium cation in the general formula (ZI) and the iodonium cation in the general formula (ZII) are shown below.

Preferred examples of the anion Z ⁻ in the general formula (ZI), the anion Z ⁻ in the general formula (ZII), the Zc ⁻ in the general formula (ZI-3), and the Z ⁻ in the general formula (ZI-4) are shown below.

The above cations and anions can be arbitrarily combined and used as the acid generator (B).

The acid generator (B) may be in the form of a small molecule compound or may be incorporated in a part of the polymer. Further, the form of the small molecule compound and the form incorporated in a part of the polymer may be used in combination.
The acid generator (B) is preferably in the form of a small molecule compound.
When the acid generator (B) is in the form of a small molecule compound, the molecular weight is preferably 3,000 or less, more preferably 2,000 or less, still more preferably 1,000 or less.
When the acid generator (B) is incorporated in a part of the polymer, it may be incorporated in a part of the resin (A) described above, or it may be incorporated in a resin different from the resin (A). May be good.
The acid generator (B) may be used alone or in combination of two or more.
The content of the acid generator (B) in the composition (the total of a plurality of types, if present) is preferably 0.1 to 20.0% by mass, preferably 0.5, based on the total solid content of the composition. It is more preferably from 15.0% by mass, still more preferably 1.0 to 15.0% by mass.
When the acid generator contains a compound represented by the above general formula (ZI-3) or (ZI-4), the content of the acid generator contained in the composition (the total of multiple types, if present). Is preferably 5 to 35% by mass, more preferably 7 to 30% by mass, based on the total solid content of the composition.

The acid dissociation constant pKa of the acid generated by decomposition of the acid generator (B) by irradiation with active light or radiation is higher than that of the acid pKa generated from the compound represented by the general formula (1) described later. Small is preferable.
The acid dissociation constant pKa of the acid generated by the decomposition of the acid generator (B) by irradiation with active light or radiation is preferably -1.00 or less, and more preferably -1.50 or less. , -2.00 or less is more preferable. The lower limit of pKa is not particularly limited, but is, for example, −5.00 or higher. pKa (acid dissociation constant) can be measured by the following method.

≪Measurement of acid dissociation constant pKa≫
In the present specification, the acid dissociation constant pKa represents the acid dissociation constant pKa in an aqueous solution, for example, in Chemistry Handbook (II) (Revised 4th Edition, 1993, edited by Japan Chemical Society, Maruzen Co., Ltd.). It is described, and the lower this value is, the higher the acid strength is. The acid dissociation constant pKa in an aqueous solution can be specifically measured by measuring the acid dissociation constant at 25 ° C. using an infinitely diluted aqueous solution, and Hammett using the following software package 1. It is also possible to obtain a value based on a database of substituent constants and publicly known literature values of. All the values of pKa described in the present specification indicate the values calculated by using this software package.
Software Package 1: Advanced Chemistry Development (ACD / Labs) Software V8.14 for Solaris (1994-2007 ACD / Labs)

<Acid diffusion control agent>
The composition of the present invention contains an acid diffusion control agent. The acid diffusion control agent acts as a quencher that traps the acid generated from the acid generator (B) or the like at the time of exposure and suppresses the reaction of the acid-degradable resin in the unexposed portion due to the excess generated acid.
The composition of the present invention may contain at least the compound represented by the general formula (1) as an acid diffusion control agent, and may contain other acid diffusion inhibitors as long as the effects of the present invention are not impaired. May be good.
In the following, the compound represented by the general formula (1) will be described as an acid diffusion control agent (C), and the other acid diffusion inhibitor will be described as an acid diffusion control agent (D).

(Acid diffusion control agent (C))
Hereinafter, the compound represented by the general formula (1) will be described.
(Compound represented by the general formula (1))

In the above formula, Ar ₁ , Ar ₂ and Ar ₃ each independently represent an aromatic hydrocarbon group.
A ₁ is substituted at the ortho position with respect to the carbon atom bonded to S ⁺ on Ar ₁ , and -L ₁ -CO _2- , -L ₂ ^- SO _3- , or -L ₃ ^- X _1- . Represents N ^{－ －} Y ₁ .
L ₁ , L ₂ and L ₃ each independently represent a single bond or a divalent linking group.
X ₁ represents -SO _2- or -CO-.
Y ₁ represents -SO _{2 - RA} or -CO-RB.
_RA and _RB each independently represent a monovalent substituent.
In addition, Ar ₁ , Ar ₂ and Ar ₃ may further have a substituent, and the above-mentioned substituents may be bonded to each other to form a ring.

The aromatic hydrocarbon group represented by Ar ₁ , Ar ₂ and Ar ₃ is either a monocyclic structure (monocyclic aromatic hydrocarbon group) or a polycyclic structure (polycyclic aromatic hydrocarbon group). May be good. The number of carbon atoms of the aromatic hydrocarbon group is not particularly limited, but 5 to 18 is preferable, and 5 to 10 is more preferable. Specific examples of the aromatic hydrocarbon group include an aryl group (phenyl group, tolyl group, xsilyl group, etc.), naphthyl group, anthryl group, phenanthryl group, indenyl group, acenabutenyl group, fluorenyl group, pyrenyl group and the like. Can be mentioned.
As the aromatic hydrocarbon group represented by Ar ₁ , Ar ₂ and Ar ₃ , a monocyclic aromatic hydrocarbon group is preferable in that the LWR performance and the CDU performance of the formed pattern are more excellent, and phenyl is preferable. Groups are more preferred.

Ar ₁ , Ar ₂ and Ar ₃ may further have a substituent. The type of the above-mentioned substituent is not particularly limited, and examples thereof include the groups exemplified in the above-mentioned substituent group T. As the substituent, a non-aromatic substituent (in addition, in the present specification, the “non-aromatic substituent” is intended to be a substituent that does not exhibit aromaticity, and has, for example, an aromatic ring. Substituents that do not exist are preferable), and alkyl groups (which may be linear, branched, or cyclic. The number of carbon atoms is preferably 1 to 20, more preferably 1 to 10, and 1 to 1 to 10. 6 is more preferable), a fluoroalkyl group (representing an alkyl group substituted with at least one fluorine atom. The number of carbon atoms is preferably 1 to 10, more preferably 1 to 4, and at least one fluorine atom. The substituted alkyl group is preferably a perfluoroalkyl group), a halogen atom (examples of the halogen atom include a fluorine atom, a chlorine atom, a bromine atom, an iodine atom and the like), and a thioalkyl group (directly). It may be chain-shaped, branched-chain-shaped, or cyclic. The number of carbon atoms is preferably 1 to 20, more preferably 1 to 10, and even more preferably 1 to 6) or an alkoxy group (linear). , Branched chain or cyclic. The number of carbon atoms is preferably 1 to 20, more preferably 1 to 10, and even more preferably 1 to 6).

Substituents substituted with Ar ₁ , Ar ₂ and Ar ₃ may be bonded to each other to form a ring. The ring may be either aromatic or non-aromatic, but is preferably non-aromatic in that the LWR performance and CDU performance of the formed pattern are more excellent. The ring may further have a substituent (for example, those exemplified in the substituent group T).

As the compound represented by the general formula (1), one or more of Ar ₁ , Ar ₂ and Ar ₃ is unsubstituted in that the LWR performance and the CDU performance of the formed pattern are more excellent. It is preferably a monocyclic aromatic hydrocarbon group of (It is intended that Ar ₁ has no substituent other than A ₁ ), and any 2 of Ar ₁ , Ar ₂ and Ar ₃ are used. It is more preferable that one or more are monocyclic aromatic hydrocarbon groups, and it is more preferable that Ar ₁ , Ar ₂ and Ar ₃ are all monocyclic aromatic hydrocarbon groups.

A ₁ is substituted at the ortho position with respect to the carbon atom bonded to S ⁺ on Ar ₁ , and -L ₁ -CO _2- , -L ₂ ^- SO _3- , or -L ₃ ^- X _1- . Represents N ^{－ －} Y ₁ .
Here, "substituting the ortho position for the carbon atom bonded to S ⁺ on Ar ₁ " means to the carbon atom at the bond position with the sulfonium cation specified in the general formula (1) in Ar ₁ . The intention is to replace A ₁ with the ortho position. In other words, A ₁ is replaced with a carbon atom adjacent to the carbon atom at the bond position with the sulfonium cation specified in the general formula (1) in Ar ₁ .

L ₁ , L ₂ and L ₃ each independently represent a single bond or a divalent linking group, and a single bond is preferable in that the LWR performance and the CDU performance of the formed pattern are more excellent.
The divalent linking group represented by L ₁ , L ₂ and L ₃ is not particularly limited, and is, for example, -O-, -CO-, and a divalent hydrocarbon group (for example, an alkylene group, an alkenylene group, an alkynylene). A group and an arylene group), and a group in which two or more of these are combined can be mentioned. The divalent linking groups represented by L ₁ , L ₂ and L ₃ include -O-, -CO-, and alkylene groups having 1 to 10 carbon atoms, which are superior in LWR performance and CDU performance. An alkenylene group having 2 to 10 carbon atoms, an alkynylene group having 2 to 10 carbon atoms, and a group in which two or more of these are combined are preferable, and -O-, -CO-, an alkylene group having 1 to 6 carbon atoms, and 2 of these are preferable. The group having the above combination is more preferable, the alkylene group having 1 to 6 carbon atoms is more preferable, and the alkylene group having 1 to 3 carbon atoms is particularly preferable.
The atom at the bond position with Ar ₁ in L ₁ , L ₂ and L ₃ is preferably an atom other than an oxygen atom. For example, even when the divalent linking group represented by L ₁ , L ₂ and L ₃ contains -O- (oxygen atom), an atom other than the oxygen atom (for example, a carbon atom) as described above. Is preferably combined with Ar ₁ .

As A ₁ , -L ₁ ^- CO _2- or -L ₃ -X ₁ ^- N --Y ₁ is preferable because the LWR performance and CDU performance of the formed pattern are more excellent.

X ₁ represents -SO _2- or -CO-.
Y ₁ represents -SO _{2 - RA} or -CO-RB.

_RA and _RB each independently represent a monovalent substituent.
The monovalent substituent represented by _RA and RB is not particularly limited, and examples thereof include the groups exemplified in the above _- mentioned substituent group T. The monovalent substituent represented by _RA and _RB may be any of an alkyl group (linear, branched or cyclic, preferably 1 to 20 carbon atoms. 1 to 10 is more preferable, 1 to 6 is more preferable, 1 to 3 is particularly preferable), an alkenyl group (linear, branched chain, or cyclic) may be used, and the number of carbon atoms is 2 to 20. It may be preferably 2 to 10, more preferably 2 to 6), or an alkynyl group (linear, branched, or cyclic. The number of carbon atoms is preferably 2 to 20. 2 to 10 is more preferable, 2 to 6 is more preferable), an alkyl group having 1 to 10 carbon atoms is more preferable, and an alkyl group having 1 to 6 carbon atoms is further preferable.
The alkyl group, alkenyl group, and alkynyl group may further have a substituent (for example, those exemplified in the substituent group T).

The pKa of the acid generated from the compound represented by the general formula (1) is preferably, for example, more than −2.00, preferably more than 1.00, in that the function as an acid diffusion control agent is more excellent. More preferably, it is more preferably 1.50 or more. The upper limit of pKa is not particularly limited, but is, for example, 14.0 or less.
pKa (acid dissociation constant) can be measured by the method described above.

The pKa of the acid generated from the compound represented by the general formula ( ₁ ) can be adjusted mainly by the type of A1.

In the composition of the present invention, the difference between the pKa of the acid generated by the compound represented by the general formula (1) and the pKa of the acid generated by the acid generator (B) is preferably 1.00 or more, 2 .00 or more is more preferable. The upper limit is not particularly limited, but is, for example, 10.0.
As described above, the acid generated by the compound represented by the general formula (1), which is an acid diffusion control agent, is relatively weak acid with respect to the acid generated from the acid generator (B). If the difference in pKa between the acid generated by the compound represented by the general formula (1) and the acid generated by the acid generator (B) is within the above numerical range, the compound represented by the general formula (1) is. It has a better function as an acid diffusion control agent.

The compound represented by the general formula (1) is preferably a compound represented by the following general formula (2) in that the LWR performance and the CDU performance of the formed pattern are more excellent. Hereinafter, the general formula (2) will be described.
(Compound represented by the general formula (2))

In the above formula, Ar ₂ , Ar ₃ , and A ₁ are synonymous with Ar ₂ , Ar ₃ , and A ₁ in the general formula (1), and the preferred embodiments are also the same.

R ₁ , R ₂ , R ₃ and R ₄ each independently represent a hydrogen atom or a non-aromatic substituent.
The substituents represented by R ₁ , R ₂ , R ₃ and R ₄ are not particularly limited as long as they are non-aromatic substituents, and are alkyl groups (linear, branched and cyclic). Any of them may be used. The number of carbon atoms is preferably 1 to 20, more preferably 1 to 10, and even more preferably 1 to 6, and represents a fluoroalkyl group (an alkyl group substituted with at least one fluorine atom). The number of carbon atoms is preferably 1 to 10, more preferably 1 to 4, and the alkyl group substituted with at least one fluorine atom is preferably a perfluoroalkyl group), a halogen atom (as a halogen atom, the halogen atom is preferable). For example, it may be any of a fluorine atom, a chlorine atom, a bromine atom, an iodine atom, etc.) and a thioalkyl group (linear, branched, or cyclic. The number of carbon atoms is 1 to 20. It is preferably 1 to 10, more preferably 1 to 6, or an alkoxy group (linear, branched, or cyclic. The number of carbon atoms is preferably 1 to 20. ~ 10 is more preferable, and 1 to 6 are even more preferable).
In addition, R ₁ , R ₂ , R ₃ , and R ₄ may be connected to each other to form a ring. The ring is preferably non-aromatic. The ring may further have a substituent (for example, those exemplified in the substituent group T). Among them, it is preferable that R ₁ , R ₂ , R ₃ and R ₄ do not combine with each other to form a ring structure in that the LWR performance and CDU performance of the formed pattern are more excellent.

Ar ₂ and Ar ₃ may further have a substituent, and the substituents may be bonded to each other to form a ring. The ring may be either aromatic or non-aromatic, but is preferably non-aromatic in that the LWR performance and CDU performance of the formed pattern are more excellent. The ring may further have a substituent (for example, those exemplified in the substituent group T).

As the compound represented by the general formula (2), R ₁ to R ₄ are all hydrogen atoms or Ar ₂ and Ar ₃ in that the LWR performance and CDU performance of the formed pattern are more excellent. It is preferable that at least one of them is an unsubstituted monocyclic aromatic hydrocarbon group. Among them, R ₁ to R ₄ are all hydrogen atoms and one of Ar ₂ and Ar ₃ is an unsubstituted monocyclic aromatic hydrocarbon group in that the LWR performance and CDU performance of the formed pattern are more excellent. Are there, Ar ₂ and Ar ₃ are both unsubstituted monocyclic aromatic hydrocarbon groups, or R ₁ to R ₄ are all hydrogen atoms and Ar ₂ and Ar ₃ are both unsubstituted. It is more preferably a monocyclic aromatic hydrocarbon group.

The compound represented by the general formula (1) can be synthesized, for example, according to a known method.

Hereinafter, specific examples of the compound represented by the above general formula (1) will be exemplified, but the present invention is not limited thereto.

The compound represented by the general formula (1) may be used alone or in combination of two or more.
In the composition of the present invention, the content of the compound represented by the general formula (1) (the total thereof when a plurality of types exist) is preferably 0.1 to 10% by mass based on the total solid content of the composition. , 0.5-8.0% by mass is more preferable.
Further, the content ratio of the compound represented by the general formula (1) to the acid generator (B) (acid generator X) (acid generator (B) / compound represented by the general formula (1)). ) Is, for example, 1/99 to 99/1, preferably 90/10 to 30/70, and more preferably 85/15 to 40/60 in terms of mass ratio.

(Acid diffusion control agent (D))
The composition of the present invention is an acid diffusion control agent other than the above-mentioned acid diffusion control agent (C) (corresponding to the compound represented by the general formula (1)) as long as the effect of the present invention is not impaired. (Hereinafter, "acid diffusion control agent (D)") may be contained.
Examples of the acid diffusion control agent (D) include a basic compound (DA), a basic compound (DB) whose basicity is reduced or disappears by irradiation with active light or radiation, and a weak acid relative to an acid generator. Acid diffusion control of onium salt (DC), low molecular weight compound (DD) having a nitrogen atom and having a group desorbed by the action of acid, or onium salt compound (DE) having a nitrogen atom in the cation part, etc. Can be used as an agent. In the composition of the present invention, a known acid diffusion control agent can be appropriately used. For example, paragraphs <0627> to <0664> of US Patent Application Publication No. 2016/0070167A1, paragraphs <0995> to <0187> of US Patent Application Publication No. 2015/0004544A1, US Patent Application Publication No. 2016/0237190A1. The known compounds disclosed in paragraphs <0403> to <0423> of the specification and paragraphs <0259> to <0328> of US Patent Application Publication No. 2016/02744558A1 are suitable as the acid diffusion control agent (D). Can be used for.

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

In the general formulas (A) and (E),
R ²⁰⁰ , R ²⁰¹ and R ²⁰² may be the same or different, and each independently has a hydrogen atom, an alkyl group (preferably 1 to 20 carbon atoms), a cycloalkyl group (preferably 3 to 20 carbon atoms) or an aryl. Represents a group (6 to 20 carbon atoms). R ²⁰¹ and R ²⁰² may be coupled to each other to form a ring.
R ²⁰³ , R ²⁰⁴ , R ²⁰⁵ and R ²⁰⁶ may be the same or different, and each independently represents an alkyl group having 1 to 20 carbon atoms.

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

As the basic compound (DA), guanidine, aminopyrrolidine, pyrazole, pyrazoline, piperazine, aminomorpholin, aminoalkylmorpholin, piperidine and the like are preferable, and imidazole structure, diazabicyclo structure, onium hydroxide structure, onium carboxylate structure, etc. A trialkylamine structure, a compound having an aniline structure or a pyridine structure, an alkylamine derivative having a hydroxyl group and / or an ether bond, an aniline derivative having a hydroxyl group and / or an ether bond, and the like are more preferable.

A basic compound (DB) (hereinafter, also referred to as “compound (DB)”) whose basicity is reduced or disappears by irradiation with active light or radiation has a proton acceptor functional group and is active light or It is a compound that is decomposed by irradiation with radiation to reduce or disappear its proton acceptor property, or to change from proton acceptor property to acidity.

A proton-accepting functional group is a functional group having a group or an electron that can electrostatically interact with a proton, and is, for example, a functional group having a macrocyclic structure such as a cyclic polyether, or a π-conjugated group. Means a functional group having a nitrogen atom with an unshared electron pair that does not contribute to. The nitrogen atom having an unshared electron pair that does not contribute to π conjugation is, for example, a nitrogen atom having a partial structure shown in the following formula.

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

The compound (DB) is decomposed by irradiation with active light or radiation to generate a compound whose proton acceptor property is reduced or disappears, or whose proton acceptor property is changed to acidic. Here, the decrease or disappearance of the proton acceptor property, or the change from the proton acceptor property to the acidity is a change in the proton acceptor property due to the addition of a proton to the proton acceptor property functional group, and is specific. Means that when a proton adduct is formed from a compound (DB) having a proton acceptor functional group and a proton, the equilibrium constant in its chemical equilibrium decreases.
The proton acceptor property can be confirmed by measuring the pH.

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

The acid dissociation constant pKa can be obtained by the method described above.

In the composition of the present invention, an onium salt (DC), which is a weak acid relative to the acid generator, can be used as the acid diffusion control agent.
When an acid generator and an onium salt that generates an acid that is relatively weak to the acid generated from the acid generator are mixed and used, the acid generator is generated by active light or irradiation with radiation. When the acid collides with an onium salt having an unreacted weak acid anion, salt exchange releases the weak acid to produce an onium salt with a strong acid anion. In this process, the strong acid is replaced with a weak acid having a lower catalytic ability, so that the acid is apparently inactivated and the acid diffusion can be controlled.

As the onium salt that is relatively weak acid with respect to the acid generator, compounds represented by the following general formulas (d1-1) to (d1-3) are preferable.

In the formula, R ⁵¹ is a hydrocarbon group which may have a substituent, and Z ^2c is a hydrocarbon group having 1 to 30 carbon atoms which may have a substituent (however, carbon adjacent to S). R ⁵² is an organic group, Y ³ is a linear, branched or cyclic alkylene group or an arylene group, and Rf is a fluorine atom. It is a hydrocarbon group containing, and M ⁺ is independently an ammonium cation, a sulfonium cation or an iodonium cation.

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

A small molecule compound (DD) having a nitrogen atom and having a group desorbed by the action of an acid (hereinafter, also referred to as “compound (DD)”) has a group desorbed by the action of an acid on the nitrogen atom. It is preferably an amine derivative having.
As the group desorbed by the action of the acid, an acetal group, a carbonate group, a carbamate group, a tertiary ester group, a tertiary hydroxyl group or a hemiaminol ether group is preferable, and a carbamate group or a hemiaminol ether group is more preferable. ..
The molecular weight of the compound (DD) is preferably 100 to 1000, more preferably 100 to 700, and even more preferably 100 to 500.
Compound (DD) may have a carbamate group having a protecting group on the nitrogen atom. The protecting group constituting the carbamate group is represented by the following general formula (d-1).

In the general formula (d-1)
Rb is independently a hydrogen atom, an alkyl group (preferably 1 to 10 carbon atoms), a cycloalkyl group (preferably 3 to 30 carbon atoms), an aryl group (preferably 3 to 30 carbon atoms), and an aralkyl group (preferably 3 to 30 carbon atoms). It preferably represents 1 to 10 carbon atoms) or an alkoxyalkyl group (preferably 1 to 10 carbon atoms). Rb may be connected to each other to form a ring.
The alkyl group, cycloalkyl group, aryl group, and aralkyl group represented by Rb are independently hydroxyl groups, cyano groups, amino groups, pyrrolidino groups, piperidino groups, morpholino groups, oxo groups and other functional groups, alkoxy groups, or halogens. It may be substituted with an atom. The same applies to the alkoxyalkyl group indicated by Rb.

As Rb, a linear or branched alkyl group, a cycloalkyl group, or an aryl group is preferable, and a linear or branched alkyl group or a cycloalkyl group is more preferable.
Examples of the ring formed by connecting the two Rbs to each other include an alicyclic hydrocarbon, an aromatic hydrocarbon, a heterocyclic hydrocarbon, and a derivative thereof.
Specific examples of the structure of the group represented by the general formula (d-1) include, but are not limited to, the structure disclosed in paragraph <0466> of the US Patent Publication No. US2012 / 0135348A1.

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

In the general formula (6)
l represents an integer of 0 to 2, m represents an integer of 1 to 3, and satisfies l + m = 3.
Ra represents a hydrogen atom, an alkyl group, a cycloalkyl group, an aryl group or an aralkyl group. When l is 2, the two Ras may be the same or different, and the two Ras may be interconnected to form a heterocycle with the nitrogen atom in the equation. This heterocycle may contain a heteroatom other than the nitrogen atom in the equation.
Rb has the same meaning as Rb in the above general formula (d-1), and the same applies to preferred examples.
In the general formula (6), the alkyl group as Ra, the cycloalkyl group, the aryl group, and the aralkyl group are each independently substituted with the alkyl group, cycloalkyl group, aryl group, and aralkyl group as Rb. As a good group, it may be substituted with a group similar to the group described above.

Specific examples of the above-mentioned Ra alkyl group, cycloalkyl group, aryl group, and aralkyl group (these groups may be substituted with the above group) include groups similar to the above-mentioned specific examples for Rb. Be done.
Specific examples of a particularly preferred compound (DD) in the present invention include, but are not limited to, the compound disclosed in paragraph <0475> of U.S. Patent Application Publication No. 2012/01335348A1.

The onium salt compound (DE) having a nitrogen atom in the cation portion (hereinafter, also referred to as “compound (DE)”) is preferably a compound having a basic moiety containing a nitrogen atom in the cation portion. The basic moiety is preferably an amino group, more preferably an aliphatic amino group. It is even more preferred that all of the atoms adjacent to the nitrogen atom in the basic moiety are hydrogen or carbon atoms. Further, from the viewpoint of improving basicity, it is preferable that an electron-withdrawing functional group (carbonyl group, sulfonyl group, cyano group, halogen atom, etc.) is not directly linked to the nitrogen atom.
Preferred specific examples of the compound (DE) include, but are not limited to, the compound disclosed in paragraph <0203> of US Patent Application Publication 2015/0309408A1.

Preferred examples of the acid diffusion control agent (D) are shown below.

In the composition of the present invention, the acid diffusion control agent (D) may be used alone or in combination of two or more.
When the acid diffusion control agent (D) is contained in the composition, the content of the acid diffusion control agent (D) (the total if a plurality of types exist) is 0.1 based on the total solid content of the composition. It is preferably ~ 10.0% by mass, more preferably 0.1 ~ 5.0% by mass.

<Hydrophobic resin (E)>
The composition of the present invention may contain a hydrophobic resin (E). The hydrophobic resin (E) is preferably a resin different from the resin (AX1) and the resin (AX2).
By including the hydrophobic resin (E) in the composition of the present invention, the static / dynamic contact angle on the surface of the sensitive light-sensitive or radiation-sensitive film can be controlled. This makes it possible to improve development characteristics, suppress outgas, improve immersion liquid followability in immersion exposure, reduce immersion defects, and the like.
The hydrophobic resin (E) is preferably designed to be unevenly distributed on the surface of the resist film, but unlike a surfactant, it does not necessarily have to have a hydrophilic group in the molecule, and is a polar / non-polar substance. It does not have to contribute to uniform mixing.

The hydrophobic resin (E) is selected from the group consisting of "fluorine atom", "silicon atom", and "CH ₃ partial structure contained in the side chain portion of the resin" from the viewpoint of uneven distribution on the surface layer of the film. It is preferable that the resin has a repeating unit having at least one kind.
When the hydrophobic resin (E) contains a fluorine atom and / or a silicon atom, the fluorine atom and / or the silicon atom in the hydrophobic resin (E) may be contained in the main chain of the resin, and the side may be contained. It may be contained in the chain.

When the hydrophobic resin (E) contains a fluorine atom, the partial structure having a fluorine atom may be a resin having an alkyl group having a fluorine atom, a cycloalkyl group having a fluorine atom, or an aryl group having a fluorine atom. preferable.

The hydrophobic resin (E) preferably has at least one group selected from the following groups (x) to (z).
(X) Acid group (y) A group that decomposes by the action of an alkaline developer and increases its solubility in an alkaline developer (hereinafter, also referred to as a polarity conversion group).
(Z) A group that decomposes by the action of an acid

Examples of the acid group (x) include a phenolic hydroxyl group, a carboxylic acid group, a fluorinated alcohol group, a sulfonic acid group, a sulfonamide group, a sulfonylimide group, a (alkylsulfonyl) (alkylcarbonyl) methylene group, and (alkylsulfonyl) (alkyl). A carbonyl) imide group, a bis (alkylcarbonyl) methylene group, a bis (alkylcarbonyl) imide group, a bis (alkylsulfonyl) methylene group, a bis (alkylsulfonyl) imide group, a tris (alkylcarbonyl) methylene group, and a tris (alkylsulfonyl) group. ) Methylene group and the like can be mentioned.
As the acid group, a fluorinated alcohol group (preferably hexafluoroisopropanol), a sulfoneimide group, or a bis (alkylcarbonyl) methylene group is preferable.

Examples of the group (y) that decomposes due to the action of the alkaline developing solution and increases the solubility in the alkaline developing solution include a lactone group, a carboxylic acid ester group (-COO-), and an acid anhydride group (-C (O) OC). (O)-), acidimide group (-NHCONH-), carboxylic acid thioester group (-COS-), carbonate ester group (-OC (O) O-), sulfate ester group (-OSO ₂ O-), and Examples thereof include a sulfonic acid ester group (-SO ₂ O-), and a lactone group or a carboxylic acid ester group (-COO-) is preferable.
Examples of the repeating unit containing these groups include repeating units in which these groups are directly bonded to the main chain of the resin, and examples thereof include repeating units made of acrylic acid ester and methacrylic acid ester. In this repeating unit, these groups may be bonded to the main chain of the resin via a linking group. Alternatively, the repeating unit may be introduced into the terminal of the resin by using a polymerization initiator or a chain transfer agent having these groups at the time of polymerization.
Examples of the repeating unit having a lactone group include the same repeating units having a lactone structure described above in the section of resin (AX1).

The content of the repeating unit having a group (y) that decomposes by the action of the alkaline developer and increases the solubility in the alkaline developer is 1 to 100 mol% with respect to all the repeating units in the hydrophobic resin (E). Is preferable, 3 to 98 mol% is more preferable, and 5 to 95 mol% is further preferable.

Examples of the repeating unit having a group (z) that decomposes by the action of an acid in the hydrophobic resin (E) include the same repeating units having an acid-degradable group described in the resin (AX1). The repeating unit having a group (z) decomposed by the action of an acid may have at least one of a fluorine atom and a silicon atom. The content of the repeating unit having the group (z) decomposed by the action of the acid is preferably 1 to 80 mol%, more preferably 10 to 80 mol%, based on all the repeating units in the hydrophobic resin (E). , 20-60 mol% is more preferred.
The hydrophobic resin (E) may further have a repeating unit different from the repeating unit described above.

The repeating unit containing a fluorine atom is preferably 10 to 100 mol%, more preferably 30 to 100 mol%, based on all the repeating units in the hydrophobic resin (E). The repeating unit containing a silicon atom is preferably 10 to 100 mol%, more preferably 20 to 100 mol%, based on all the repeating units in the hydrophobic resin (E).

On the other hand, particularly when the hydrophobic resin (E) contains a _CH3 partial structure in the side chain portion, a form in which the hydrophobic resin (E) does not substantially contain fluorine atoms and silicon atoms is also preferable. Further, it is preferable that the hydrophobic resin (E) is substantially composed of only repeating units composed of only atoms selected from carbon atoms, oxygen atoms, hydrogen atoms, nitrogen atoms and sulfur atoms.

The weight average molecular weight of the hydrophobic resin (E) in terms of standard polystyrene is preferably 1,000 to 100,000, more preferably 1,000 to 50,000.

The total content of the residual monomer and / or the oligomer component contained in the hydrophobic resin (E) is preferably 0.01 to 5% by mass, more preferably 0.01 to 3% by mass. The dispersity (Mw / Mn) is preferably in the range of 1 to 5, and more preferably in the range of 1 to 3.

As the hydrophobic resin (E), a known resin can be appropriately selected and used alone or as a mixture thereof. For example, known resins disclosed in paragraphs <0451> to <0704> of U.S. Patent Application Publication 2015/016883A1 and paragraphs <0340> to <0356> of U.S. Patent Application Publication 2016/0274458A1. Can be suitably used as the hydrophobic resin (E). Further, the repeating unit disclosed in paragraphs <0177> to <0258> of US Patent Application Publication No. 2016/0237190A1 is also preferable as the repeating unit constituting the hydrophobic resin (E).

A preferred example of the monomer corresponding to the repeating unit constituting the hydrophobic resin (E) is shown below.

The hydrophobic resin (E) may be used alone or in combination of two or more.
It is preferable to mix and use two or more kinds of hydrophobic resins (E) having different surface energies from the viewpoint of achieving both immersion liquid followability and development characteristics in immersion exposure.
The content of the hydrophobic resin (E) in the composition is preferably 0.01 to 10.0% by mass, more preferably 0.05 to 8.0% by mass, based on the total solid content in the composition.

<Solvent (F)>
The composition of the present invention may contain a solvent.
In the composition of the present invention, a known resist solvent can be appropriately used. For example, paragraphs <0665> to <0670> of US Patent Application Publication No. 2016/0070167A1, paragraphs <0210> to <0235> of US Patent Application Publication No. 2015/0004544A1, US Patent Application Publication No. 2016/0237190A1. The known solvents disclosed in paragraphs <0424> to <0426> of the specification and paragraphs <0357> to <0366> of the US Patent Application Publication No. 2016/02744558A1 can be preferably used.
Examples of the solvent that can be used when preparing the composition include alkylene glycol monoalkyl ether carboxylate, alkylene glycol monoalkyl ether, lactic acid alkyl ester, alkyl alkoxypropionic acid, and cyclic lactone (preferably having 4 to 10 carbon atoms). Examples thereof include organic solvents such as monoketone compounds (preferably having 4 to 10 carbon atoms) which may have a ring, alkylene carbonate, alkyl alkoxyacetate, and alkyl pyruvate.

As the organic solvent, a mixed solvent in which a solvent having a hydroxyl group in the structure and a solvent having no hydroxyl group may be used may be used.
As the solvent having a hydroxyl group and the solvent having no hydroxyl group, the above-mentioned exemplary compounds can be appropriately selected, but as the solvent containing a hydroxyl group, alkylene glycol monoalkyl ether, alkyl lactate and the like are preferable, and propylene glycol monomethyl ether (propylene glycol monomethyl ether). PGME), propylene glycol monoethyl ether (PGEE), methyl 2-hydroxyisobutyrate, or ethyl lactate is more preferred. Further, as the solvent having no hydroxyl group, alkylene glycol monoalkyl ether acetate, alkylalkoxypropionate, monoketone compound which may have a ring, cyclic lactone, alkyl acetate and the like are preferable, and among these, propylene. Glycol monomethyl ether acetate (PGMEA), ethyl ethoxypropionate, 2-heptanone, γ-butyrolactone, cyclohexanone, cyclopentanone or butyl acetate are more preferred, propylene glycol monomethyl ether acetate, γ-butyrolactone, ethyl ethoxypropionate, Cyclohexanone, cyclopentanone or 2-heptanone are more preferred. Propylene carbonate is also preferable as the solvent having no hydroxyl group.
The mixing ratio (mass ratio) of the solvent having a hydroxyl group and the solvent having no hydroxyl group is 1/99 to 99/1, preferably 10/90 to 90/10, more preferably 20/80 to 60/40. preferable. A mixed solvent containing 50% by mass or more of a solvent having no hydroxyl group is preferable in terms of coating uniformity.
The solvent preferably contains propylene glycol monomethyl ether acetate, and may be a propylene glycol monomethyl ether acetate single solvent or a mixed solvent of two or more kinds containing propylene glycol monomethyl ether acetate.

<Crosslinking agent (G)>
The composition of the present invention may contain a compound that crosslinks the resin by the action of an acid (hereinafter, also referred to as a cross-linking agent (G)). As the cross-linking agent (G), a known compound can be appropriately used. For example, known compounds disclosed in paragraphs <0379> to <0431> of U.S. Patent Application Publication 2016 / 0147154A1 and paragraphs <0064> to <0141> of U.S. Patent Application Publication 2016/0282720A1. Can be suitably used as the cross-linking agent (G).
The cross-linking agent (G) is a compound having a cross-linking group capable of cross-linking the resin, and examples of the cross-linking group include a hydroxymethyl group, an alkoxymethyl group, an acyloxymethyl group, an alkoxymethyl ether group, and an oxylan ring. And the oxetane ring and the like.
The crosslinkable group is preferably a hydroxymethyl group, an alkoxymethyl group, an oxylan ring or an oxetane ring.
The cross-linking agent (G) is preferably a compound (including a resin) having two or more cross-linking groups.
The cross-linking agent (G) is more preferably a phenol derivative, a urea-based compound (compound having a urea structure) or a melamine-based compound (compound having a melamine structure) having a hydroxymethyl group or an alkoxymethyl group.
The cross-linking agent may be used alone or in combination of two or more.
The content of the cross-linking agent (G) is preferably 1.0 to 50% by mass, preferably 3.0 to 40% by mass, and further preferably 5.0 to 30% by mass with respect to the total solid content of the resist composition. preferable.

<Surfactant (H)>
The composition of the present invention may contain a surfactant. When a surfactant is contained, a fluorine-based and / or a silicon-based surfactant (specifically, a fluorine-based surfactant, a silicon-based surfactant, or a surfactant having both a fluorine atom and a silicon atom). Is preferable.

When the composition of the present invention contains a surfactant, a pattern having good sensitivity and resolution and few adhesions and development defects can be obtained when an exposure light source of 250 nm or less, particularly 220 nm or less is used.
Fluorine-based and / or silicon-based surfactants include the surfactants described in paragraph <0276> of US Patent Application Publication No. 2008/0248425.
Further, other surfactants other than the fluorine-based and / or silicon-based surfactants described in paragraph <0280> of Japanese Patent Application Publication No. 2008/0248425 can also be used.

These surfactants may be used alone or in combination of two or more.
When the composition of the present invention contains a surfactant, the content of the surfactant is preferably 0.0001 to 2.0% by mass, preferably 0.0005 to 1.0, based on the total solid content of the composition. % By mass is more preferred.
On the other hand, when the content of the surfactant is 10 ppm or more with respect to the total solid content of the composition, the surface uneven distribution of the hydrophobic resin (E) is increased. Thereby, the surface of the sensitive light-sensitive or radiation-sensitive film can be made more hydrophobic, and the water followability at the time of immersion exposure is improved.

(Other additives)
The compositions of the present invention further include other additives such as acid growth agents, dyes, plasticizers, photosensitizers, light absorbers, alkali-soluble resins, dissolution inhibitors, and dissolution accelerators. May be good.

<Preparation method>
The solid content concentration of the composition of the present invention is usually preferably 1.0 to 10% by mass, more preferably 2.0 to 5.7% by mass, still more preferably 2.0 to 5.3% by mass. The solid content concentration is the mass percentage of the mass of other resist components excluding the solvent with respect to the total mass of the composition.

The film thickness of the sensitive light-sensitive or radiation-sensitive film made of the composition of the present invention is preferably 90 nm or less, more preferably 85 nm or less, from the viewpoint of improving the resolving power. Such a film thickness can be obtained by setting the solid content concentration in the composition to an appropriate range to give an appropriate viscosity and improving the coatability or the film forming property.

In the composition of the present invention, the above-mentioned components are dissolved in a predetermined organic solvent, preferably the above-mentioned mixed solvent, filtered through a filter, and then applied onto a predetermined support (substrate) for use. The pore size of the filter used for filter filtration is preferably 0.1 μm or less, more preferably 0.05 μm or less, still more preferably 0.03 μm or less. The filter is preferably made of polytetrafluoroethylene, polyethylene, or nylon. In filter filtration, for example, as disclosed in Japanese Patent Application Publication No. 2002-62667 (Japanese Patent Laid-Open No. 2002-62667), cyclic filtration may be performed, and a plurality of types of filters may be connected in series or in parallel. It may be connected to and filtered. Also, the composition may be filtered multiple times. Further, the composition may be degassed before and after the filter filtration.

<Use>
The composition of the present invention relates to a sensitive light-sensitive or radiation-sensitive resin composition whose properties change in response to irradiation with active light or radiation. More specifically, the composition of the present invention comprises a semiconductor manufacturing process such as an IC (Integrated Circuit), a circuit board manufacturing such as a liquid crystal or a thermal head, a molding structure for imprinting, another photofabrication step, or a photofabrication step. The present invention relates to a sensitive light-sensitive or radiation-sensitive resin composition used for producing a flat plate printing plate or an acid-curable composition. The pattern formed in the present invention can be used in an etching step, an ion implantation step, a bump electrode forming step, a rewiring forming step, a MEMS (Micro Electro Electro Mechanical Systems), and the like.

[Pattern formation method]
The present invention also relates to a pattern forming method using the above-mentioned sensitive light-sensitive or radiation-sensitive resin composition. Hereinafter, the pattern forming method of the present invention will be described. In addition to the description of the pattern forming method, the sensitive light-sensitive or radiation-sensitive film of the present invention will also be described.

The pattern forming method of the present invention is
(I) A step of forming a resist film (sensitive light-sensitive or radiation-sensitive film) on a support by the above-mentioned sensitive light-sensitive or radiation-sensitive resin composition (resist film forming step).
(Ii) A step (exposure step) of exposing the resist film (irradiating with active light rays or radiation), and
(Iii) A step of developing the exposed resist film using a developing solution (development step).
Have.

The pattern forming method of the present invention is not particularly limited as long as it includes the steps (i) to (iii) above, and may further include the following steps.
In the pattern forming method of the present invention, the exposure method in the (ii) exposure step may be immersion exposure.
The pattern forming method of the present invention preferably includes (iv) preheating (PB: PreBake) step before the (ii) exposure step.
The pattern forming method of the present invention preferably includes (v) post-exposure heating (PEB: Post Exposure Bake) step after (ii) exposure step and before (iii) development step.
The pattern forming method of the present invention may include (ii) an exposure step a plurality of times.
The pattern forming method of the present invention may include (iv) a preheating step a plurality of times.
The pattern forming method of the present invention may include (v) a post-exposure heating step a plurality of times.

In the pattern forming method of the present invention, the above-mentioned (i) film forming step, (ii) exposure step, and (iii) developing step can be performed by a generally known method.
Further, if necessary, a resist underlayer film (for example, SOG (Spin On Glass), SOC (Spin On Carbon), and antireflection film) may be formed between the resist film and the support. As a material constituting the resist underlayer film, a known organic or inorganic material can be appropriately used.
A protective film (top coat) may be formed on the upper layer of the resist film. As the protective film, a known material can be appropriately used. For example, US Patent Application Publication No. 2007/0178407, US Patent Application Publication No. 2008/0087466, US Patent Application Publication No. 2007/0275326, US Patent Application Publication No. 2016/0299432, The composition for forming a protective film disclosed in US Patent Application Publication No. 2013/02444438 and International Patent Application Publication No. 2016/157988A can be preferably used. The composition for forming a protective film preferably contains the above-mentioned acid diffusion control agent.
A protective film may be formed on the upper layer of the resist film containing the above-mentioned hydrophobic resin.

The support is not particularly limited, and is generally used in a semiconductor manufacturing process such as an IC, a circuit board manufacturing process such as a liquid crystal or a thermal head, and other photolithography lithography processes. A substrate can be used. Specific examples of the support include an inorganic substrate such as silicon, SiO ₂ , and SiN.

The heating temperature is preferably 70 to 130 ° C., more preferably 80 to 120 ° C. in both the (iv) preheating step and (v) post-exposure heating step.
The heating time is preferably 30 to 300 seconds, more preferably 30 to 180 seconds, still more preferably 30 to 90 seconds in both the (iv) pre-heating step and (v) post-exposure heating step.
The heating can be performed by means provided in the exposure apparatus and the developing apparatus, and may be performed by using a hot plate or the like.

The wavelength of the light source used in the exposure process is not limited, and examples thereof include infrared light, visible light, ultraviolet light, far ultraviolet light, polar ultraviolet light (EUV), X-ray, and electron beam. Among these, far-ultraviolet light is preferable, the wavelength thereof is preferably 250 nm or less, more preferably 220 nm or less, still more preferably 1 to 200 nm. Specifically, it is a KrF excimer laser (248 nm), an ArF excimer laser (193 nm), an F2 excimer laser ₍ 157 nm), an X-ray, an EUV (13 nm), an electron beam or the like, and is a KrF excimer laser, an ArF excimer laser, etc. EUV or electron beam is preferred.

(Iii) In the developing step, it may be an alkaline developer or a developer containing an organic solvent (hereinafter, also referred to as an organic developer).

As the alkaline developer, a quaternary ammonium salt typified by tetramethylammonium hydroxide is usually used, but in addition to this, alkaline aqueous solutions such as inorganic alkalis, primary to tertiary amines, alcohol amines, and cyclic amines are also used. It can be used.
Further, the alkaline developer may contain an appropriate amount of alcohols and / or a surfactant. The alkaline concentration of the alkaline developer is usually 0.1 to 20% by mass. The pH of the alkaline developer is usually 10 to 15.
The time for developing with an alkaline developer is usually 10 to 300 seconds.
The alkali concentration, pH, and development time of the alkaline developer can be appropriately adjusted according to the pattern to be formed.

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

Examples of the ketone solvent include 1-octanone, 2-octanone, 1-nonanonone, 2-nonanonone, acetone, 2-heptanone (methylamylketone), 4-heptanone, 1-hexanone, 2-hexanone, and diisobutylketone. Cyclohexanone, methylcyclohexanone, phenylacetone, methylethylketone, methylisobutylketone, acetylacetone, acetonylacetone, ionone, diacetonyl alcohol, acetylcarbinol, acetophenone, methylnaphthylketone, isophorone, propylene carbonate and the like can be mentioned.

Examples of the ester solvent include methyl acetate, butyl acetate, ethyl acetate, isopropyl acetate, pentyl acetate, isoamyl acetate, amyl acetate, propylene glycol monomethyl ether acetate, ethylene glycol monoethyl ether acetate, diethylene glycol monobutyl ether acetate, and diethylene glycol monoethyl. Ether acetate, ethyl-3-ethoxypropionate, 3-methoxybutyl acetate, 3-methyl-3-methoxybutyl acetate, methyl formic acid, ethyl forerate, butyl forerate, propyl forerate, ethyl lactate, butyl lactate, propyl lactate, butane Examples thereof include butyl acetate, methyl 2-hydroxyisobutyrate, isoamyl acetate, isobutyl isobutyrate, butyl propionate and the like.

As the alcohol-based solvent, the amide-based solvent, the ether-based solvent, and the hydrocarbon-based solvent, the solvents disclosed in paragraphs <0715> to <0718> of US Patent Application Publication No. 2016/0070167A1 can be used.

A plurality of the above solvents may be mixed, or may be mixed with a solvent other than the above or water. The water content of the developer as a whole is preferably less than 50% by mass, more preferably less than 20% by mass, further preferably less than 10% by mass, most preferably 0% by mass or more and less than 5% by mass, and substantially contains water. Not particularly preferred.
The content of the organic solvent in the organic developer is preferably 50 to 100% by mass, more preferably 80 to 100% by mass, further preferably 90 to 100% by mass, and 95 to 100% by mass with respect to the total amount of the developer. % Is particularly preferable.

The organic developer may contain an appropriate amount of a known surfactant, if necessary.

The content of the surfactant is usually 0.001 to 5% by mass, preferably 0.005 to 2% by mass, more preferably 0.01 to 0.5% by mass, based on the total amount of the developing solution.

The organic developer may contain the above-mentioned acid diffusion control agent.

Examples of the developing method include a method of immersing the substrate in a tank filled with a developing solution for a certain period of time (dip method), a method of raising the developing solution on the surface of the substrate by surface tension and allowing it to stand still for a certain period of time (paddle method), and a substrate. A method of spraying the developer on the surface (spray method) or a method of continuously discharging the developer while scanning the developer discharge nozzle at a constant speed on a substrate rotating at a constant speed (dynamic discharge method) can be mentioned. Be done.

A step of developing with an alkaline aqueous solution (alkaline developing step) and a step of developing with a developer containing an organic solvent (organic solvent developing step) may be combined. As a result, the pattern can be formed without dissolving only the region of the intermediate exposure intensity, so that a finer pattern can be formed.

(Iii) It is preferable to include a step of washing with a rinsing solution (rinsing step) after the developing step.

As the rinsing solution used in the rinsing step after the developing step using the alkaline developer, for example, pure water can be used. Pure water may contain an appropriate amount of a surfactant. In this case, after the developing step or the rinsing step, a process of removing the developing solution or the rinsing solution adhering to the pattern with a supercritical fluid may be added. Further, after the rinsing treatment or the treatment with the supercritical fluid, a heat treatment may be performed to remove the water remaining in the pattern.

The rinsing solution used in the rinsing step after the developing step using the developing solution containing an organic solvent is not particularly limited as long as it does not dissolve the pattern, and a general solution containing an organic solvent can be used. As the rinsing solution, a rinsing solution containing at least one organic solvent selected from the group consisting of a hydrocarbon solvent, a ketone solvent, an ester solvent, an alcohol solvent, an amide solvent, and an ether solvent shall be used. Is preferable.
Specific examples of the hydrocarbon solvent, the ketone solvent, the ester solvent, the alcohol solvent, the amide solvent, and the ether solvent include the same as those described for the developing solution containing the organic solvent.
As the rinsing liquid used in the rinsing step in this case, a rinsing liquid containing a monohydric alcohol is more preferable.

Examples of the monohydric alcohol used in the rinsing step include linear, branched or cyclic monohydric alcohols. Specifically, 1-butanol, 2-butanol, 3-methyl-1-butanol, tert-butyl alcohol, 1-pentanol, 2-pentanol, 1-hexanol, 4-methyl-2-pentanol, 1 -Heptanol, 1-octanol, 2-hexanol, cyclopentanol, 2-heptanol, 2-octanol, 3-hexanol, 3-heptanol, 3-octanol, 4-octanol, and methylisobutylcarbinol can be mentioned. Examples of the monohydric alcohol having 5 or more carbon atoms include 1-hexanol, 2-hexanol, 4-methyl-2-pentanol, 1-pentanol, 3-methyl-1-butanol, methyl isobutylcarbinol and the like. ..

A plurality of each component may be mixed, or may be used by mixing with an organic solvent other than the above.
The water content in the rinse solution is preferably 10% by mass or less, more preferably 5% by mass or less, and even more preferably 3% by mass or less. By setting the water content to 10% by mass or less, good development characteristics can be obtained.

The rinse solution may contain an appropriate amount of a surfactant.
In the rinsing step, the substrate developed with an organic developer is washed with a rinsing solution containing an organic solvent. The cleaning treatment method is not particularly limited, but for example, a method of continuously discharging the rinse liquid onto a substrate rotating at a constant speed (rotational coating method), or immersing the substrate in a tank filled with the rinse liquid for a certain period of time. Examples thereof include a method (dip method) and a method of spraying a rinse liquid on the substrate surface (spray method). Above all, it is preferable to perform a cleaning treatment by a rotary coating method, and after cleaning, rotate the substrate at a rotation speed of 2,000 to 4,000 rpm to remove the rinse liquid from the substrate. It is also preferable to include a heating step (Post Bake) after the rinsing step. By this heating step, the developing solution and the rinsing solution remaining between the patterns and inside the patterns are removed. In the heating step after the rinsing step, the heating temperature is usually 40 to 160 ° C., preferably 70 to 95 ° C., and the heating time is usually 10 seconds to 3 minutes, preferably 30 seconds to 90 seconds.

The sensitive light-sensitive or radiation-sensitive resin composition of the present invention, and various materials used in the pattern forming method of the present invention (for example, a resist solvent, a developing solution, a rinsing solution, an antireflection film forming composition, or The composition for forming a top coat, etc.) preferably does not contain impurities such as metal components, isomers, and residual monomers. The content of these impurities contained in the above-mentioned various materials is preferably 1 ppm or less, more preferably 100 ppt or less, further preferably 10 ppt or less, and substantially not contained (below the detection limit of the measuring device). Is particularly preferable.

Examples of the method for removing impurities such as metals from the above-mentioned various materials include filtration using a filter. The filter pore diameter is preferably 10 nm or less, more preferably 5 nm or less, and even more preferably 3 nm or less. As the material of the filter, a filter made of polytetrafluoroethylene, polyethylene, or nylon is preferable. The filter may be one that has been pre-cleaned with an organic solvent. In the filter filtration step, a plurality of types of filters may be connected in series or in parallel for use. When using a plurality of types of filters, filters having different pore diameters and / or materials may be used in combination. Further, various materials may be filtered a plurality of times, and the step of filtering the various materials a plurality of times may be a circulation filtration step. The filter preferably has a reduced amount of eluate as disclosed in Japanese Patent Application Publication No. 2016-201426 (Japanese Patent Laid-Open No. 2016-201426).
In addition to filter filtration, impurities may be removed by an adsorbent, or filter filtration and an adsorbent may be used in combination. As the adsorbent, a known adsorbent can be used, and for example, an inorganic adsorbent such as silica gel or zeolite, or an organic adsorbent such as activated carbon can be used. Examples of the metal adsorbent include those disclosed in Japanese Patent Application Publication No. 2016-206500 (Japanese Patent Laid-Open No. 2016-206500).
Further, as a method for reducing impurities such as metals contained in the various materials, a raw material having a low metal content is selected as a raw material constituting the various materials, and filter filtration is performed on the raw materials constituting the various materials. Alternatively, a method such as lining the inside of the apparatus with Teflon (registered trademark) to perform distillation under conditions in which contamination is suppressed as much as possible can be mentioned. It is also preferable to apply glass lining treatment to all the steps of the manufacturing equipment for synthesizing various materials (resin, photoacid generator, etc.) of the resist component in order to reduce impurities such as metals to the order of ppt. The preferred conditions for filter filtration performed on the raw materials constituting the various materials are the same as the above-mentioned conditions.

The above-mentioned various materials are described in US Patent Application Publication No. 2015/0227049, Japanese Patent Application Publication No. 2015-123351 (Japanese Patent Laid-Open No. 2015-123351), etc. in order to prevent contamination with impurities. It is preferable to store it in a container.

A method for improving the surface roughness of the pattern may be applied to the pattern formed by the pattern forming method of the present invention. Examples of the method for improving the surface roughness of the pattern include a method of treating the pattern with plasma of a gas containing hydrogen disclosed in US Patent Application Publication No. 2015/010497. In addition, Japanese Patent Application Publication No. 2004-235468 (Japanese Patent Laid-Open No. 2004-235468), US Patent Application Publication No. 2010/0020297, Proc. of SPIE Vol. A known method as described in 832883280N-1 “EUV Resist Curing Technology for LWR Resistion and Etch Sensitivity Enhancement” may be applied.
Further, the pattern formed by the above method is a spacer process disclosed in, for example, Japanese Patent Application Publication No. 1991-270227 (Japanese Patent Laid-Open No. 3-270227) and US Patent Application Publication No. 2013/209941. Can be used as a core material (Core).

[Manufacturing method of electronic device]
The present invention also relates to a method for manufacturing an electronic device, including the above-mentioned pattern forming method. The electronic device manufactured by the method for manufacturing an electronic device of the present invention is suitably mounted on an electric electronic device (for example, a home appliance, an OA (Office Automation) related device, a media related device, an optical device, a communication device, etc.). Will be done.

〔Compound〕
The present invention also relates to a compound represented by the general formula (1) and a compound represented by the general formula (2).
Specific embodiments of the compound represented by the general formula (1) and the compound represented by the general formula (2) are as described above.

Hereinafter, the present invention will be described in more detail based on examples. The materials, amounts, ratios, treatment contents, treatment procedures, etc. shown in the following examples can be appropriately changed as long as they do not deviate from the gist of the present invention. Therefore, the scope of the present invention should not be construed as limiting by the examples shown below.

[Preparation of Actinic Cheilitis or Radiation Sensitive Resin Composition]
The various components contained in the actinic cheilitis or actinic cheilitis resin compositions shown in Table 3 are shown below.
<Resin (AX1)>
The resins (A1 to A6) shown in Table 3 are shown below.
The weight average molecular weight (Mw) and the dispersity (Mw / Mn) of the resins A1 to A6 were measured by GPC (carrier: tetrahydrofuran (THF)) (in terms of polystyrene). The composition ratio (mol% ratio) of the resin was measured by ¹³ C-NMR (nuclear magnetic resonance).

<Acid generator (B)>
The structures of the acid generators (B) (compounds B1 to B10) (corresponding to the acid generator X) shown in Table 3 are shown below.

Table 1 shows the pKa of the acid generated from the above-mentioned acid generator (B) (compounds B1 to B10). The measurement of pKa was performed by the method described above.

<Acid diffusion control agent>
(Compound (C) represented by the general formula (1))
The structures of the compounds (compounds C1 to C18) represented by the general formula (1) shown in Table 3 are shown below. In addition, an example of synthesizing compound C1 is also shown as an example.

<< Synthesis Example 1: Synthesis of compound C1 >>
Ethyl 2-iodobenzoate (3.3 g) was dissolved in THF (20 mL) placed in a container, and then the internal temperature was cooled to −10 ° C. Next, an isopropylmagnesium chloride-lithium chloride complex (THF solution, 11.9 g) was added dropwise to the cooled mixed solution so that the internal temperature did not exceed 0 ° C., and the mixture was stirred at −10 ° C. for 30 minutes (reaction solution 1). ).
Diphenyl sulfoxide (3.2 g) was dissolved in THF (20 mL) placed in a container, and then the internal temperature was cooled to −10 ° C. Next, trifluoromethanesulfonic anhydride (3.4 g) was added dropwise to the cooled mixed solution so that the internal temperature did not exceed 0 ° C., and the mixture was stirred at 0 ° C. for 30 minutes (reaction solution 2).
Subsequently, the reaction solution 1 was added dropwise to the container containing the reaction solution 2 so that the internal temperature did not exceed 0 ° C., and then the reaction was carried out at room temperature for 12 hours. Methylene chloride (100 mL) and distilled water (100 mL) were added to the obtained reaction solution, and the layers were separated. Then, the extracted organic layer was washed with distilled water (50 mL) four times, and then the solvent was distilled off. Further, the obtained residue was purified by a column to obtain a purified product.
The purified product obtained by the above step was dissolved in methylene chloride (16 mL), 0.2N sodium hydroxide (16 mL) was further added, and the mixture was reacted at 40 ° C. for 4 hours. The obtained reaction solution was separated, and the aqueous layer was extracted 5 times with methylene chloride (15 mL), and then the solvent was distilled off. The obtained solid was washed with diisopropyl ether (5 mL), the solvent was removed, and the mixture was dried to obtain C1 (0.26 g).

Further, the same operation as in the synthesis example of the above compound C1 was carried out to synthesize the compounds C2 to C24 described later.

(Comparative Acid Diffusion Control Agent (D))
The structures of the comparative acid diffusion regulators (Compounds D1 to D4) shown in Table 3 are shown below.

(PKa of acid diffusion control agent)
Table 2 shows the pKa of the acid generated from the compounds C1 to C24 and the pKa of the acid generated from the compounds D1 to D4. The measurement of pKa was performed by the method described above.

<Preparation of Actinic Cheilitis or Radiation Sensitive Resin Composition>
Each component shown in Table 3 was mixed so that the solid content concentration was 3.3% by mass. Then, the obtained mixed solution is first filtered through a polyethylene filter having a pore size of 50 nm, then a nylon filter having a pore diameter of 10 nm, and finally a polyethylene filter having a pore diameter of 5 nm, thereby causing actinic cheilitis or radiation sensitivity. A sex resin composition was prepared. In the actinic cheilitis or radiation-sensitive resin composition, the solid content means all the components other than the solvent (F). The obtained sensitive light-sensitive or radiation-sensitive resin composition was used in Examples and Comparative Examples.

[Pattern formation and various evaluations]
<Pattern formation 1: ArF immersion exposure, organic solvent development>
The composition for forming an organic antireflection film ARC29SR (manufactured by Nissan Chemical Industries, Ltd.) was applied onto a silicon wafer and heated at 205 ° C. for 60 seconds to form an antireflection film having a film thickness of 95 nm. The sensitive light-sensitive or radiation-sensitive resin compositions of Examples and Comparative Examples were applied onto the obtained antireflection film and heated at 100 ° C. for 60 seconds (PB: Prebake) to obtain a resist film having a film thickness of 85 nm. Was formed.
The resist film on the silicon wafer obtained by the above procedure is subjected to ArF excimer laser immersion scanner (manufactured by ASML; XT1700i, NA1.20, C-Quad, outer sigma 0.900, inner sigma 0.812, XY deflection. ) Was used to expose through a 6% halftone mask with a 1: 1 line and space pattern with a line width of 44 nm. Ultrapure water was used as the immersion liquid. Then, the resist film after exposure is heated at 105 ° C. for 60 seconds (PEB: Post Exposure Bake), then developed with a negative developer (organic developer, butyl acetate) for 30 seconds by the paddle method, and further. Rinse with a rinse solution (methylisobutylcarbinol (MIBC)) for 30 seconds by the paddle method. Subsequently, this silicon wafer was spin-dried at a rotation speed of 4000 rpm for 30 seconds to form a 1: 1 line-and-space pattern with a line width of 44 nm.

<Performance evaluation: LWR performance (nm)>
The obtained 44 nm 1: 1 line-and-space pattern was observed from above the pattern using a length-measuring scanning electron microscope (S-8840, manufactured by Hitachi, Ltd.). At this time, the line width was measured at 50 points in the range of the edge of 2 μm in the longitudinal direction of the line pattern, and the standard deviation (3σ) was calculated for the measurement variation of the measured line width. The smaller the standard deviation (3σ) value, the better the pattern of LWR performance.
The evaluation of LWR performance was carried out based on the following five-step criteria. The evaluation results are shown in Table 3.

(Evaluation criteria)
"5": LWR <3.0 nm
"4": 3.0 nm ≤ LWR <4.0 nm
"3": 4.0 nm ≤ LWR <5.0 nm
"2": 5.0 nm ≤ LWR <6.0 nm
"1": 6.0 nm ≤ LWR

<Pattern formation 2: ArF immersion exposure, organic solvent development>
An organic antireflection film ARC29SR (manufactured by Brewer) is applied on a silicon wafer and baked at 205 ° C. for 60 seconds to form an antireflection film having a film thickness of 98 nm. A sexual or radiation-sensitive resin composition was applied and baked at 100 ° C. for 60 seconds to form a resist film having a film thickness of 90 nm.
The wafer on which the resist film obtained by the above procedure was formed was subjected to an ArF excimer laser immersion scanner (manufactured by ASML; XT1700i, NA (numerical aperture) 1.20, C-Quad, outer sigma 0.98, inner sigma 0. Using 89, XY deflection), a contact hole pattern with a diameter of 45 nm was exposed via a 6% halftone mask. The exposure amount having the above-mentioned pattern size was defined as the optimum exposure amount. Ultrapure water was used as the immersion liquid. Then, after heating at the PEB temperature set to 90 ° C., it was developed with butyl acetate which is an organic developer for 30 seconds, and spin-dried to obtain a whole pattern.

<Performance evaluation: CDU performance (nm)>
In one shot exposed with the above optimum exposure amount ( _Eopt ), arbitrary 25 holes (that is, a total of 500 holes) were measured for each region in 20 regions having a distance of 1 μm from each other. , These standard deviations (σ) were obtained, and 3σ was calculated. The smaller the value, the smaller the variation in dimensions, indicating that the performance is good.
The evaluation of CDU performance was carried out based on the following five-step criteria. The evaluation results are shown in Table 3.

(Evaluation criteria)
"5": CDU <4.0 nm
"4": 4.0 nm ≤ CDU <4.5 nm
"3": 4.5 nm ≤ CDU <5.0 nm
"2": 5.0 nm ≤ CDU <6.0 nm
"1": 6.0 nm ≤ CDU

In addition, in Table 3, the content (mass%) of each component means the content with respect to the total solid content.
Further, in Table 3, "pKa (B)" corresponds to pKa of the acid generated from the acid generator (B) (compounds B1 to B10) (the same as that shown in Table 1). ..
Further, in Table 3, "pKa (A1)" and "pKa (A2)" are pKa of an acid generated from a compound represented by the general formula (1) (compounds C1 to C24), and a comparative acid. Each corresponds to the pKa of the acid generated from the diffusion control agent (Compounds D1 to D4) (the same as those listed in Table 2).

From the results in Table 3, it was confirmed that the LWR and CDU of the formed pattern were both excellent according to the sensitive light-sensitive or radiation-sensitive resin composition of the example.
Further, from the comparison of Examples 1, 4, 10 and 12, in the compound represented by the general formula (1), at least one or more of Ar ₁ , Ar ₂ and Ar ₃ is unsubstituted monocyclic aromatic hydrocarbon. When it is a hydrogen group (in other words, in the compound represented by the general formula (2), R ₁ to R ₄ are all hydrogen atoms, or at least one of Ar ₂ and Ar ₃ is an unsubstituted single ring. When it was an aromatic hydrocarbon group (comparison between Examples 1, 4, and 10 and Example 12), it was confirmed that the LWR and CDU of the formed pattern were both superior.

Further, from the comparison of Examples 1, 4, 10 and 12, in the compound represented by the general formula (1), at least two or more of Ar ₁ , Ar ₂ and Ar ₃ are unsubstituted monocyclic aromatic hydrocarbons. When it is a hydrogen group (in other words, in the compound represented by the general formula (2), R ₁ to R ₄ are all hydrogen atoms and one of Ar ₂ and Ar ₃ is an unsubstituted monocyclic aromatic hydrocarbon. Whether it is a group, Ar ₂ and Ar ₃ are both unsubstituted monocyclic aromatic hydrocarbon groups, or R ₁ to R ₄ are all hydrogen atoms and Ar ₂ and Ar ₃ are both absent. In the case of substituted monocyclic aromatic hydrocarbon groups (comparison between Examples 1 and 4 and Examples 10 and 12), it was confirmed that the LWR and CDU of the formed patterns were both superior. rice field.

Further, from the comparison between Examples 1 and Examples 13 and 14, when L ₁ to L ₃ are single bonds in the compound represented by the general formula (1), the LWR and CDU of the formed pattern are any of them. Was confirmed to be better.
Further, from the comparison of Examples 1, 2 and 15 to 18, in the compound represented by the general formula (1), A ₁ is -L ₁ -CO _2- or -L ₃ ^- X ₁ ^- N-. When -Y ₁ , it was confirmed that both the LWR and CDU of the formed pattern were superior.

Further, from the comparison between Example 1 and Examples 19 and 20, when the compound represented by the general formula (1) is the compound represented by the general formula (2), the LWR of the formed pattern is obtained. And CDU were both confirmed to be superior.

Further, from the comparison between Example 21 and Example 22, when Ar ₁ has a non-aromatic substituent in the compound represented by the general formula (1), both the LWR and the CDU of the formed pattern are both. It was confirmed to be better.

On the other hand, the sensitive light-sensitive or radiation-sensitive resin composition of the comparative example did not meet the desired requirements.

Claims (10)

With resin
An acid generator that generates acid by irradiation with active light or radiation,
Contains acid diffusion regulators,
A sensitive light-sensitive or radiation-sensitive resin composition, wherein the acid diffusion control agent contains a compound represented by the following general formula (1).

In the above formula, Ar ₁ , Ar ₂ and Ar ₃ each independently represent an aromatic hydrocarbon group.
A ₁ is substituted at the ortho position with respect to the carbon atom bonded to S ⁺ on Ar ₁ , and -L ₁ -CO _2- , -L ₂ ^- SO _3- , or -L ₃ ^- X _1- . Represents N ^{－ －} Y ₁ .
L ₁ represents a divalent linking group.
L ₂ and L ₃ each independently represent a single bond or a divalent linking group.
X ₁ represents -SO _2- or -CO-.
Y ₁ represents -SO _{2 - RA} or -CO-RB.
_RA and _RB each independently represent a monovalent substituent.
In addition, Ar ₁ , Ar ₂ and Ar ₃ may further have a substituent, and the substituents may be bonded to each other to form a ring. The actinic light-sensitive or radiation-sensitive resin composition according to claim 1, wherein the compound represented by the general formula (1) is a compound represented by the following general formula (2).

In the above formula, Ar ₂ and Ar ₃ each independently represent a monocyclic aromatic hydrocarbon group.
R ₁ , R ₂ , R ₃ and R ₄ each independently represent a hydrogen atom or a non-aromatic substituent.
A ₁ represents -L ₁ -CO _2- , -L ₂ ^- SO _3- ^, or -L ₃ ^- X ₁ -N --Y ₁ .
L ₁ represents a divalent linking group.
L ₂ and L ₃ each independently represent a single bond or a divalent linking group.
X ₁ represents -SO _2- or -CO-.
Y ₁ represents -SO _{2 - RA} or -CO-RB.
_RA and _RB each independently represent a monovalent substituent.
In addition, Ar ₂ and Ar ₃ may further have a substituent, and the substituents may be bonded to each other to form a ring. The sensitive light-sensitive or radiation-sensitive radiation according to claim 2, wherein R ₁ to R ₄ are all hydrogen atoms, or at least one of Ar ₂ and Ar ₃ is an unsubstituted monocyclic aromatic hydrocarbon group. Sex resin composition. Whether R ₁ to R ₄ are all hydrogen atoms and one of Ar ₂ and Ar ₃ is an unsubstituted monocyclic aromatic hydrocarbon group.
Both Ar ₂ and Ar ₃ are unsubstituted monocyclic aromatic hydrocarbon groups, or
The sensitive light-sensitive or radiation-sensitive resin composition according to claim 2, wherein R ₁ to R ₄ are all hydrogen atoms and Ar ₂ and Ar ₃ are both unsubstituted monocyclic aromatic hydrocarbon groups. .. The sensitive light-sensitive or radiation-sensitive resin according to any one of claims 1 to 4, wherein A ₁ is -L ₁ ^- CO _2- or -L ₃ ^- X ₁ -N --Y ₁ . Composition. The actinic or radiation-sensitive resin composition according to claim 5, wherein L ₃ is a single bond. With resin
An acid generator that generates acid by irradiation with active light or radiation,
Contains acid diffusion regulators,
A sensitive light-sensitive or radiation-sensitive resin composition, wherein the acid diffusion control agent contains a compound represented by the following general formula (1).

In the above formula, Ar ₁ , Ar ₂ And Ar ₃ Represents each independently an aromatic hydrocarbon group.
Also, Ar ₁ , Ar ₂ And Ar ₃ May further have a substituent, and the substituents may be bonded to each other to form a ring. However, Ar ₁ , Ar ₂ And Ar ₃ At least one of them has a halogen atom as a substituent.
A ₁ Is Ar ₁ S on ^＋ Substitutes the ortho position for the carbon atom bonded to, and -L ₁ -CO ₂ ^- Represents.
L ₁ Represents a single bond. A resist film formed by using the sensitive light-sensitive or radiation-sensitive resin composition according to any one of claims 1 to 7 . A resist film forming step of forming a resist film using the sensitive light-sensitive or radiation-sensitive resin composition according to any one of claims 1 to 7 .
The exposure process for exposing the resist film and
A pattern forming method comprising a developing step of developing the exposed resist film with a developing solution. A method for manufacturing an electronic device, including the pattern forming method according to claim 9 .