WO2019123895A1

WO2019123895A1 - Active-light-sensitive or radiation-sensitive resin composition, resist film, pattern formation method, method for manufacturing electronic device, and compound

Info

Publication number: WO2019123895A1
Application number: PCT/JP2018/042011
Authority: WO
Inventors: 稔上村; 恵士山本; 研由後藤; 三千紘白川; 光宏藤田
Original assignee: 富士フイルム株式会社
Priority date: 2017-12-22
Filing date: 2018-11-13
Publication date: 2019-06-27
Also published as: JPWO2019123895A1; TW201927746A; TWI787400B; JP6997803B2

Abstract

Provided is an active-light-sensitive or radiation-sensitive resin composition that can be used to form a pattern having excellent pattern line width roughness (LRW) and critical dimension uniformity (CDU). Also provided are a resist film that uses the active-light-sensitive or radiation-sensitive resin composition, a pattern formation method, and a method for manufacturing an electronic device. A novel compound is also provided. The active-light-sensitive or radiation-sensitive resin composition comprises: a resin; an acid generating agent that generates an acid through irradiation with active light rays or radiation; and an acid diffusion control agent, the acid diffusion control agent including a compound expressed by the general formula (1).

Description

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

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

Conventionally, in the manufacturing process of semiconductor devices such as integrated circuits (ICs) and large scale integrated circuits (LSIs), 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 film is formed using an actinic ray-sensitive or radiation-sensitive resin composition containing (A) the following (A) to (C): Forming process,
(A) A resin in which the polarity is increased by the action of an acid to decrease the solubility in a developer containing an organic solvent,
(B) a compound capable of generating an acid upon irradiation with an actinic ray or radiation, and (C) having a cation site and an anion site in the same molecule, and the cation site and the anion site are covalently linked A method of forming a pattern, comprising the steps of: (1) exposing the film; and (2) developing the exposed film using a developer containing an organic solvent to form a negative pattern. Is disclosed. Moreover, in the said patent document 1, the following two types of betaine type compounds are disclosed as (C) component.

The component (B) is a so-called acid generator, and generates an acid upon irradiation with an actinic ray or radiation in the exposure step (step (a)). The generated acid mainly contributes to the deprotection reaction of the acid-degradable resin (the component (A)).

JP, 2014-170205, A

The present inventors refer to Patent Document 1 and use acid generation generally used to cause a deprotection reaction of a resin component (a deprotection reaction of an acid-degradable resin) or to cause a crosslinking reaction of a resin component. And the betaine type compound were examined by preparing an actinic ray sensitive or radiation sensitive resin composition containing the agent (hereinafter referred to as "acid generator X") and the above betaine type compound. Of the acid generator X generates an acid which 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 area (neutralization Have been known to function as
On the other hand, the present inventors have found that the above-mentioned betaine type compound easily forms aggregates (for example, dimers) in the actinic ray-sensitive or radiation-sensitive resin composition and is difficult to be uniformly dispersed in the system. It became clear. As a result, a film of an actinic ray-sensitive or radiation-sensitive resin composition containing an acid generator X and the above-mentioned betaine type compound (hereinafter, a "film of an actinic-ray-sensitive or radiation-sensitive resin composition" In some cases, due to the non-uniform presence of the above-mentioned betaine type compound, the diffusion inhibition (neutralization) of the acid generated from the acid generator X by the above-mentioned betaine type compound during the exposure step is The pattern did not progress uniformly, and it was revealed that the formed pattern had not necessarily sufficient fluctuation in pattern line width (LWR (line width roughness)) and in-plane uniformity (CDU (critical dimension uniformity)).

Then, this invention makes it a subject to provide the actinic-ray-sensitive or radiation-sensitive resin composition which can form the pattern excellent in the fluctuation | variation (LWR) of a pattern line width, and in-plane uniformity (CDU).
Another object of the present invention is to provide a resist film, a pattern forming method, and a method of manufacturing an electronic device using the actinic ray-sensitive or radiation-sensitive resin composition.
Another object of the present invention is to provide novel compounds.

As a result of intensive studies to achieve the above-mentioned problems, the present inventors have found that an actinic ray-sensitive or radiation-sensitive resin containing an acid generator and a compound represented by the general formula (1) as an acid diffusion control agent. According to the composition, it was found that the above problems could be solved, and the present invention was completed.
That is, it discovered that the said subject was solvable by the following structures.

[1] Resin,
An acid generator which generates an acid upon irradiation with actinic rays or radiation;
And an acid diffusion control agent,
An actinic ray-sensitive or radiation-sensitive resin composition, wherein the acid diffusion control agent contains at least a compound represented by the general formula (1).
[2] The actinic ray-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), all of R ₁ to R ₄ are hydrogen atoms, or at least one of Ar ₂ and Ar ₃ is an unsubstituted monocyclic aromatic hydrocarbon group, [2] The actinic ray sensitive or radiation sensitive resin composition as described in 4.
[4] In the general formula (2), all of R ₁ to R ₄ are hydrogen atoms, and one of Ar ₂ and Ar ₃ is an unsubstituted monocyclic aromatic hydrocarbon group,
Or both of Ar ₂ and Ar ₃ are unsubstituted monocyclic aromatic hydrocarbon groups, or
The actinic ray-sensitive or radiation-sensitive resin composition as described in [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 general formula (2), _{A 1} _is, -L 1 -CO ₂ _^-, or _-L 3 _-X 1 ^-N - is -Y _1, [1] to [4 The actinic ray-sensitive or radiation-sensitive resin composition according to any one of the above.
[6] The actinic ray-sensitive or radiation-sensitive resin composition as described in [5], wherein L ₁ and L ₃ are a single bond.
[7] A resist film formed using the actinic ray-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 actinic ray-sensitive or radiation-sensitive resin composition according to any one of [1] to [6];
An exposure step of exposing the resist film;
And b. Developing the exposed resist film with a developing solution.
[9] A method of manufacturing an electronic device, comprising the pattern formation 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), all of R ₁ to R ₄ are hydrogen atoms, or at least one of Ar ₂ and Ar ₃ is an unsubstituted monocyclic aromatic hydrocarbon group, [11] The compound as described in.
[13] In the general formula (2), all of R ₁ to R ₄ are hydrogen atoms, and one of Ar ₂ and Ar ₃ is an unsubstituted monocyclic aromatic hydrocarbon group,
Or both of Ar ₂ and Ar ₃ are unsubstituted monocyclic aromatic hydrocarbon groups, or
The compound according to [11], wherein all of R ₁ to R ₄ are hydrogen atoms, and Ar ₂ and Ar ₃ are both unsubstituted monocyclic aromatic hydrocarbon groups.
[14] General formula (1) or the general formula (2), _{A 1} _is, -L 1 -CO ₂ _^-, or _-L 3 _-X 1 ^-N - is -Y _1, [10] - [13 ] The compound in any one of-.
[15] The compound according to [14], wherein L ₁ and L ₃ are a single bond.

According to the present invention, it is possible to provide an actinic ray-sensitive or radiation-sensitive resin composition capable of forming a pattern excellent in pattern line width fluctuation (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 of manufacturing an electronic device using the actinic ray-sensitive or radiation-sensitive resin composition.
Furthermore, according to the present invention, novel compounds can be provided.

Hereinafter, the present invention will be described in detail.
Although the description of the configuration requirements described below may be made based on the representative embodiments of the present invention, the present invention is not limited to such embodiments.
In the present specification, the term "actinic ray" or "radiation" refers to, for example, the emission line spectrum of a mercury lamp, far ultraviolet light represented by an excimer laser, extreme ultraviolet (EUV light), X-rays, and electron beams (EB). Means Electron Beam) and the like. By "light" herein is meant actinic radiation or radiation.
Unless otherwise specified, the “exposure” in the present specification includes not only exposure by the bright line spectrum of a mercury lamp, far ultraviolet rays represented by an excimer laser, extreme ultraviolet rays, X rays, EUV light, etc., but also electron beams and Also includes drawing by particle beam such as ion beam.
In the present specification, “to” is used in the meaning including the numerical values described before and after it as the lower limit value and the upper limit value.

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

With respect to the notation of groups (atomic groups) in the present specification, the notation not describing substitution and non-substitution also 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).

Moreover, in the present specification, the type of substituent, the position of the substituent, and the number of substituents when “it may have a substituent” is not particularly limited. The number of substituents may, for example, be one, two, three or more. Examples of the substituent may include monovalent nonmetal atomic groups other than hydrogen atoms, and may be selected, for example, from the following substituent group T.
(Substituent T)
As the substituent T, halogen atoms such as fluorine atom, chlorine atom, bromine atom and iodine atom; alkoxy groups such as methoxy group, ethoxy group and tert-butoxy group; aryloxy groups such as phenoxy group and p-tolyloxy group; Alkoxycarbonyl groups such as methoxycarbonyl group, butoxycarbonyl group and phenoxycarbonyl group; acyloxy groups such as acetoxy group, propionyloxy group and benzoyloxy group; acetyl group, benzoyl group, isobutyryl group, acryloyl group, methacryloyl group and methoxalyl group Alkyl groups such as methylsulfanyl group and tert-butylsulfanyl group; arylsulfanyl groups such as phenylsulfanyl group and p-tolylsulfanyl group; alkyl group; cycloalkyl group Aryl group; heteroaryl group; hydroxyl group; carboxy group; formyl group; sulfo group; cyano group; alkylaminocarbonyl group; arylaminocarbonyl group; sulfonamido group; silyl group; amino group; monoalkylamino group; Arylamino groups; as well as combinations thereof.

Actinic Ray-Sensitive or Radiation-Sensitive Resin Composition
The actinic ray-sensitive or radiation-sensitive resin composition of the present invention (hereinafter also referred to as "the composition of the present invention") comprises a resin and an acid generator which generates an acid upon irradiation with an actinic ray or radiation. Also referred to as “acid generator X”) and an acid diffusion control agent, the acid diffusion control agent at least includes a compound represented by General Formula (1) described later.

The feature of the present invention is that the compound represented by the general formula (1) is contained as an acid diffusion control agent.
Hereinafter, after describing the mechanism of action of the compound represented by the general formula (1) as an acid diffusion control agent, structural features of the compound represented by the general formula (1) will be described.

<Action Mechanism of Compound Represented by General Formula (1) as Acid Diffusion Control Agent>
The compound represented by the general formula (1) receives an actinic ray or radiation to generate an acid. An acid generated from the compound represented by the general formula (1) is generally used to cause a deprotection reaction of a resin component (a deprotection reaction of an acid-degradable resin) or to cause a crosslinking reaction of a resin component. It becomes a weak acid relatively to the acid generator (acid generator X). For this reason, in the resist film system during and / or after exposure, apparent proton exchange between the acid generated by the acid generator X and the anion of the acid generated from the compound represented by the general formula (1) A reaction occurs. As a result, the acid generator X neutralizes the acid generated, and the diffusion of the acid generated from the acid generator X to the unexposed area is suppressed.

<Structural Features of Compound Represented by 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 a sulfonium cation Point of substitution at the ortho position with respect to the carbon atom to be
The inventors of the present invention have found that the betaine type compound described in Patent Document 1 is apt to be aggregated in the actinic ray-sensitive or radiation-sensitive resin composition (it is easy to form a multimer such as a dimer). It is presumed to be in the intramolecular polarization of the compound of type. More specifically, it is believed that the above-mentioned betaine type compound is separated from the positive charge and the negative charge in the molecule too much and is aggregated with other molecules for charge neutralization.
On the other hand, in the compound represented by the general formula (1), since the anionic group represented by A ₁ and the cation site of the sulfur atom represented by S ⁺ are structurally close to each other, the actinic ray sensitivity or It is hard to aggregate in the radiation sensitive resin composition. Therefore, the compound represented by the general formula (1) is uniformly dispersed and present in the resist film system. As a result, the 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) in the resist film system during and / or after the exposure is I speculate that it will progress uniformly.
With 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 any one or more of an acid represented by the following general formula (1X) and an acid represented by the following general formula (1Y) I guess. That is, depending on the structure thereof, an acid represented by the following general formula (1X) is generated alone, or an acid represented by the following general formula (1Y) is generated alone, or It is presumed that both the acid represented by 1X) and the acid represented by the following general formula (1Y) are generated.
Incidentally, in the following general formula (1X) and the following general formula _(1Y), Ar _1, Ar 2, Ar _3, and _{A 1,} _Ar 1 in the formula _(1), Ar 2, Ar _3, and _{A 1} It 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 points described above, it is presumed that the acid diffusion control agent also has a betaine structure, which also contributes to the improvement of LWR performance and CDU performance. As an acid diffusion controller having an acid diffusion control mechanism (action mechanism of acid generator X neutralization) similar to that of the compound represented by the general formula (1), for example, triphenylsulfonium salt etc. are known However, in comparison with the case where these acid diffusion control agents are used, the resist film is less likely to be plasticized when the acid diffusion control agent having a betaine structure is used. For this reason, it is considered that the resist film after exposure is difficult to be dissolved unevenly at the time of development, and as a result, it 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 resist composition or a negative resist composition. Further, it may be a resist composition for alkali 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 resin (A), resin (AX1), resin (AX2) etc. can be used, for example, Especially, resin (AX1) is preferable.

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

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

A well-known resin can be used suitably as resin (AX1). For example, paragraphs <0055> to <0191> of U.S. Patent Application Publication 2016 / 0274458A1, paragraphs <0035> to <0085> of U.S. Patent Application Publication 2015 / 0004544A1, and U.S. Patent Application Publication 2016 / 0147150A1. Known resins 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) which is decomposed and eliminated by the action of acid.
As a polar group, a carboxy group, a phenolic hydroxyl group, a fluorinated alcohol group, a sulfonic acid group, a sulfonamide group, a sulfonyl imide group, (alkylsulfonyl) (alkyl carbonyl) methylene group, (alkyl sulfonyl) (alkyl carbonyl) imide group , Bis (alkyl carbonyl) methylene group, bis (alkyl carbonyl) imide group, bis (alkyl sulfonyl) methylene group, bis (alkyl sulfonyl) imide group, tris (alkyl carbonyl) methylene group, and tris (alkyl sulfonyl) methylene group Acid groups (groups dissociable in 2.38 mass% tetramethylammonium hydroxide aqueous solution), and alcoholic hydroxyl groups.

The alcoholic hydroxyl group is a hydroxyl group bonded to a hydrocarbon group, and is a hydroxyl group other than a hydroxyl group (phenolic hydroxyl group) bonded directly to an aromatic ring, and an electron attractive group such as a fluorine atom at the α position as a hydroxyl group. Excludes aliphatic alcohols substituted with sex groups (eg, hexafluoroisopropanol group 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 carboxy group, phenolic hydroxyl group, fluorinated alcohol group (preferably hexafluoroisopropanol group), and sulfonic acid group.

A preferred group as the acid-degradable group is a group obtained by substituting a hydrogen atom of these groups with a group (leaving group) which is released by the action of an acid.
As the group (leaving group) capable of leaving by the action of an acid, _{_{_{e.g., -C (R 36) (R}}} 37) (R 38), - C (R 36) (R 37) (OR 39), and - C (R ₀₁ ) (R ₀₂ ) (OR ₃₉ ) and the like.
In the formula, each of R ₃₆ to R ₃₉ independently represents an alkyl group, a cycloalkyl group, an aryl group, an aralkyl group or an alkenyl group. R ₃₆ and R ₃₇ may combine with each other to form a ring.
Each of R ₀₁ and R ₀₂ independently represents a hydrogen atom, an alkyl group, a cycloalkyl group, an aryl group, an aralkyl group or an alkenyl group.

The alkyl group represented by R ₃₆ to R ₃₉ , R ₀₁ and R ₀₂ is preferably an alkyl group having a carbon number of 1 to 8, and examples thereof include a methyl group, an ethyl group, a propyl group, an n-butyl group and a sec- A butyl group, a hexyl group, an octyl group etc. are mentioned.
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 a carbon number of 3 to 8, 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 a carbon number of 6 to 20, and examples thereof include an adamantyl group, a norbornyl group, an isobornyl group, a camphanyl group, a dicyclopentyl group, an α-pinel group and a tricyclodecanyl group, Tetracyclododecyl group, and androstanyl group etc. are mentioned. In addition, at least one carbon atom in the cycloalkyl group may be substituted by a hetero atom such as an oxygen atom.
The aryl group represented by R ₃₆ to R ₃₉ , R ₀₁ and R ₀₂ is preferably an aryl group having a carbon number of 6 to 10, 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 a carbon number of 7 to 12, 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 a carbon number of 2 to 8, 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). The cycloalkyl group is preferably 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. .

As the acid-degradable group, a cumyl ester group, an enol ester group, an acetal ester group, or a tertiary alkyl ester group is 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 decomposable 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.
Each of Rx ₁ to Rx ₃ independently represents an alkyl group or a cycloalkyl group.
Any two of Rx ₁ to Rx ₃ may be combined to form a ring structure or may not be formed.

Examples of the divalent linking group represented by T include an alkylene group, an arylene group, -COO-Rt-, and -O-Rt-. In formula, Rt represents an alkylene group, a cycloalkylene group, or an arylene group.
T is preferably a single bond or -COO-Rt-. Rt is preferably a chain alkylene group having 1 to 5 carbon atoms, and more preferably -CH ₂ -,-(CH ₂ ) _2- or-(CH ₂ ) _3- .
As T, a single bond is more preferable.

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 a methyl group, an ethyl group, an n-propyl group, an isopropyl group, n- Preferred is a butyl group, an isobutyl group, or a t-butyl group. The carbon number of the alkyl group is preferably 1 to 10, more preferably 1 to 5, and still more preferably 1 to 3. In the alkyl group represented by Rx ₁ , Rx ₂ and Rx ₃ , a part of carbon-carbon bonds may be a double bond.
As a cycloalkyl group represented by Rx ₁ , Rx ₂ and Rx ₃ , monocyclic cycloalkyl group such as cyclopentyl group and cyclohexyl group or norbornyl group, tetracyclodecanyl group, tetracyclododecanyl group, and Polycyclic cycloalkyl groups such as an adamantyl group are preferred.

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

Although the specific example of the monomer corresponded to the repeating unit represented by general formula (AI) below is given, this invention is not restrict | limited to these specific examples. The following specific example corresponds to the case where Xa ₁ in General Formula (AI) is a methyl group, but Xa ₁ can be optionally substituted with a hydrogen atom, a halogen atom, or a monovalent organic group.

It is also preferable that the resin (AX1) have, as a repeating unit having an acid degradable group, the repeating units described in paragraphs <0336> to <0369> of US Patent Application Publication 2016/0070167 A1.

In addition, the resin (AX1) is decomposed by the action of the acid described in paragraphs <0363> to <0364> of US Patent Application Publication 2016 / 0070167A1 as a repeating unit having an acid-degradable group to be alcoholic. You may have a repeating unit containing the group which produces a hydroxyl group.

The resin (AX1) may contain a single type of repeating unit having an acid-degradable group, or may contain two or more types in combination.

The content of repeating units having an acid decomposable group contained in the resin (AX1) (the total of the repeating units having an acid degradable group, in the case where there are a plurality of repeating units having an acid degradable group) 10 to 90 mol% is preferable, 20 to 80 mol% is more preferable, and 30 to 70 mol% is more preferable.

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 lactone structure or a 5- to 7-membered sultone structure is preferable. Among them, those in which another ring structure is fused to a 5- to 7-membered ring lactone structure to form a bicyclo structure or spiro structure, or a 5- to 7-membered ring in a form to form a bicyclo structure or spiro structure More preferred are those in which other ring structures are fused to a sultone structure.
The resin (AX1) has a lactone structure represented by any one of the following formulas (LC1-1) to (LC1-21), or any one of the following formulas (SL1-1) to (SL1-3) It is further preferable to have a repeating unit having a sultone structure represented. Also, a lactone structure or a sultone structure may be directly bonded to the main chain. Preferred structures include general formula (LC1-1), general formula (LC1-4), general formula (LC1-5), general formula (LC1-8), general formula (LC1-16), or general formula (LC1) And lactone structures represented by the formula -21) or sultone structures represented by the general formula (SL1-1).

The lactone structure moiety or the sultone structure moiety may or may not have a substituent (Rb ₂ ). Preferred examples of the substituent (Rb ₂ ) include an alkyl group having 1 to 8 carbon atoms, a cycloalkyl group having 4 to 7 carbon atoms, an alkoxy group having 1 to 8 carbon atoms, an alkoxycarbonyl group having 2 to 8 carbon atoms, and a carboxy group And a halogen atom, a hydroxyl group, a cyano group, an acid decomposable group and the like, and an alkyl group having 1 to 4 carbon atoms, a cyano group or an acid decomposable group is preferable. n ₂ represents an integer of 0 to 4; When n ₂ is 2 or more, plural substituents (Rb ₂ ) may be the same or different. Moreover, two or more substituents (Rb ₂ ) may be combined to form a ring.

As a 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 repetition of the structure represented by -R ₀ -Z- and represents an integer of 0 to 5, preferably 0 or 1, and more preferably 0. When n is 0, -R ₀ -Z- is absent, resulting in a single bond.
R ₀ represents an alkylene group, a cycloalkylene group, or a combination thereof. If R ₀ is plural, R ₀ each independently represents a 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, each 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 R ₀ 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 structure.
The repeating unit having a cyclic carbonate structure is preferably a repeating unit represented by the following general formula (A-1).

In general formula (A-1), R _A 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.
R _A ² represents a substituent. When n is 2 or more, R _A ² independently represents a substituent.
A represents a single bond or a divalent linking group.
Z represents an atomic group which forms a monocyclic or polycyclic structure with a group represented by —O—C (OO) —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 described in paragraphs <0370> to <0414> of US Patent Application Publication No. 2016 / 0070167A1. It is also preferred to have the repeating unit described in

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

Specific examples of the monomer corresponding to the repeating unit represented by the general formula (III) and specific examples of the monomer corresponding to the repeating unit represented by the general formula (A-1) will be given below. 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 R _A ¹ in the general formula (A-1) are a methyl group, but R ₇ and R _A ¹ are a hydrogen atom, a halogen atom Or a monovalent organic group may optionally be substituted.

In addition to the above monomers, the following monomers are also suitably used as a raw material of the resin (AX1).

Content of repeating unit having at least one selected from the group consisting of lactone structure, sultone structure, and carbonate structure contained in resin (AX1) (selected from the group consisting of lactone structure, sultone structure, and carbonate structure 5 to 70 mol% is preferable with respect to all the repeating units in resin (AX1), and, when two or more repeating units which have at least 1 sort exist are two or more, 10 to 65 mol% is more preferable, and 20 to 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, and a fluorinated alcohol group.
The repeating unit having a polar group is preferably a repeating unit having an alicyclic hydrocarbon structure substituted with a polar group. Moreover, it is preferable that the repeating unit which has a polar group does not have an acid degradable group. As an alicyclic hydrocarbon structure in the alicyclic hydrocarbon structure substituted by the polar group, an adamantyl group or a norbornane group is preferable.

Although the specific example of the monomer corresponded to the repeating unit which has a polar group below is given, this invention is not restrict | limited to these specific examples.

Other specific examples of the repeating unit having a polar group include the repeating units disclosed in paragraphs <0415> to <0433> of US Patent Application Publication 2016/0070167 A1.
The resin (AX1) may have a repeating unit having a polar group singly or in combination of two or more.
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%, relative to all the repeating units in the resin (AX1).

The resin (AX1) may further have a repeating unit having neither an acid-degradable group nor a polar group. It is preferable that the repeating unit which does not have any of an acid-degradable group and a polar group 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 the monomer corresponding to the repeating unit having neither an acid-degradable group nor a polar group are shown below.

Other specific examples of the repeating unit having neither an acid degradable group nor a polar group include the repeating units disclosed in paragraph <0433> of US Patent Application Publication No. 2016/0070167 A1. .
The resin (AX1) may have a single type of repeating unit having neither an acid-degradable group nor a polar group, and may have two or more types in combination.
The content of the repeating unit having neither an acid decomposable 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.

The resin (AX1) has, besides the above-mentioned repeating structural units, dry etching resistance, standard developer suitability, substrate adhesion, resist profile, or resolution, heat resistance, which are generally necessary characteristics of the resist, and You may have various repeating structural units in order to adjust a sensitivity etc.
Examples of such repeating structural units include, but not limited to, repeating structural units corresponding to a predetermined monomer.

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

When the composition of the present invention is for ArF exposure, it is preferable that the resin (AX1) substantially does not have an aromatic group from the viewpoint of ArF light transmittance. More specifically, the repeating unit having an aromatic group is preferably 5 mol% or less, more preferably 3 mol% or less, based on all the repeating units in the resin (AX1), and ideally It is more preferable that the monomer have 0 mol%, that is, it does not have a repeating unit having an aromatic group. In addition, the resin (AX1) preferably has a monocyclic or polycyclic alicyclic hydrocarbon structure.

In the resin (AX1), it is preferable that all of the repeating units be composed of (meth) acrylate repeating units. In this case, all repeating units may be methacrylate repeating units, all repeating units may be acrylate repeating units, and all repeating units may be methacrylate repeating units and acrylate repeating units. Although it can be used, it is preferable that an acrylate-type repeating unit is 50 mol% or less with respect to all the repeating units of 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. More preferably, the resin (AX1) has a repeating unit containing a phenolic hydroxyl group. As a repeating unit containing a phenolic hydroxyl group, a hydroxystyrene repeating unit or a hydroxystyrene (meth) acrylate repeating unit is mentioned.
When the composition of the present invention is for KrF exposure, EB exposure or EUV exposure, the resin (AX1) is a group from which hydrogen atoms of phenolic hydroxyl groups are decomposed and released by the action of 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). Preferably, 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 still more preferably 3,000 to 20,000. The dispersion degree (Mw / Mn) is usually 1.0 to 3.0, preferably 1.0 to 2.6, more preferably 1.0 to 2.0, and still more preferably 1.1 to 2.0. preferable.

As the resin (AX1), one type may be used alone, or two or more types may be used in combination.
In the composition of the present invention, the content of the resin (AX1) is generally 20.0% by mass or more in many cases, preferably 40.0% by mass or more, based on the total solid content. % By mass or more is more preferable, and 80.0% by mass or more is even more preferable. Although an upper limit in particular is not restrict | limited, 99.5 mass% or less is preferable, 99.0 mass% or less is more preferable, 97.0 mass% or less is still more preferable.

(Resin (AX2))
The resin (AX2) is an alkali-soluble resin having a phenolic hydroxyl group.
In addition, when the composition of this invention contains resin (AX2), the composition of this invention contains the crosslinking agent (G) mentioned later with resin (AX2). The crosslinking agent (G) may be in the form of being supported by the resin (AX2).
When the composition of the present invention contains a resin (AX2), the formed pattern is usually a negative pattern.
Among them, as the resin (AX2), it is preferable to have a repeating unit having a phenolic hydroxyl group. In addition, the resin (AX2) may have the acid-degradable group described above.

As a repeating unit which has a phenolic hydroxyl group which resin (AX2) has, 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.

As a bivalent coupling group represented by B ', it is synonymous with T in General formula (AI), and its preferable aspect is also the same.
As an aromatic ring group represented by Ar ', a benzene ring is preferable.
Although m is not particularly limited as long as it is an integer of 1 or more, for example, 1 to 4 is preferable, 1 to 3 is more preferable, and 1 or 2 is more preferable.

Resin (AX2) may be used individually by 1 type, and may use 2 or more types together.
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 in many cases, preferably 40% by mass or more, and more preferably 50% by mass or more. Although the upper limit in particular is not restrict | limited, 99 mass% or less is preferable, 90 mass% or less is more preferable, and 85 mass% or less is still more preferable.
Preferred examples of the resin (AX2) include the resins disclosed in paragraphs <0142> to <0347> of US Patent Application Publication 2016/0282720 A1.

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

<Acid Generator (B)>
The composition of the present invention contains a compound capable of generating an acid upon irradiation with an actinic ray or radiation (hereinafter, also referred to as "acid generator (B)").
The acid generator (B) mentioned here is an acid generator generally used to cause a deprotecting reaction of a resin component (a deprotecting reaction of an acid-degradable resin) or to cause a crosslinking reaction of a resin component. (The acid generator X mentioned above corresponds, and the compound represented by above-mentioned General formula (1) is not contained in an acid generator (B).
As the acid generator (B), a compound capable of generating an organic acid upon irradiation with an actinic ray or radiation is preferable. Examples include sulfonium salt compounds, iodonium salt compounds, diazonium salt compounds, phosphonium salt compounds, imidosulfonate compounds, oxime sulfonate compounds, diazodisulfone compounds, disulfone compounds, and o-nitrobenzyl sulfonate compounds.

As the acid generator (B), known compounds capable of generating an acid upon irradiation with an actinic ray 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 2016/0070167 A1; paragraphs <0086> to <0094> of U.S. Patent Application Publication 2015/0004544 A1, and U.S. Patent Application Publication 2016 / The known compounds disclosed in paragraphs <0323> to <0402> of the specification of 237190 A1 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),
Each of R ₂₀₁ , R ₂₀₂ and R ₂₀₃ independently represents an organic group.
The carbon number of the organic group as R ₂₀₁ , R ₂₀₂ and R ₂₀₃ is generally 1 to 30, preferably 1 to 20.
In addition, two of R ₂₀₁ to R ₂₀₃ may be combined to form a ring structure, and the ring may contain an oxygen atom, a sulfur atom, an ester bond, an amide bond, or a carbonyl group. As a group formed by two _{members out} of R ₂₀₁ to R ₂₀₃ , an alkylene group (for example, a butylene group, a pentylene group and the like), and —CH ₂ —CH ₂ —O—CH ₂ —CH ₂ — are It can be mentioned.
Z ^- represents an anion.

Preferred embodiments of the cation in the general formula (ZI) include the corresponding groups in the compound (ZI-1), the compound (ZI-2), the compound (ZI-3) and the compound (ZI-4) described later. Be
The acid generator (B) may be a compound having a plurality of structures represented by general formula (ZI). For example, at least one of _R 201 _{~ R 203} of the compound represented by formula (ZI), at least one of _R 201 _{~ R 203} of another compound represented by formula (ZI) is a single bond 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 arylsulfonium compound in which at least one of R ₂₀₁ to R _{203 in} the general formula (ZI) is an aryl group, that is, a compound having an arylsulfonium as a cation.
In the arylsulfonium compound, all of R ₂₀₁ to R ₂₀₃ may be aryl groups, or a part of R ₂₀₁ to R ₂₀₃ may be an aryl group, and the remainder may be an alkyl group or a cycloalkyl group.
Examples of arylsulfonium compounds include triarylsulfonium compounds, diarylalkylsulfonium compounds, aryldialkylsulfonium compounds, diarylcycloalkylsulfonium compounds, and aryldicycloalkylsulfonium compounds.

The aryl group contained in the arylsulfonium compound is preferably a phenyl group or a naphthyl group, more preferably a phenyl group. The aryl group may be an aryl group having a heterocyclic structure having an oxygen atom, a nitrogen atom, or a sulfur atom or the like. As the heterocyclic structure, pyrrole residue, furan residue, thiophene residue, indole residue, benzofuran residue, benzothiophene residue and the like can be mentioned. When the arylsulfonium compound has two or more aryl groups, the two or more aryl groups may be the same or different.
The alkyl or cycloalkyl group which the arylsulfonium compound optionally has is a linear alkyl group having 1 to 15 carbon atoms, a branched alkyl group having 3 to 15 carbon atoms, or 3 to 15 carbon atoms. Preferred examples of the cycloalkyl group include methyl group, ethyl group, propyl group, n-butyl group, sec-butyl group, t-butyl group, cyclopropyl group, cyclobutyl group and cyclohexyl group.

The aryl group, alkyl group and cycloalkyl group represented by R ₂₀₁ to R ₂₀₃ are each independently an alkyl group (for example, 1 to 15 carbon atoms), a cycloalkyl group (for example, 3 to 15 carbon atoms), 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 each of R ₂₀₁ to R ₂₀₃ in formula (ZI) independently represents an organic group having no aromatic ring. Here, the aromatic ring also includes an aromatic ring containing a hetero atom.
The organic group having no aromatic ring as R ₂₀₁ to R ₂₀₃ generally has 1 to 30 carbon atoms, and preferably 1 to 20 carbon atoms.
Each of _R201 to _R203 independently is preferably an alkyl group, a cycloalkyl group, an allyl group or a vinyl group, and a linear or branched 2-oxoalkyl group, a 2-oxocycloalkyl group or an alkoxy group. A carbonylmethyl group is more preferable, and a linear or branched 2-oxoalkyl group is more preferable.

As the alkyl group and cycloalkyl group of _R201 to _R203, a linear alkyl group having 1 to 10 carbon atoms or a branched alkyl group having 3 to 10 carbon atoms (eg, methyl group, ethyl group, propyl group, A butyl group and a pentyl group) or a cycloalkyl group having a carbon number of 3 to 10 (eg, a cyclopentyl group, a cyclohexyl group, and a norbornyl group) is preferable.
R ₂₀₁ to R ₂₀₃ may be further substituted by 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 a compound represented by the following general formula (ZI-3) and having a phenacylsulfonium salt structure.

In the general formula (ZI-3),
Each of R _1c to R _5c independently represents a hydrogen atom, an alkyl group, a cycloalkyl group, an aryl group, an alkoxy group, an aryloxy group, an alkoxycarbonyl group, an alkylcarbonyloxy group, a cycloalkylcarbonyloxy group, a halogen atom or a hydroxyl group. , A nitro group, an alkylthio group or an 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.
Each of R _x and R _y independently represents an alkyl group, a cycloalkyl group, a 2-oxoalkyl group, a 2-oxocycloalkyl group, an alkoxycarbonylalkyl group, an allyl group or a vinyl group.

Any two or more of R _1c to R _5c , R _5c and R _6c , R _6c and R _7c , R _5c and R _x , and R _x and R _y respectively combine to form a ring structure Each of the ring structures 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 an aromatic or non-aromatic hydrocarbon ring, an aromatic or non-aromatic heterocycle, and a polycyclic fused ring in which two or more of these rings are combined. The ring structure includes 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 bonding 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.
The group formed by combining R _5c and R _6c and R _5c and R _x is preferably a single bond or an alkylene group. As an alkylene group, a methylene group, ethylene group, etc. are mentioned.
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 of 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 a substituent.
R ₁₄ represents a group having 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 cycloalkyl group. These groups may have a substituent. When there are a plurality of R _{14 's} , they each independently represent the above-mentioned group such as a hydroxyl group.
Each R ₁₅ independently represents an alkyl group, a cycloalkyl group or a naphthyl group. These groups may have a substituent. Two R _{15 s} may be bonded to each other to form a ring. When two R ₁₅ bonds to each other to form a ring, the ring skeleton may contain a heteroatom such as an oxygen atom or a nitrogen atom. In one aspect, it is preferable that two R ₁₅ be an alkylene group and bond to each other to form a ring structure.
Z ^- represents an anion.

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

Next, general formulas (ZII) and (ZIII) will be described.
In formulas (ZII) and (ZIII), each of R ₂₀₄ to R ₂₀₇ independently represents an aryl group, an alkyl group or a cycloalkyl group.
The aryl group represented by R ₂₀₄ to R ₂₀₇ is preferably a phenyl group or a naphthyl group, more preferably a phenyl group. 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 or the like. Examples of the skeleton of the aryl group having a heterocyclic structure include pyrrole, furan, thiophene, indole, benzofuran, and benzothiophene.
As the alkyl group and cycloalkyl group represented by R ₂₀₄ to R ₂₀₇ , a linear alkyl group having 1 to 10 carbon atoms, a branched alkyl group having 3 to 10 carbon atoms (eg, methyl group, ethyl group, A propyl group, a butyl group, a pentyl group and the like) or a cycloalkyl group having a carbon number of 3 to 10 (eg, a cyclopentyl group, a cyclohexyl group, a norbornyl group and the like) 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 may be possessed by the aryl group, alkyl group and cycloalkyl group represented by R ₂₀₄ to R ₂₀₇ include, for example, an alkyl group (for example, having 1 to 15 carbon atoms) and a cycloalkyl group (for example, carbon And an aryl group (for example, 6 to 15 carbon atoms), an alkoxy group (for example, 1 to 15 carbon atoms), a halogen atom, a hydroxyl group, and a phenylthio group.
Z ^- represents an anion.

Z in the general formula (ZI) ^-, Z in the general formula (ZII) ^-, Zc in formula (ZI-3) ^-, and Z in the general formula (ZI-4) ^- as the following general formula (3) The anions represented are preferred.

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

Xf represents a fluorine atom or an alkyl group substituted with at least one fluorine atom. The carbon number of this alkyl group is preferably 1 to 10, and more preferably 1 to 4. Moreover, as an alkyl group substituted by 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 be a fluorine atom.

Each of R ₄ and R ₅ independently represents a hydrogen atom, a fluorine atom, an alkyl group, or an alkyl group substituted with at least one fluorine atom. When a plurality of R ₄ and R ₅ are present, R ₄ and R ₅ may be the same or different.
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 specific examples and preferred embodiments of Xf in the general formula (3).

L represents a divalent linking group. When a plurality of L are present, L may be the same or different.
Examples of the divalent linking group include, for example, -COO-(-C (= O) -O-), -OCO-, -CONH-, -NHCO-, -CO-, -O-, -S-,- SO—, —SO ₂ —, an alkylene group (preferably having a carbon number of 1 to 6), a cycloalkylene group (preferably having a carbon number of 3 to 15), an alkenylene group (preferably having a carbon number of 2 to 6) Examples thereof include combined divalent linking groups and the like. Among them, -COO -, - OCO -, - CONH -, - NHCO -, - CO -, - O -, - SO 2 -, - COO- alkylene group -, - OCO- alkylene group -, - CONH- alkylene group -, or -NHCO- alkylene group - are preferred, -COO -, - OCO -, - CONH -, - SO 2 -, - COO- alkylene group -, or -OCO- alkylene group - is more preferable.

W represents an organic group containing a cyclic structure. Among these, a cyclic organic group is preferable.
As a cyclic organic group, an alicyclic group, an aryl group, and a heterocyclic group are mentioned, for example.
The alicyclic group may be monocyclic or polycyclic. As a monocyclic alicyclic group, monocyclic cycloalkyl groups, such as a cyclopentyl group, a cyclohexyl group, and a cyclooctyl group, are mentioned, for example. Examples of polycyclic alicyclic groups include polycyclic cycloalkyl groups such as norbornyl group, tricyclodecanyl group, tetracyclodecanyl group, tetracyclododecanyl group, and adamantyl group. Among them, an alicyclic group 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 is preferable.

The aryl group may be monocyclic or polycyclic. Examples of the aryl group include phenyl group, naphthyl group, phenanthryl group, and anthryl group.
The heterocyclic group may be monocyclic or polycyclic. The polycyclic type can suppress the diffusion of the acid more. The heterocyclic group may have aromaticity 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. The hetero ring having no aromaticity includes, for example, tetrahydropyran ring, lactone ring, sultone ring, and decahydroisoquinoline ring. Examples of lactone ring and sultone ring include lactone structure and sultone structure exemplified in the above-mentioned resin. As a heterocycle in the heterocycle 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. As this substituent, for example, an alkyl group (which may be linear or branched and having 1 to 12 carbon atoms is preferable), a cycloalkyl group (monocyclic, polycyclic, and spirocyclic) Any of them, preferably having 3 to 20 carbon atoms, aryl (preferably having 6 to 14 carbons), hydroxyl, alkoxy, ester, amide, urethane, ureido, thioether, sulfonamide And sulfonate ester groups. The carbon constituting the cyclic organic group (carbon contributing to ring formation) may be carbonyl carbon.

As the anion represented by the general formula (3), SO ₃ ^-- CF ₂ -CH ₂ -OCO- (L) q'-W, SO ₃ ^-- CF ₂ -CHF-CH ₂ -OCO- (L) _{^{_{q'-W, SO 3 - -CF}}} 2 -COO- (L) q'-W, SO 3 - -CF 2 -CF 2 -CH 2 -CH 2 - (L) q-W, or, SO ₃ ^- -CF ₂ -CH (CF ₃ ) -OCO- (L) q'-W is preferred. Here, L, q and W are the same as in the general formula (3). q 'represents an integer of 0 to 10;

In one embodiment, Z in formula (ZI) ^-, Z in the general formula (ZII) ^-, Zc in formula (ZI-3) ^-, and Z in the general formula (ZI-4) ^- as is generally the following The anion represented by Formula (4) is also preferable.

In general formula (4),
Each of X ^B1 and X ^B2 independently represents a hydrogen atom or a monovalent organic group having no fluorine atom. X ^B1 and X ^B2 are preferably hydrogen atoms.
Each of X ^B3 and X ^B4 independently represents a hydrogen atom or a monovalent organic group. At least one of X ^B3 and X ^B4 is preferably a fluorine atom or a monovalent organic group having a fluorine atom, and both of X ^B3 and X ^B4 are a fluorine atom or a monovalent organic group having a fluorine atom Is more preferred. More preferably, both X ^B3 and X ^B4 are a fluorine-substituted alkyl group.
L, q 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 formula (ZI-3) ^-, and Z in the general formula (ZI-4) ^- as the following general formula (5) The anions represented are also preferred.

In General Formula (5), each Xa independently represents a fluorine atom or an alkyl group substituted with at least one fluorine atom. Each Xb independently represents a hydrogen atom or an organic group having no 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 formula (ZI-3) ^-, and Z in the general formula (ZI-4) ^- may be a benzenesulfonic acid anion Preferably, it is a benzenesulfonic acid anion substituted by a branched alkyl group or a cycloalkyl group.

Z in the general formula (ZI) ^-, the formula Z in (ZII) ^-, Zc in formula (ZI-3) ^- Z in, and the general formula (ZI-4) ^- The following general formula (SA1) The aromatic sulfonate anion represented by is also preferable.

In the formula (SA1),
Ar represents an aryl group, and may further have a substituent other than a sulfonate anion and a-(D-B) group. Examples of the substituent which may further have include a fluorine atom and a hydroxyl group.

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

B represents a hydrocarbon group.

Preferably, D is a single bond, and B is an aliphatic hydrocarbon structure. B is more preferably isopropyl or cyclohexyl.

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

Generally the anion Z in formula (ZI) ^-, the anion in the general formula (ZII) Z ^-, Zc in formula (ZI-3) ^-, and the general formula Z in (ZI-4) ^- shows the preferred embodiment below.

The above-mentioned cations and anions can be optionally combined and used as an acid generator (B).

The acid generator (B) may be in the form of a low molecular weight compound, or may be in the form of being incorporated into a part of a polymer. Also, the form of the low molecular weight compound and the form incorporated into a part of the polymer may be used in combination.
The acid generator (B) is preferably in the form of a low molecular weight compound.
When the acid generator (B) is in the form of a low molecular weight compound, the molecular weight is preferably 3,000 or less, more preferably 2,000 or less, and still more preferably 1,000 or less.
When the acid generator (B) is in the form of being incorporated into a part of a polymer, it may be incorporated into a part of the resin (A) described above, and is incorporated into a resin different from the resin (A) It is also good.
The acid generator (B) may be used alone or in combination of two or more.
In the composition, the content of the acid generator (B) (the total of two or more kinds thereof) is preferably 0.1 to 20.0% by mass based on the total solid content of the composition, 0.5 -15.0% by mass is more preferable, and 1.0-15.0% by mass is more preferable.
When the compound represented by the above general formula (ZI-3) or (ZI-4) is contained as the acid generator, the content of the acid generator contained in the composition (if there is more than one, the total amount thereof) Is preferably 5 to 35% by mass, and 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) upon irradiation with actinic rays or radiation is more than the pKa of the acid generated from the compound represented by the general formula (1) described later. It is preferable to be small.
The acid dissociation constant pKa of the acid generated by decomposition of the acid generator (B) upon irradiation with actinic rays or radiation is preferably -1.00 or less, more preferably -1.50 or less. And -2.00 or less. The lower limit value of pKa is not particularly limited, and is, for example, -5.00 or more. 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 refers to the acid dissociation constant pKa in an aqueous solution, and, for example, to Chemical Handbook (II) (revised 4th edition, 1993, edited by The Chemical Society of Japan, Maruzen Co., Ltd.) As described, the lower the value, the higher the acid strength. Specifically, the acid dissociation constant pKa in an aqueous solution can be measured by measuring the acid dissociation constant at 25 ° C. using an infinite dilution aqueous solution, and Hammett using the following software package 1 Values based on substituent constants of and the database of known literature values can also be determined by calculation. All the pKa values described in the present specification indicate 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 traps an acid generated from the acid generator (B) or the like at the time of exposure, and acts as a quencher to suppress the reaction of the acid decomposable resin in the unexposed area by the extra generated acid.
The composition of the present invention only needs to contain at least the compound represented by the general formula (1) as an acid diffusion control agent, and includes other acid diffusion inhibitors within the range not to impair the effects of the present invention. It is also good.
In addition, in the following, the compound represented by General formula (1) is demonstrated as an acid diffusion control agent (C), and the other acid diffusion prevention agent is demonstrated as an acid diffusion control agent (D).

(Acid diffusion control agent (C))
Hereinafter, the compound represented by General formula (1) is demonstrated.
(Compound represented by the general formula (1))

In the above formulae, Ar ₁ , Ar ₂ and Ar ₃ each independently represent an aromatic hydrocarbon group.
A ₁ is substituted ortho to the carbon atom bonded to the ^{S +} on Ar _1, _{_{^{_{and, -L 1 -CO 2 -, -L}}}} 2 -SO 3 -, or _-L 3 -X ₁ - N ^-- Y ₁ represents.
Each of L ₁ , L ₂ and L ₃ independently represents a single bond or a divalent linking group.
X ₁ represents -SO _2- or -CO-.
Y ₁ represents an _-SO 2 -R _A, or _{-CO-R B.}
Each of R _A and R _B independently represents a monovalent substituent.
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 any of a monocyclic structure (monocyclic aromatic hydrocarbon group) and a polycyclic structure (polycyclic aromatic hydrocarbon group), It is also good. The carbon number of the aromatic hydrocarbon group is not particularly limited, but is preferably 5 to 18, and more preferably 5 to 10. Specific examples of the above-mentioned aromatic hydrocarbon group include aryl group (phenyl group, tolyl group, xylyl group etc.), naphthyl group, anthryl group, phenanthryl group, indenyl group, acenabutenyl group, fluorenyl group, pyrenyl group etc. It can be mentioned.
Among the aromatic hydrocarbon groups represented by Ar ₁ , Ar ₂ and Ar ₃ , monocyclic aromatic hydrocarbon groups are preferable among them in that LWR performance and 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 kind in particular of the said substituent is not restrict | limited, The group illustrated by the substituent group T mentioned above is mentioned. As a substituent, a non-aromatic substituent (note that, in the present specification, “non-aromatic substituent” means a substituent that does not exhibit aromaticity, and for example, it has an aromatic ring) Substituent groups are preferable, and may be an alkyl group (linear, branched or cyclic), preferably having 1 to 20 carbon atoms, more preferably 1 to 10 carbon atoms, and 1 to 10 carbon atoms. 6, 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. Also, at least one fluorine atom is preferable. The substituted alkyl group is preferably a perfluoroalkyl group, a halogen atom (for example, a fluorine atom, a chlorine atom, a bromine atom, an iodine atom, etc. may be mentioned as the halogen atom), a thioa A Kyl group (which may be linear, branched or cyclic, preferably has 1 to 20 carbon atoms, more preferably 1 to 10, still more preferably 1 to 6), or an alkoxy group (It may be linear, branched or cyclic. The number of carbon atoms is preferably 1 to 20, more preferably 1 to 10, and still more preferably 1 to 6).

The substituents substituted by Ar < ₁ >, Ar < ₂ > and Ar < ₃ > may mutually combine and the ring may be formed. The ring may be either aromatic or non-aromatic, but is preferably non-aromatic from the viewpoint that the LWR performance and CDU performance of the formed pattern are more excellent. The above-mentioned ring may further have a substituent (for example, one exemplified in the substituent group T).

Among the compounds represented by the general formula (1), at least one of Ar ₁ , Ar ₂ and Ar ₃ is unsubstituted, in that LWR performance and CDU performance of the formed pattern are more excellent. Preferably a monocyclic aromatic hydrocarbon group of the following (note that Ar ₁ is intended to have no substituent other than A ₁ ), any one of Ar ₁ , Ar ₂ and Ar ₃ More preferably, 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 ortho to the carbon atom bonded to the ^{S +} on Ar _1, _{_{^{_{and, -L 1 -CO 2 -, -L}}}} 2 -SO 3 -, or _-L 3 -X ₁ - N ^-- Y ₁ represents.
Here, "substituted ortho to the carbon atom bonded to the S ⁺ on Ar _1" in Ar _1, to the carbon atom of the coupling position with the explicit the sulfonium cation in formula (1) a ₁ in the ortho position Te is intended to replace. In other words, A ₁ substitutes the carbon atom adjacent to the carbon atom at the bonding position with the sulfonium cation specified in 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 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 but, for example, -O-, -CO-, a divalent hydrocarbon group (eg, an alkylene group, an alkenylene group, an alkynylene) Group, and an arylene group), and the group which combined these 2 or more are mentioned. Among the divalent linking groups represented by L ₁ , L ₂ and L ₃ , —O—, —CO—, an alkylene group having 1 to 10 carbon atoms, among others, in terms of superior 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 combination of two or more of them are preferable, and -O-, -CO-, an alkylene group having 1 to 6 carbon atoms, or 2 The group combined as above is more preferable, the alkylene group having 1 to 6 carbon atoms is further preferable, and the alkylene group having 1 to 3 carbon atoms is particularly preferable.
The atom at the bonding position to Ar ₁ in L ₁ , L ₂ and L ₃ is preferably other than an oxygen atom. For example, even if the divalent linking group represented by L ₁ , L ₂ and L ₃ contains —O— (oxygen atom), an atom other than oxygen atom (eg, carbon atom) as described above Preferably bind to Ar ₁ .

The A _1, in that the LWR performance and CDU performance of the pattern to be formed more _excellent, -L 1 -CO ₂ _^-, or _-L 3 _-X ₁ ^-N - -Y 1 are preferred.

X ₁ represents -SO _2- or -CO-.
Y ₁ represents an _-SO 2 -R _A, or _{-CO-R B.}

Each of R _A and R _B independently represents a monovalent substituent.
The monovalent substituent represented by R _A and R _B is not particularly limited, but includes the groups exemplified in the above-mentioned Substituent Group T. Among the monovalent substituents represented by R _A and R _B , an alkyl group (a linear, branched or cyclic group may be used, among which the carbon number is preferably 1 to 20, 1 to 10 is more preferable, 1 to 6 is further preferable, and 1 to 3 is particularly preferable), and an alkenyl group (linear, branched or cyclic) may be used. Is preferable, 2 to 10 is more preferable, and 2 to 6 is further preferable), or an alkynyl group (which may be linear, branched or cyclic), preferably having 2 to 20 carbon atoms. 2 to 10 is more preferable, 2 to 6 is further 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, the alkenyl group and the alkynyl group may further have a substituent (for example, those exemplified for the substituent group T).

The pKa of the acid generated from the compound represented by the general formula (1) is, for example, preferably -2.00 or more and is 1.00 or more, in that the function as the acid diffusion control agent is more excellent. Is more preferably 1.50 or more. The upper limit of pKa is not particularly limited, and 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 A ₁ .

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 from the acid generator (B) is preferably 1.00 or more, 2 .00 or more is more preferable. The upper limit value 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 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 from the acid generator (B) is within the above numerical range, the compound represented by the general formula (1) is The function as an acid diffusion control agent is more excellent.

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 formula (2))

In the above _formula, Ar 2, Ar _3, and _{A 1} is represented by the general formula (1) of _Ar 2, Ar _3, and have the same meanings as _{A 1,} preferred embodiments are also the same.

Each of R ₁ , R ₂ , R ₃ and R ₄ independently represents a hydrogen atom or a nonaromatic substituent.
The substituent represented by R ₁ , R ₂ , R ₃ , and R ₄ is not particularly limited as long as it is a non-aromatic substituent, and an alkyl group (linear, branched, or cyclic The carbon number is preferably 1 to 20, more preferably 1 to 10, and still more preferably 1 to 6, and a fluoroalkyl group (an alkyl group substituted with at least one fluorine atom). The carbon number is preferably 1 to 10, and more preferably 1 to 4. Further, as an alkyl group substituted with at least one fluorine atom, a perfluoroalkyl group is preferable, a halogen atom (as a halogen atom) For example, a fluorine atom, a chlorine atom, a bromine atom, an iodine atom and the like can be mentioned), a thioalkyl group (a linear, branched or cyclic one may be used. The carbon number is 1 to 20) Good 1 to 10 is more preferable, and 1 to 6 is further preferable), or an alkoxy group (linear, branched or cyclic), preferably having 1 to 20 carbon atoms. 1 to 10 is more preferable, and 1 to 6 is further preferable).
R ₁ , R ₂ , R ₃ and R ₄ may be linked to each other to form a ring. The ring is preferably nonaromatic. The above-mentioned ring may further have a substituent (for example, one exemplified in the substituent group T). Among them, R ₁ , R ₂ , R ₃ and R ₄ preferably 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 from the viewpoint that the LWR performance and CDU performance of the formed pattern are more excellent. The above-mentioned ring may further have a substituent (for example, one exemplified in the substituent group T).

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

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

Hereinafter, although the specific example of a compound represented by the said General formula (1) is illustrated, this invention is not limited to this.

The compounds represented by the above 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) (in the case of a plurality of such compounds, the total thereof) is preferably 0.1 to 10% by mass based on the total solid content of the composition 0.5 to 8.0% by mass is more preferable.
In addition, 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 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.

(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 effects of the present invention are not impaired. (Hereafter, "acid diffusion control agent (D)") may be included.
As the acid diffusion control agent (D), for example, a basic compound (DA), a basic compound (DB) whose basicity decreases or disappears upon irradiation with an actinic ray or radiation, a relatively weak acid to an acid generator Diffusion control of onium salt (DC), low molecular weight compound (DD) having nitrogen atom and having a group capable of leaving by the action of acid, or onium salt compound (DE) having nitrogen atom in the cation part It can be used as an agent. In the composition of the present invention, known acid diffusion control agents can be suitably used. For example, paragraphs <0627> to <0664> of U.S. Patent Application Publication 2016/0070167 A1; paragraphs <0095> to <0187> of U.S. Patent Application Publication 2015/0004544 A1, U.S. Patent Application Publication 2016/0237190 A1 The known compounds disclosed in paragraphs <0403> to <0423> of the specification and paragraphs <0259> to <0328> of US Patent Application Publication 2016/0274458 A1 are suitable as the acid diffusion control agent (D) It can be used for

The basic compound (DA) is preferably a compound having a structure represented by the following formulas (A) to (E).

In the general formulas (A) and (E),
R ²⁰⁰ , R ²⁰¹ and R ^{202, which} may be the same or different, each independently represent a hydrogen atom, an alkyl group (preferably having a carbon number of 1 to 20), a cycloalkyl group (preferably having a carbon number of 3 to 20) or an aryl Represents a group (having 6 to 20 carbon atoms). R ²⁰¹ and R ²⁰² may bond to each other to form a ring.
R ²⁰³ , R ²⁰⁴ , R ²⁰⁵ and R ^{206, which} may be the same or different, each independently represent 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 not be substituted.
As the alkyl group having a substituent, 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.
The alkyl group in the general formulas (A) and (E) is more preferably unsubstituted.

The basic compound (DA) is preferably guanidine, aminopyrrolidine, pyrazole, pyrazoline, piperazine, aminomorpholine, aminoalkylmorpholine, piperidine or the like, and has an imidazole structure, a diazabicyclo structure, an onium hydroxide structure, an onium carboxylate structure, Compounds having a trialkylamine structure, an aniline structure or a pyridine structure, alkylamine derivatives having a hydroxyl group and / or an ether bond, or aniline derivatives having a hydroxyl group and / or an ether bond are more preferable.

A basic compound (DB) (hereinafter also referred to as "compound (DB)") whose basicity is reduced or eliminated by irradiation with actinic rays or radiation has a proton acceptor functional group, and an actinic ray or radiation. It is a compound which is decomposed by irradiation with radiation to decrease, disappear, or change from proton acceptor property to acidity.

The proton acceptor 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 cyclic polyether or π conjugated Means a functional group having a nitrogen atom having a non-covalent electron pair that does not contribute to The nitrogen atom having a noncovalent electron pair not contributing to the π conjugation is, for example, a nitrogen atom having a partial structure shown in the following formula.

Examples of preferable partial structures of the proton acceptor functional group include a crown ether structure, an azacrown ether structure, a primary to tertiary amine structure, a pyridine structure, an imidazole structure, and a pyrazine structure.

The compound (DB) decomposes upon irradiation with an actinic ray or radiation to reduce or eliminate the proton acceptor property, or generates a compound which has been changed from the proton acceptor property to the acidity. Here, the reduction 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 caused by the addition of a proton to the proton acceptor functional group, and is specifically described 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 performing pH measurement.

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

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

In the composition of the present invention, an onium salt (DC) which becomes a relatively weak acid to the acid generator can be used as an acid diffusion control agent.
When a mixture of an acid generator and an onium salt that generates an acid that is relatively weak to the acid generated from the acid generator is used, the acid generator is generated from the acid generator by irradiation with actinic ray or radiation. When the acid collides with the onium salt with unreacted weak acid anion, the salt exchange releases the weak acid to form an onium salt with strong acid anion. In this process, since the strong acid is exchanged to a weak acid having a lower catalytic ability, the acid is apparently inactivated to control the acid diffusion.

Compounds represented by the following formulas (d1-1) to (d1-3) are preferable as the onium salt which is relatively weak to the acid generator.

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 (but carbon adjacent to S) Fluorine atom is not substituted), R ⁵² is an organic group, Y ³ is a linear, branched or cyclic alkylene group or arylene group, and R f is a fluorine atom And each of 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 in the general formula (ZI) and the iodonium cation exemplified in the general formula (ZII).

The low molecular weight compound (DD) having a nitrogen atom and having a group capable of leaving by the action of an acid (hereinafter also referred to as “compound (DD)”) has a group leaving by the action of an acid on the nitrogen atom It is preferable that it is an amine derivative which it has.
As a group leaving by the action of an acid, an acetal group, a carbonate group, a carbamate group, a tertiary ester group, a tertiary hydroxyl group, or a hemiaminal ether group is preferable, and a carbamate group or a hemiaminal ether group is more preferable. .
The molecular weight of the compound (DD) is preferably 100 to 1000, more preferably 100 to 700, and still more preferably 100 to 500.
The compound (DD) may have a carbamate group having a protecting group on the nitrogen atom. The protective group constituting the carbamate group is represented by the following general formula (d-1).

In the general formula (d-1),
Each Rb independently represents 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), an aralkyl group (preferably Preferably, it represents 1 to 10 carbon atoms, or an alkoxyalkyl group (preferably 1 to 10 carbon atoms). R b may be linked to each other to form a ring.
The alkyl group, cycloalkyl group, aryl group and aralkyl group represented by R b are each independently a hydroxyl group, a cyano group, an amino group, a pyrrolidino group, a piperidino group, a morpholino group, an oxo group etc., an alkoxy group, or a halogen It may be substituted by an atom. The same applies to the alkoxyalkyl group represented by Rb.

As R b, 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.
As a ring which two Rb mutually connects and forms, alicyclic hydrocarbon, aromatic hydrocarbon, heterocyclic hydrocarbon, its derivative (s), etc. are mentioned.
Specific structures of the group represented by formula (d-1) include, but are not limited to, the structures disclosed in paragraph <0466> of US Patent Publication No. US 2012/0135348 A1.

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 l + m = 3 is satisfied.
Ra represents a hydrogen atom, an alkyl group, a cycloalkyl group, an aryl group or an aralkyl group. When l is 2, two Ras may be the same or different, and two Ras may be mutually linked to form a heterocyclic ring with the nitrogen atom in the formula. The hetero ring may contain a hetero atom other than the nitrogen atom in the formula.
Rb has the same meaning as Rb in formula (d-1), and the preferred examples are also the same.
In the general formula (6), each of the alkyl group, cycloalkyl group, aryl group and aralkyl group as Ra is independently substituted with an alkyl group, cycloalkyl group, aryl group and aralkyl group as Rb. It may be substituted by the same group as the group described above as a preferable group.

Specific examples of the alkyl group, cycloalkyl group, aryl group, and aralkyl group (these groups may be substituted with the above group) of the above Ra include the same groups as the specific examples described above for Rb. Be
Specific examples of particularly preferable compound (DD) in the present invention include, but are not limited to, the compounds disclosed in paragraph <0475> of US Patent Application Publication 2012/0135348 A1.

The onium salt compound (DE) having a nitrogen atom in the cation part (hereinafter, also referred to as a "compound (DE)") is preferably a compound having a basic site containing a nitrogen atom in the cation part. The basic moiety is preferably an amino group, more preferably an aliphatic amino group. More preferably, all atoms adjacent to the nitrogen atom in the basic site are hydrogen atoms or carbon atoms. Further, from the viewpoint of improving basicity, it is preferable that an electron-withdrawing functional group (such as a carbonyl group, a sulfonyl group, a cyano group, and a halogen atom) is not directly linked to the nitrogen atom.
Preferred specific examples of the compound (DE) include, but are not limited to, the compounds disclosed in paragraph <0203> of US Patent Application Publication No. 2015/0309408 A1.

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

In the composition of this invention, an acid diffusion control agent (D) may be used individually by 1 type, and may use 2 or more types together.
When the acid diffusion control agent (D) is contained in the composition, the content of the acid diffusion control agent (D) (if there is more than one type, the total thereof) is 0.1 based on the total solids of the composition. The content is preferably in the range of 10.0% by mass and more preferably 0.1% by mass to 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), the composition of the present invention can control the static / dynamic contact angle on the surface of the actinic ray-sensitive or radiation-sensitive film. This makes it possible to improve development characteristics, suppress outgassing, improve immersion liquid followability in immersion exposure, and reduce immersion defects.
The hydrophobic resin (E) is preferably designed to be localized on the surface of the resist film, but unlike a surfactant, it does not have to have a hydrophilic group in the molecule, and it is necessary to use polar / nonpolar substances. It does not have to contribute to mixing uniformly.

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 localization to the membrane surface layer It is preferable that it is resin which has a repeating unit which has at least 1 sort of.
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, It may be contained in the chain.

When the hydrophobic resin (E) contains a fluorine atom, it is 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 as a partial structure 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 which is decomposed by the action of an alkali developer to increase the solubility in the alkali developer (hereinafter, also referred to as a polarity converting group).
(Z) a group which is decomposed by the action of an acid

Examples of the acid group (x) include phenolic hydroxyl group, carboxylic acid group, fluorinated alcohol group, sulfonic acid group, sulfonamide group, sulfonylimide group, (alkylsulfonyl) (alkylcarbonyl) methylene group, (alkylsulfonyl) (alkyl Carbonyl) imide group, bis (alkyl carbonyl) methylene group, bis (alkyl carbonyl) imide group, bis (alkyl sulfonyl) methylene group, bis (alkyl sulfonyl) imide group, tris (alkyl carbonyl) methylene group, and tris (alkyl sulfonyl) group And the like) and the like.
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) which is decomposed by the action of an alkali developer to increase the solubility in the alkali developer include lactone group, carboxylic acid ester group (-COO-), and acid anhydride group (-C (O) OC). (O)-), acid imide group (-NHCONH-), carboxylic acid thioester group (-COS-), carbonate group (-OC (O) O-), sulfate group (-OSO ₂ O-), and A sulfonic acid ester group (—SO ₂ O—) and the like can be mentioned, and a lactone group or a carboxylic acid ester group (—COO—) is preferable.
As a repeating unit containing these groups, it is a repeating unit which these groups are directly couple | bonded with the principal chain of resin, for example, the repeating unit etc. by acrylic acid ester and methacrylic acid ester are mentioned, for example. In this repeating unit, these groups may be bonded to the main chain of the resin via a linking group. Alternatively, this repeating unit may be introduced at the end of the resin by using a polymerization initiator or chain transfer agent having these groups at the time of polymerization.
As a repeating unit which has a lactone group, the thing similar to the repeating unit which has the lactone structure previously demonstrated by the term of resin (AX1) is mentioned, for example.

The content of the repeating unit having a group (y) which is decomposed by the action of the alkali developer to increase the solubility in the alkali 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 more preferable.

The repeating unit which has group (z) which decomposes | disassembles by the effect | action of an acid in hydrophobic resin (E) is a thing similar to the repeating unit which has an acid degradable group mentioned by resin (AX1). The repeating unit having a group (z) capable of decomposing under 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 a group (z) capable of decomposing by the action of an acid is preferably 1 to 80 mol%, more preferably 10 to 80 mol%, based on all the repeating units in the hydrophobic resin (E). And 20 to 60 mol% is more preferable.
The hydrophobic resin (E) may further have another repeating unit other than the above-described repeating unit.

The repeating unit containing a fluorine atom is preferably 10 to 100% by mole, and more preferably 30 to 100% by mole, relative to all repeating units in the hydrophobic resin (E). In addition, the repeating unit containing a silicon atom is preferably 10 to 100% by mole, and more preferably 20 to 100% by mole, relative to all repeating units in the hydrophobic resin (E).

On the other hand, it is also preferable that the hydrophobic resin (E) substantially does not contain a fluorine atom and a silicon atom, particularly when the hydrophobic resin (E) contains a CH ₃ partial structure in the side chain portion. Further, the hydrophobic resin (E) is preferably substantially constituted only by a repeating unit constituted only by an atom selected from a carbon atom, an oxygen atom, a hydrogen atom, a nitrogen atom and a sulfur atom.

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

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

As hydrophobic resin (E), well-known resin can be suitably selected and used as an individual or a mixture thereof. For example, known resins disclosed in paragraphs <0451> to <0704> of US Patent Application Publication No. 2015/0168830 A1 and in paragraphs <0340> to <0356> of US Patent Application Publication No. 2016/0274458 A1. Can be suitably used as the hydrophobic resin (E). In addition, repeating units disclosed in paragraphs <0177> to <0258> of US Patent Application Publication No. 2016/0237190 A1 are also preferable as repeating units constituting the hydrophobic resin (E).

Preferred examples of the monomer corresponding to the repeating unit constituting the hydrophobic resin (E) are shown below.

Hydrophobic resin (E) may be used individually by 1 type, and may use 2 or more types together.
It is preferable to mix and use 2 or more types of hydrophobic resin (E) from which surface energy differs, from a viewpoint of coexistence of immersion liquid followability and image development characteristic in liquid immersion exposure.
The content of the hydrophobic resin (E) in the composition is preferably 0.01 to 10.0% by mass, and more preferably 0.05 to 8.0% by mass, with respect to 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, known resist solvents can be appropriately used. For example, paragraphs <0665> to <0670> of U.S. Patent Application Publication 2016 / 0070167A1; paragraphs <0210> to <0235> of U.S. Patent Application Publication 2015 / 0004544A1, U.S. Patent Application Publication 2016 / 0237190A1 Known solvents disclosed in paragraphs <0424> to <0426> of the specification and paragraphs <0357> to <0366> of US Patent Application Publication 2016/0274458 A1 can be suitably used.
Examples of solvents that can be used when preparing the composition include, for example, alkylene glycol monoalkyl ether carboxylate, alkylene glycol monoalkyl ether, lactic acid alkyl ester, alkyl alkoxypropionate, cyclic lactone (preferably having a carbon number of 4 to 10), Examples thereof include organic solvents such as a monoketone compound (preferably having a carbon number of 4 to 10) which may have a ring, an alkylene carbonate, an alkyl alkoxyacetate, and an alkyl pyruvate.

As an organic solvent, you may use the mixed solvent which mixed the solvent which has a hydroxyl group in a structure, and the solvent which does not have a hydroxyl group.
As the solvent having a hydroxyl group and the solvent having no hydroxyl group, the above-mentioned exemplified compounds can be appropriately selected, but as the solvent containing a hydroxyl group, alkylene glycol monoalkyl ether, alkyl lactate or the like is preferable, and 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, alkyl alkoxy propionate, a monoketone compound which may have a ring, cyclic lactone, alkyl acetate and the like are preferable, and among these, propylene is preferable. Glycol monomethyl ether acetate (PGMEA), ethyl ethoxy propionate, 2-heptanone, γ-butyrolactone, cyclohexanone, cyclopentanone or butyl acetate is more preferable, and propylene glycol monomethyl ether acetate, γ-butyrolactone, ethyl ethoxy propionate, Further preferred is cyclohexanone, cyclopentanone or 2-heptanone. Propylene carbonate is also preferred as the solvent having no hydroxyl group.
The mixing ratio (mass ratio) of the solvent having a hydroxyl group to the solvent having no hydroxyl group is 1/99 to 99/1, preferably 10/90 to 90/10, and 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 view of coating uniformity.
The solvent preferably contains propylene glycol monomethyl ether acetate, and may be propylene glycol monomethyl ether acetate alone 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 which crosslinks the resin by the action of an acid (hereinafter, also referred to as a crosslinking agent (G)). A well-known compound can be used suitably as a crosslinking agent (G). For example, known compounds disclosed in paragraphs <0379> to <0431> of US Patent Application Publication No. 2016/0147154 A1 and in paragraphs <0064> to <0141> of US Patent Application Publication No. 2016/0282720 A1. Can be suitably used as the crosslinking agent (G).
The crosslinking agent (G) is a compound having a crosslinkable group capable of crosslinking the resin, and as the crosslinkable group, a hydroxymethyl group, an alkoxymethyl group, an acyloxymethyl group, an alkoxymethyl ether group, an oxirane ring, And oxetane rings.
The crosslinkable group is preferably a hydroxymethyl group, an alkoxymethyl group, an oxirane ring or an oxetane ring.
The crosslinking agent (G) is preferably a compound (including a resin) having two or more crosslinkable groups.
The crosslinking agent (G) is more preferably a phenol derivative, a urea compound (a compound having a urea structure) or a melamine compound (a compound having a melamine structure) having a hydroxymethyl group or an alkoxymethyl group.
A crosslinking agent may be used individually by 1 type, and may use 2 or more types together.
The content of the crosslinking agent (G) is preferably 1.0 to 50% by mass, more 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 the surfactant is contained, a fluorine-based and / or 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 preferred.

When the composition of the present invention contains a surfactant, when an exposure light source of 250 nm or less, particularly 220 nm or less is used, it is possible to obtain a pattern with less adhesion and development defects with good sensitivity and resolution.
As the fluorine-based and / or silicon-based surfactant, the surfactants described in paragraph <0276> of US Patent Application Publication No. 2008/0248425 can be mentioned.
In addition to the fluorine-based and / or silicon-based surfactants described in paragraph <0280> of US Patent Application Publication No. 2008/0248425, other surfactants 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, and 0.0005 to 1.0% with respect to 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 based on the total solid content of the composition, the surface uneven distribution of the hydrophobic resin (E) is increased. As a result, the surface of the actinic ray-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 composition of the present invention further contains other additives such as an acid multiplying agent, a dye, a plasticizer, a photosensitizer, a light absorber, an alkali soluble resin, a dissolution inhibitor, and a dissolution accelerator. It is also 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, and still more preferably 2.0 to 5.3% by mass. The solid content concentration is a mass percentage of the mass of the other resist components excluding the solvent, with respect to the total mass of the composition.

In addition, 90 nm or less is preferable from a viewpoint of a resolution improvement, and, as for the film thickness of the actinic ray sensitive or radiation sensitive film which consists of a composition of this invention, 85 nm or less is more preferable. 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 coating property or the film forming property.

The composition of the present invention is used by dissolving the above-mentioned components in a predetermined organic solvent, preferably the above-mentioned mixed solvent, filtering it, and then applying it on a predetermined support (substrate). 0.1 micrometer or less is preferable, as for the pore size of the filter used for filter filtration, 0.05 micrometer or less is more preferable, and 0.03 micrometer or less is still more preferable. The filter is preferably made of polytetrafluoroethylene, polyethylene or nylon. In filter filtration, as disclosed in, for example, Japanese Patent Application Publication No. 2002-62667 (Japanese Patent Application Laid-Open No. 2002-62667), cyclic filtration may be performed, and a plurality of types of filters are connected in series or in parallel. May be connected to The composition may also be filtered multiple times. Furthermore, the composition may be subjected to a degassing treatment and the like before and after the filter filtration.

<Use>
The composition of the present invention relates to an actinic ray-sensitive or radiation-sensitive resin composition which changes its property in response to irradiation with an actinic ray or radiation. More specifically, the composition of the present invention can be used in semiconductor manufacturing processes such as IC (Integrated Circuit), production of circuit substrates such as liquid crystals or thermal heads, production of imprint mold structures, other photofabrication processes, or The present invention relates to an actinic ray-sensitive or radiation-sensitive resin composition used for producing a lithographic printing plate or an acid-curable composition. The pattern formed in the present invention can be used in an etching process, an ion implantation process, a bump electrode formation process, a rewiring formation process, MEMS (Micro Electro Mechanical Systems), and the like.

[Pattern formation method]
The present invention also relates to a method of forming a pattern using the actinic ray-sensitive or radiation-sensitive resin composition. Hereinafter, the pattern formation method of the present invention will be described. The actinic ray-sensitive or radiation-sensitive film of the present invention is also described together with the description of the pattern formation method.

The pattern formation method of the present invention is
(I) forming a resist film (an actinic ray-sensitive or radiation-sensitive film) on the support by the actinic ray-sensitive or radiation-sensitive resin composition described above (resist film-forming step)
(Ii) exposing the resist film (irradiating with an actinic ray or radiation) (exposure step), and
(Iii) developing the exposed resist film using a developer (developing step),
Have.

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

In the pattern formation method of the present invention, the above-described (i) film formation step, (ii) exposure step, and (iii) development step can be carried out by generally known methods.
In addition, if necessary, a resist underlayer film (for example, SOG (Spin On Glass), SOC (Spin On Carbon), and an antireflective film) may be formed between the resist film and the support. As a material which comprises a resist underlayer film, well-known organic type or inorganic type material can be used suitably.
A protective film (top coat) may be formed on the upper layer of the resist film. A well-known material can be used suitably as a protective film. For example, U.S. Patent Application Publication No. 2007/0178407, U.S. Patent Application Publication No. 2008/0085466, U.S. Patent Application Publication No. 2007/0275326, U.S. Patent Application Publication No. 2016/0299432, The composition for protective film formation disclosed by US Patent Application Publication No. 2013/0244438 and International Patent Application Publication No. 2016 / 157988A can be suitably used. As a composition for protective film formation, what contains the acid diffusion control agent mentioned above is preferable.
A protective film may be formed on the upper layer of the resist film containing the hydrophobic resin described above.

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

The heating temperature is preferably 70 to 130 ° C., and more preferably 80 to 120 ° C. in any of the (iv) pre-heating step and (v) post-exposure heating step.
The heating time is preferably 30 to 300 seconds, more preferably 30 to 180 seconds, and still more preferably 30 to 90 seconds in any of 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 using a hot plate or the like.

The light source wavelength used in the exposure step is not limited, and examples thereof include infrared light, visible light, ultraviolet light, far ultraviolet light, extreme ultraviolet light (EUV), X-rays, and electron beams. Among these, far ultraviolet light is preferable, and its wavelength is preferably 250 nm or less, more preferably 220 nm or less, and still more preferably 1 to 200 nm. Specifically, KrF excimer laser (248 nm), ArF excimer laser (193 nm), _{F 2} excimer laser (157 nm), X-ray, EUV (13 nm), or an electron beam or the like, KrF excimer laser, ArF excimer laser, EUV or electron beam is preferred.

(Iii) In the developing step, the developing solution may be either an alkali developing solution or a developing solution containing an organic solvent (hereinafter, also referred to as an organic developing solution).

Usually, quaternary ammonium salts represented by tetramethyl ammonium hydroxide are used as the alkali developing solution, but in addition to this, alkaline aqueous solutions such as inorganic alkali, primary to tertiary amines, alcohol amines, and cyclic amines are also used. It is usable.
Furthermore, the alkali developer may contain an appropriate amount of an alcohol and / or a surfactant. The alkali concentration of the alkali developer is usually 0.1 to 20% by mass. The pH of the alkaline developer is usually 10-15.
The time for developing using an alkaline developer is usually 10 to 300 seconds.
The alkali concentration, pH, and development time of the alkali 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 ketone solvents, ester solvents, alcohol solvents, amide solvents, ether solvents, and hydrocarbon solvents. Is preferred.

Examples of ketone solvents include 1-octanone, 2-octanone, 1-nonanone, 2-nonanone, acetone, 2-heptanone (methyl amyl ketone), 4-heptanone, 1-hexanone, 2-hexanone, diisobutyl ketone, Examples include cyclohexanone, methylcyclohexanone, phenylacetone, methyl ethyl ketone, methyl isobutyl ketone, acetylacetone, acetonylacetone, ionone, diacetonyl alcohol, acetylcarbinol, acetophenone, methylnaphthyl ketone, isophorone, propylene carbonate and the like.

As ester solvents, for example, methyl acetate, butyl acetate, ethyl acetate, isopropyl acetate, pentyl acetate, isopentyl acetate, amyl acetate, propylene glycol monomethyl ether acetate, ethylene glycol monoethyl ether acetate, diethylene glycol monobutyl ether acetate, diethylene glycol monoethyl Ether acetate, ethyl 3-ethoxy propionate, 3-methoxybutyl acetate, 3-methyl-3-methoxybutyl acetate, methyl formate, ethyl formate, butyl formate, propyl formate, ethyl lactate, butyl lactate, butyl lactate, butane And butyl acid, methyl 2-hydroxyisobutyrate, isoamyl acetate, isobutyl isobutyrate, and butyl propionate.

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. 2016/0070167 A1 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, still more preferably less than 10% by mass, and most preferably 0% by mass to less than 5% by mass. It is particularly preferred not to
The content of the organic solvent to the organic developer is preferably 50 to 100% by mass, more preferably 80 to 100% by mass, still more preferably 90 to 100% by mass, with respect to the total amount of the developer. % Is particularly preferred.

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

The content of the surfactant is usually 0.001 to 5% by mass, preferably 0.005 to 2% by mass, and more preferably 0.01 to 0.5% by mass, with respect to the total amount of the developer.

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

As a developing method, for example, a method of immersing the substrate in a bath filled with a developer for a certain time (dip method), a method of raising the developer on the substrate surface by surface tension and standing still for a certain time (paddle method) The method of spraying the developer on the surface (spray method) or the method of continuing to discharge the developer while scanning the developer discharge nozzle at a constant speed on the substrate rotating at a constant speed (dynamic dispense method), etc. are mentioned. Be

The step of developing using an aqueous alkali solution (alkali developing step) and the step of developing using a developer containing an organic solvent (organic solvent developing step) may be combined. As a result, since pattern formation can be performed without dissolving only the region of intermediate exposure intensity, a finer pattern can be formed.

(Iii) It is preferable that the process (rinse process) wash | cleaned using a rinse agent is included after the image development process.

The rinse liquid used for the rinse process after the image development process using an alkaline developing solution can use a pure water, for example. The pure water may contain an appropriate amount of surfactant. In this case, after the development step or the rinse step, a process of removing the developer or rinse solution adhering on the pattern with a supercritical fluid may be added. Furthermore, heat treatment may be performed to remove moisture remaining in the pattern after the rinse treatment or treatment with a supercritical fluid.

The rinse solution used for the rinse process after the development process using the developing solution containing an organic solvent does not have a restriction | limiting in particular if it is a thing which does not melt | dissolve a pattern, The solution containing a common organic solvent can be used. As the rinse solution, a rinse solution containing at least one organic solvent selected from the group consisting of hydrocarbon solvents, ketone solvents, ester solvents, alcohol solvents, amide solvents, and ether solvents is used. Is preferred.
Specific examples of the hydrocarbon-based solvent, the ketone-based solvent, the ester-based solvent, the alcohol-based solvent, the amide-based solvent, and the ether-based solvent include the same as those described in the developer containing an organic solvent.
As the rinse solution used in the rinse step in this case, a rinse solution containing a monohydric alcohol is more preferable.

Examples of the monohydric alcohol used in the rinse step include linear, branched or cyclic monohydric alcohol. 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 methyl isobutyl carbinol. 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, and methyl isobutyl carbinol. .

A plurality of each component may be mixed, or may be mixed with an organic solvent other than the above.
10 mass% or less is preferable, 5 mass% or less is more preferable, and 3 mass% or less is still more preferable. 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 surfactant.
In the rinse step, the substrate subjected to development using an organic developer is washed using a rinse solution containing an organic solvent. The method of cleaning treatment is not particularly limited. For example, a method of continuously discharging the rinse liquid onto the substrate rotating at a constant speed (rotation coating method), and immersing the substrate in a bath filled with the rinse liquid for a fixed time Examples include a method (dip method) or a method of spraying a rinse liquid on a substrate surface (spray method). Above all, it is preferable to carry out cleaning treatment by spin coating, and after cleaning, rotate the substrate at a rotational speed of 2,000 to 4,000 rpm to remove the rinse solution from the substrate. It is also preferable to include a heating step (Post Bake) after the rinsing step. By this heating step, the developer and the rinse 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 actinic ray-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, resist solvent, developer, rinse solution, composition for forming an antireflective film, or It is preferable that the composition for top coat formation etc. does not contain impurities, such as a metal component, an isomer, and a residual monomer. The content of these impurities contained in the various materials described above is preferably 1 ppm or less, more preferably 100 ppt or less, still more preferably 10 ppt or less, and substantially not including it (the detection limit of the measuring device or less) Is particularly preferred.

As a method of removing impurities, such as a metal, from said various materials, the filtration using a filter is mentioned, for example. The pore size of the filter is preferably 10 nm or less, more preferably 5 nm or less, and still more preferably 3 nm or less. As a material of the filter, a filter made of polytetrafluoroethylene, polyethylene or nylon is preferable. The filter may be one previously washed with an organic solvent. In the filter filtration step, plural types of filters may be connected in series or in parallel. When multiple types of filters are used, filters with different pore sizes and / or different materials may be used in combination. Also, the various materials may be filtered a plurality of times, and the step of filtering a plurality of times may be a circulation filtration step. As the filter, one having a reduced elution product as disclosed in Japanese Patent Application Publication No. 2016-201426 (Japanese Patent Application Laid-Open No. 2016-201426) is preferable.
In addition to filter filtration, removal of impurities by adsorbent may be performed, and filter filtration and adsorbent may be used in combination. A known adsorbent can be used as the adsorbent. 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).
In addition, as a method of reducing impurities such as metals contained in the above-mentioned various materials, filter filtration is performed on the materials constituting the various materials, in which the material having a small metal content is selected as the materials constituting the various materials. Alternatively, the inside of the apparatus may be lined with Teflon (registered trademark) or the like, and distillation may be carried out under conditions that minimize contamination as much as possible. It is also preferable to treat the glass lining in all steps of the manufacturing equipment for synthesizing various materials (resin and photoacid generator etc.) of the resist component in order to reduce impurities such as metal to the ppt order. The preferable conditions in the filter filtration performed with respect to the raw material which comprises various materials are the same as the conditions mentioned above.

The various materials described above are described in, for example, US Patent Application Publication No. 2015/0227049, Japanese Patent Application Publication No. 2015-123351 (Japanese Patent Application Publication No. 2015-123351), and the like in order to prevent contamination of impurities. Are preferably stored in a container.

A method of improving the surface roughness of the pattern may be applied to the pattern formed by the pattern forming method of the present invention. As a method of improving the surface roughness of the pattern, for example, a method of processing the pattern by plasma of a gas containing hydrogen disclosed in US Patent Application Publication No. 2015/0104957 can be mentioned. 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 may be applied as described in 8328 83280 N-1 “EUV Resist Curing Technique for LWR Reduction and Etch Selectivity Enhancement”.
Also, the pattern formed by the above method is, for example, the spacer process disclosed in Japanese Patent Application Publication No. 1991-270227 (Japanese Patent Application Laid-Open No. 3-270227) and US Patent Application Publication No. 2013/0209941. It can be used as a core material (Core).

[Method of Manufacturing Electronic Device]
The present invention also relates to a method of manufacturing an electronic device, including the pattern forming method described above. The electronic device manufactured by the method of manufacturing an electronic device of the present invention is suitably installed in an electric / electronic device (for example, a home appliance, an office automation (OA) related device, a media related device, an optical device, a communication device, etc.) Be done.

〔Compound〕
The present invention also relates to the compound represented by the general formula (1) and the compound represented by the general formula (2).
The 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 used, proportions, treatment contents, treatment procedures and the like shown in the following examples can be appropriately changed without departing from the spirit of the present invention. Accordingly, the scope of the present invention should not be construed as limited by the following examples.

[Preparation of actinic ray-sensitive or radiation-sensitive resin composition]
The various components contained in the actinic ray-sensitive or radiation-sensitive resin composition 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 degree of dispersion (Mw / Mn) of the resins A1 to A6 were measured by GPC (carrier: tetrahydrofuran (THF)) (equivalent to polystyrene). The compositional 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 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, a synthesis example of the compound C1 is shown as an example.

Synthesis Example 1: Synthesis of Compound C1
After ethyl 2-iodobenzoate (3.3 g) was dissolved in THF (20 mL) contained in a vessel, the internal temperature was cooled to -10.degree. Then, isopropylmagnesium chloride-lithium chloride complex (THF solution, 11.9 g) was added dropwise to the cooled mixture so that the internal temperature did not exceed 0 ° C., and the mixture was stirred at −10 ° C. for 30 minutes (reaction liquid 1 ).
After dissolving diphenyl sulfoxide (3.2 g) in THF (20 mL) contained in a vessel, the internal temperature was cooled to −10 ° C. Next, trifluoromethanesulfonic anhydride (3.4 g) was added dropwise to the cooled mixture so that the internal temperature did not exceed 0 ° C., and the mixture was stirred at 0 ° C. for 30 minutes (reaction liquid 2).
Then, after dripping the reaction liquid 1 so that internal temperature might not exceed 0 degreeC in the container which accommodated the reaction liquid 2, it was made to react at room temperature for 12 hours. To the resulting reaction solution, methylene chloride (100 mL) and distilled water (100 mL) were added to separate the layers. Then, the extracted organic layer was washed four times with distilled water (50 mL), and the solvent was evaporated. Further, the obtained residue was purified by column to obtain a purified product.
The purified product obtained by the above step was dissolved in methylene chloride (16 mL), 0.2 N sodium hydroxide (16 mL) was further added, and the mixture was reacted at 40 ° C. for 4 hours. The reaction solution obtained was separated, and the aqueous layer was extracted five times with methylene chloride (15 mL), and then the solvent was evaporated. The obtained solid was washed with diisopropyl ether (5 mL), the solvent was removed, and C1 (0.26 g) was obtained by drying.

Further, the same operation as in the synthesis example of the above-mentioned compound C1 was performed to synthesize the following compounds C2 to C24.

(Comparative acid diffusion control agent (D))
The structures of comparative acid diffusion control agents (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 ray-sensitive or radiation-sensitive resin composition>
Each component shown in Table 3 was mixed so that solid content concentration might be 3.3 mass%. Next, the resulting mixed solution is first filtered through a polyethylene filter with a pore size of 50 nm, then with a nylon filter with a pore size of 10 nm, and finally with a polyethylene filter with a pore size of 5 nm. Resin composition was prepared. In addition, in actinic-ray-sensitive or radiation-sensitive resin composition, solid content means all components other than a solvent (F). The obtained actinic ray 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>
A composition ARC29SR (manufactured by Nissan Chemical Industries, Ltd.) for forming an organic antireflective film was coated on a silicon wafer and heated at 205 ° C. for 60 seconds to form an antireflective film with a film thickness of 95 nm. The actinic ray-sensitive or radiation-sensitive resin compositions of Examples and Comparative Examples are coated on the obtained antireflective film, and heating (PB: Prebake) is performed at 100 ° C. for 60 seconds to obtain a resist film having a film thickness of 85 nm. Formed.
ArF excimer laser immersion scanner (manufactured by ASML; XT 1700 i, NA 1.20, C-Quad, outer sigma 0.900, inner sigma 0.812, XY deflection) ) Was exposed through a 6: 1 halftone mask with a 1: 1 line and space pattern of 44 nm line width. Ultrapure water was used as the immersion liquid. Thereafter, the resist film after exposure is heated at 105 ° C. for 60 seconds (PEB: Post Exposure Bake), and then developed with a negative developer (organic developer, butyl acetate) for 30 seconds by a paddle method, and A rinse solution (methyl isobutyl carbinol (MIBC)) was used to rinse by a paddle method for 30 seconds. Subsequently, the silicon wafer was spin-dried at a rotational 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 the top of the pattern using a scanning electron microscope (S-8840, manufactured by Hitachi, Ltd.). Under the present circumstances, 50 points of line widths were measured about the range of edge 2 micrometer of the longitudinal direction of a line pattern, and the standard deviation (3 (sigma)) was calculated about the measurement dispersion of the measured line widths. The smaller the value of the standard deviation (3σ), the better the LWR performance is.
In addition, evaluation of LWR performance was implemented based on the following five-step standard. 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 antireflective film ARC29SR (manufactured by Brewer) is coated on a silicon wafer and baked at 205 ° C. for 60 seconds to form an antireflective film having a film thickness of 98 nm, and the actinic ray of the example and comparative example is formed thereon. A radiation-sensitive 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 is formed is exposed 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. A contact hole pattern of 45 nm in diameter was exposed through a 6% halftone mask using an X.Y. 89 polarization). The amount of exposure to achieve the pattern size described above was taken as the optimum amount of exposure. Ultrapure water was used as the immersion liquid. Thereafter, the PEB was heated at a temperature set at 90 ° C., and then developed for 30 seconds with an organic developer, butyl acetate, and spin-dried to obtain a hole pattern.

<Performance evaluation: CDU performance (nm)>
Within one shot exposed at the above optimum exposure (E _opt ), the arbitrary 25 (ie, a total of 500) hole sizes are measured for each region in 20 regions with a distance of 1 μm. These standard deviations (σ) were determined to calculate 3σ. The smaller the value is, the smaller the variation in size is, which indicates that the performance is good.
The CDU performance was evaluated based on the following five levels. 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 Table 3, the content (% by mass) of each component means the content relative to the total solid content.
Further, in Table 3, "pKa (B)" corresponds to the pKa of the acid generated from the acid generator (B) (compounds B1 to B10) (the same as that listed in Table 1) .
In Table 3, “pKa (A1)” and “pKa (A2)” refer to the pKa of the acid generated from the compound represented by the general formula (1) (compounds C1 to C24), and the comparative acid These correspond to the pKa of the acids generated from the diffusion control agents (compounds D1 to D4) (the same as those listed in Table 2).

From the results of Table 3, according to the actinic ray-sensitive or radiation-sensitive resin composition of Examples, it was confirmed that both LWR and CDU of the formed pattern were excellent.
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 are unsubstituted single-ring aromatic carbonized When it is a hydrogen group (in other words, in the compound represented by the general formula (2), all of R ₁ to R ₄ are hydrogen atoms, or at least one of Ar ₂ and Ar ₃ is an unsubstituted single ring In the case of the aromatic hydrocarbon group (Examples 1, 4 and 10 and the comparison with Example 12), it was confirmed that both LWR and CDU of the formed pattern were 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 single-ring aromatic carbonized When it is a hydrogen group (in other words, in the compound represented by the general formula (2), a monocyclic aromatic hydrocarbon in which all of R ₁ to R ₄ are hydrogen atoms and one of Ar ₂ and Ar ₃ is unsubstituted Or Ar ₂ and Ar ₃ are both unsubstituted monocyclic aromatic hydrocarbon groups, or all of R ₁ to R ₄ are hydrogen atoms and both Ar ₂ and Ar ₃ are absent. When it is a substituted single ring aromatic hydrocarbon group (comparison of Examples 1 and 4 with Examples 10 and 12), it is confirmed that LWR and CDU of the formed pattern are both superior. The

Further, from the comparison between Example 1 and Examples 13 and 14, in the compound represented by the general formula (1), when L ₁ to L ₃ are single bonds, LWR and CDU of the formed pattern are either It was also confirmed that it was better.
Further, from the comparison of Examples 1, 2, and 15-18, 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 LWR and CDU of the formed pattern were superior.

Moreover, when the compound represented by General formula (1) is a compound represented by General formula (2) from the contrast with Example 1 and Example 19 and Example 20, LWR of the pattern formed is obtained. And CDU were all confirmed to be better.

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

On the other hand, the actinic ray-sensitive or radiation-sensitive resin composition of the comparative example did not satisfy the desired requirements.

Claims

With resin,
An acid generator which generates an acid upon irradiation with actinic rays or radiation;
And an acid diffusion control agent,
An actinic ray sensitive or radiation sensitive resin composition, wherein the acid diffusion control agent comprises a compound represented by the following general formula (1).

In the above formulae, Ar 1 , Ar 2 and Ar 3 each independently represent an aromatic hydrocarbon group.
A 1 is substituted ortho to the carbon atom bonded to the S + on Ar 1, and, -L 1 -CO 2 -, -L 2 -SO 3 -, or -L 3 -X 1 - N -- Y 1 represents.
Each of L 1 , L 2 and L 3 independently represents a single bond or a divalent linking group.
X 1 represents -SO 2- or -CO-.
Y 1 represents an -SO 2 -R A, or -CO-R B.
Each of R A and R B independently represents a monovalent substituent.
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-ray-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 formulae, Ar 2 and Ar 3 each independently represent a monocyclic aromatic hydrocarbon group.
Each of R 1 , R 2 , R 3 and R 4 independently represents a hydrogen atom or a nonaromatic substituent.
A 1 is, -L 1 -CO 2 -, -L 2 -SO 3 -, or -L 3 -X 1 -N - represents a -Y 1.
Each of L 1 , L 2 and L 3 independently represents a single bond or a divalent linking group.
X 1 represents -SO 2- or -CO-.
Y 1 represents an -SO 2 -R A, or -CO-R B.
Each of R A and R B independently represents a monovalent substituent.
Ar 2 and Ar 3 may further have a substituent, and the substituents may be bonded to each other to form a ring.
3. The actinic ray-sensitive or radiation-sensitive compound according to claim 2, wherein all of R 1 to R 4 are hydrogen atoms, or at least one of Ar 2 and Ar 3 is an unsubstituted monocyclic aromatic hydrocarbon group. Resin composition.
All of R 1 to R 4 are hydrogen atoms, and one of Ar 2 and Ar 3 is an unsubstituted monocyclic aromatic hydrocarbon group,
Or both of Ar 2 and Ar 3 are unsubstituted monocyclic aromatic hydrocarbon groups, or
3. The actinic ray-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. .
A 1 is, -L 1 -CO 2 -, or -L 3 -X 1 -N - is -Y 1, ray- according to any one of claims 1 to 4 or radiation-sensitive resin Composition.
The actinic ray-sensitive or radiation-sensitive resin composition according to claim 5, wherein L 1 and L 3 are single bonds.
A resist film formed using the actinic ray-sensitive or radiation-sensitive resin composition according to any one of claims 1 to 6.
A resist film forming step of forming a resist film using the actinic ray sensitive or radiation sensitive resin composition according to any one of claims 1 to 6;
An exposure step of exposing the resist film;
And developing the exposed resist film with a developer.
The manufacturing method of an electronic device containing the pattern formation method of Claim 8.
The compound represented by following General formula (1).

In the above formulae, Ar 1 , Ar 2 and Ar 3 each independently represent an aromatic hydrocarbon group.
A 1 is substituted ortho to the carbon atom bonded to the S + on Ar 1, and, -L 1 -CO 2 -, -L 2 -SO 3 -, or -L 3 -X 1 - N -- Y 1 represents.
Each of L 1 , L 2 and L 3 independently represents a single bond or a divalent linking group.
X 1 represents -SO 2- or -CO-.
Y 1 represents an -SO 2 -R A, or -CO-R B.
Each of R A and R B independently represents a monovalent substituent.
However, the atom at the bonding position to Ar 1 in L 1 , L 2 and L 3 is not an oxygen atom.
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 compound represented by following General formula (2).

In the above formulae, Ar 2 and Ar 3 each independently represent a monocyclic aromatic hydrocarbon group.
Each of R 1 , R 2 , R 3 and R 4 independently represents a hydrogen atom or a nonaromatic substituent.
A 1 is, -L 1 -CO 2 -, -L 2 -SO 3 -, or -L 3 -X 1 -N - represents a -Y 1.
Each of L 1 , L 2 and L 3 independently represents a single bond or a divalent linking group.
X 1 represents -SO 2- or -CO-.
Y 1 represents an -SO 2 -R A, or -CO-R B.
Each of R A and R B independently represents a monovalent substituent.
However, the atom at the bonding position to Ar 1 in L 1 , L 2 and L 3 is not an oxygen atom.
Ar 2 and Ar 3 may further have a substituent, and the substituents may be bonded to each other to form a ring.
The compound according to claim 11, wherein all of R 1 to R 4 are hydrogen atoms, or at least one of Ar 2 and Ar 3 is an unsubstituted monocyclic aromatic hydrocarbon group.
All of R 1 to R 4 are hydrogen atoms, and one of Ar 2 and Ar 3 is an unsubstituted monocyclic aromatic hydrocarbon group,
Or both of Ar 2 and Ar 3 are unsubstituted monocyclic aromatic hydrocarbon groups, or
The compound according to claim 11, wherein all of R 1 to R 4 are a hydrogen atom, and Ar 2 and Ar 3 are both unsubstituted monocyclic aromatic hydrocarbon groups.
A 1 is, -L 1 -CO 2 -, or -L 3 -X 1 -N - is -Y 1, a compound according to any one of claims 10-13.
L 1 and L 3 is a single bond, A compound according to claim 14.