TW201927746A - Active-light-sensitive or radiation-sensitive resin composition, resist film, pattern formation method, method for manufacturing electronic device, and compound - Google Patents

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

Photosensitized or radiation-sensitive resin composition, resist film, pattern forming method, method for manufacturing electronic component, and compound

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

Conventionally, in the manufacturing steps of semiconductor devices such as IC (Integrated Circuit) and LSI (Large Scale Integrated Circuit), lithography using a chemically amplified resist composition has been performed. Fine processing.

For example, in Japanese Patent Document 1, as a pattern forming method using a chemically amplified resist composition, the following pattern forming method is disclosed: "having (a) by actinic rays containing the following (A) to (C) Process for forming a film with a radioactive or radiation-sensitive resin composition; (A) a resin having reduced solubility in a developer containing an organic solvent by increasing the polarity of the action of an acid; (B) a photochemical ray or radiation Compounds that generate an acid by irradiation and (C) a compound having a cation site and an anion site in the same molecule, and the cation site and the anion site are connected by covalent bonding, (2) a process of exposing the film; And (3) a process of developing the above-exposed film using a developing solution containing an organic solvent to form a negative pattern. " In addition, in the aforementioned Japanese Patent Document 1, as the component (C), the following two types of betaine-type compounds are disclosed.

The component (B) is a so-called acid generator, and generates an acid upon exposure to actinic rays or radiation in an exposure process (process (2)). The generated acid mainly contributes to the deprotection reaction of the acid-decomposable resin (the (A) component).

[Chemical Formula 1] [Prior Art Literature] [Patent Literature]

[Patent Document 1] Japanese Patent Laid-Open No. 2014-170205

The present inventors made reference to Japanese Patent Document 1, and prepared an acid generator (hereinafter, referred to as an acid generator (hereinafter, referred to as "protection reaction") for initiating a deprotection reaction of a resin component "Acid generator X".) And the photosensitizing radiation or radiation-sensitive resin composition of the above-mentioned betaine-type compound, as a result of investigation, it was found that when the above-mentioned betaine-type compound is irradiated with actinic radiation or radiation, The acid generated by the acid generator X is a relatively weak acid, and functions as an acid diffusion control agent (neutralizing agent) that controls diffusion to the unexposed portion of the acid generated from the acid generator X. On the other hand, the present inventors have confirmed that the betaine-type compound easily forms aggregates (for example, dimers) in a photosensitized or radiation-sensitive resin composition, and is not easily dispersed uniformly in the system. As a result, it was confirmed that the betaine-type compound is unevenly present in a film containing a photosensitized or radioactive resin composition of the acid generator X and the betaine-type compound (hereinafter, sometimes the "The film of a photosensitized or radiation-sensitive resin composition" is also referred to as a "resist film".) Therefore, when the exposure process is performed, the betaine compound diffuses the acid generated from the acid generator X. Suppresses (neutralizes) the implementation of non-uniformity, thereby reducing the pattern line width fluctuation (LWR (line width roughness)) and in-plane uniformity (CDU (critical dimension uniformity; critical dimension uniformity) )) Not necessarily enough.

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

As a result of intensive research in order to solve the above-mentioned problems, the inventors have found that a photoresistive or radiation-sensitive resin composition containing an acid generator and an acid diffusion control agent represented by the general formula (1) can be solved. The above-mentioned subject has completed the present invention. That is, it was found that the above problems can be solved by the following configuration.

[1] A actinic radiation- or radiation-sensitive resin composition comprising: a resin; an acid generator that generates an acid upon irradiation with actinic radiation or radiation; and an acid diffusion control agent, at least the acid diffusion control agent It includes a compound represented by the general formula (1). [2] The photosensitive radiation- 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] The photosensitive radiation- or radiation-sensitive resin composition according to [2], wherein in the general formula (2), R ₁ to R ₄ are all hydrogen atoms or at least one of Ar ₂ and Ar ₃ It is an unsubstituted monocyclic aromatic hydrocarbon group. [4] The photosensitized or radiation-sensitive resin composition according to [2], wherein in the general formula (2), R ₁ to R ₄ are all hydrogen atoms and one of Ar ₂ and Ar ₃ is Unsubstituted monocyclic aromatic hydrocarbon group, or Ar ₂ and Ar ₃ are both unsubstituted monocyclic aromatic hydrocarbon group, or R ₁ to R ₄ are all hydrogen atoms, and Ar ₂ and Ar ₃ are both unsubstituted Monocyclic aromatic hydrocarbon group. [5] The photosensitized radiation- or radiation-sensitive resin composition according to any one of [1] to [4], wherein in the general formula (1) or (2), A ₁ is -L ₁ -CO ₂ ^- or -L ₃ -X ₁ -N ^-- Y ₁ . [6] The photosensitized or radioactive resin composition according to [5], wherein L ₁ and L ₃ are single bonds. [7] A resist film formed using the photosensitive radiation-sensitive or radiation-sensitive resin composition according to any one of [1] to [6]. [8] A pattern forming method, comprising: a resist film forming process, forming a resist film using the photosensitive radiation- or radiation-sensitive resin composition according to any one of [1] to [6] An exposure process for exposing the resist film; and a development process for developing the exposed resist film using a developing solution. [9] A method for manufacturing an electronic component, including the pattern forming method according to [8]. [10] A compound represented by the general formula (1). [11] A compound represented by the general formula (2). [12] The compound according to [11], wherein in the general formula (2), R ₁ to R ₄ are each a hydrogen atom or at least one of Ar ₂ and Ar ₃ is an unsubstituted monocyclic aromatic hydrocarbon group . [13] The compound according to [11], wherein in the general formula (2), R ₁ to R ₄ are all hydrogen atoms and one of Ar ₂ and Ar ₃ is an unsubstituted monocyclic aromatic hydrocarbon group, Or, Ar ₂ and Ar ₃ are both unsubstituted monocyclic aromatic hydrocarbon groups, or R ₁ to R ₄ are all hydrogen atoms and Ar ₂ and Ar ₃ are both unsubstituted monocyclic aromatic hydrocarbon groups. [14] The compound according to any one of [10] to [13], wherein in the general formula (1) or (2), A ₁ is -L ₁ -CO ₂ ^- or -L _3- X ₁ -N ^-- Y ₁ . [15] The compound according to [14], wherein L ₁ and L ₃ are single bonds. [Inventive effect]

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

Hereinafter, the present invention will be described in detail. The description of the constituent elements described below may be completed based on the representative embodiments of the present invention, but the present invention is not limited to these embodiments. "Actinic rays" or "radiation" in this specification means, for example, a bright line spectrum of a mercury lamp, far ultraviolet rays represented by an excimer laser, extreme ultraviolet rays (EUV light: Extreme Ultraviolet), X-rays, and electron beams (EB: Electron Beam) and so on. "Light" in this specification means actinic rays or radiation. Unless otherwise specified, "exposure" in this specification includes not only exposure by bright line spectrum of a mercury lamp, extreme ultraviolet, extreme ultraviolet, X-ray, and EUV light represented by an excimer laser, but also exposure by an electron beam And particle beams such as ion beams. In this specification, "~" is used as a meaning including the numerical value before and after it as a lower limit value and an upper limit value.

In this specification, (meth) acrylate means an acrylate and a methacrylate. In this specification, the weight average molecular weight (Mw), number average molecular weight (Mn), and dispersion (also referred to as molecular weight distribution) of the resin (Mw / Mn) are defined as the use of GPC (gel permeation chromatography) GPC measurement (Gel Permeation Chromatography) device (HLC-8120GPC manufactured by TOSOH CORPORATION) (solvent: tetrahydrofuran, flow rate (sample injection amount): 10 μL, column: TSK gel Multipore HXL-M manufactured by TOSOH CORPORATION, column temperature: 40 ° C , Flow rate: 1.0mL / min, Detector: Polystyrene conversion value of differential index detector (Refractive Index Detector).

Regarding the label of the group (atomic group) in this specification, the undescribed and unsubstituted labels include those having no substituent and those having a substituent. For example, "alkyl" includes not only alkyl groups (unsubstituted alkyl groups) having no substituents, but also alkyl groups (substituted alkyl groups) having substituents.

In addition, in this specification, the type of the substituent, the position of the substituent, and the number of the substituent are not particularly limited when it is indicated that “may have a substituent”. The number of substituents may be, for example, one, two, three or more. Examples of the substituent include a monovalent non-metallic atomic group other than a hydrogen atom, and for example, a substituent group T which can be selected from the following. (Substituent T) Examples of the substituent T include halogen atoms such as fluorine atom, chlorine atom, bromine atom, and iodine atom; alkoxy groups such as methoxy, ethoxy, and tertiary butoxy; phenoxy and Aryloxy groups such as p-tolyloxy; alkoxycarbonyl groups such as methoxycarbonyl, butoxycarbonyl, and phenoxycarbonyl; fluorenyloxy groups such as ethoxyl, propoxyl, and benzyloxy; Methenyl, isobutylamyl, propenyl, methacryl and methoxalyl groups; alkylsulfanyl groups such as methylsulfanyl and tertiary butylsulfanyl; phenyl Aryl sulfanyl groups such as sulfanyl and p-toluylsulfanyl; alkyl groups; cycloalkyl groups; aryl groups; heteroaryl groups; hydroxyl groups; carboxyl groups; formyl groups; sulfo groups; cyano groups; alkylaminocarbonyl groups; Arylaminocarbonyl; sulfonamido; formamidine; amine; monoalkylamino; dialkylamino; arylamino; and combinations of these.

[Photosensitized radioactive or radiation-sensitive resin composition] The photosensitized radioactive or radiation-sensitive resin composition (hereinafter, also referred to as "the composition of the present invention") of the present invention contains a resin and actinic rays. Or an acid generator (hereinafter, also referred to as “acid generator X”) that generates an acid or irradiation with radiation, and an acid diffusion control agent that contains at least a compound represented by the general formula (1) described later.

As a characteristic point of this invention, the point which contains the compound represented by General formula (1) as an acid-diffusion control agent is mentioned. Hereinafter, the mechanism of action of the acid diffusion control agent as the compound represented by the general formula (1) will be described, and then the structural characteristics of the compound represented by the general formula (1) will be described.

<Mechanism of action of an acid diffusion control agent as a compound represented by the general formula (1)> The compound represented by the general formula (1) generates an acid upon irradiation with actinic rays or radiation. An acid generator (acid generator) which is generally used to initiate a deprotection reaction (deprotection reaction of an acid-decomposable resin) of a resin component or a crosslinking reaction of a resin component with respect to an acid generated from a compound represented by the general formula (1) X) becomes relatively weak acid. Therefore, in the resist film system during and / or after exposure, a significant proton exchange between the acid generated from the acid generator X and the anion of the acid generated from the compound represented by the general formula (1) occurs. reaction. As a result, the acid generated from the acid generator X is neutralized, and the diffusion of the acid generated from the acid generator X to the unexposed portion is suppressed.

<Structural characteristics of the compound represented by the general formula (1)> As a structural characteristic point of the compound represented by the general formula (1), an anionic group represented by A ₁ is bonded to a sulfonium cation The S ⁺ bonded carbon atom on Ar ₁ (aromatic hydrocarbon group) is substituted ortho to this. The present inventors have speculated that the reason why the betaine-type compound described in Japanese Patent Document 1 easily aggregates in photosensitized or radiation-sensitive resin compositions (multimers such as dimers are likely to form) is due to the betaine-type compound. Intramolecular polarization of a compound. In more detail, it is considered that the positive charge and the negative charge in the molecule of the betaine-type compound are too far apart, and therefore they aggregate with other molecules for neutralization of the charge. In contrast, the anionic group represented by A ₁ and the cationic site of the sulfur atom represented by S ⁺ are structurally close, and therefore the compound represented by the general formula (1) is not easily composed of a photosensitive resin or a radiation-sensitive resin. Condensation. Therefore, the compound represented by the general formula (1) also exists uniformly dispersed in the resist film system. As a result, it is estimated that in the resist film system during and / or after the exposure, the diffusion suppression (neutralization of the acid generated from the compound represented by the general formula (1) to the acid generated from the acid generator X is uniformly performed) ). According to the aforementioned mechanism of action, the pattern formed by the composition of the present invention has excellent LWR performance and CDU performance. The acid generated from the compound represented by the general formula (1) is presumed to be any one or more of an acid represented by the following general formula (1X) and an acid represented by the following general formula (1Y). That is, it is presumed that depending on the structure, an acid represented by the following general formula (1X) alone is produced, or an acid represented by the following general formula (1Y) is alone produced, or both are represented by the following general formula (1X) An acid and an acid represented by the following general formula (1Y). Further, in the following formula (1X) and the following formula _{(1Y), Ar 1, Ar} 2, Ar 3 and A ₁ in the general formula (1), Ar _1, Ar _2, Ar ₃ is A ₁ and The meaning is the same. General formula (1X): Ar ₁ -A ₁ -H General formula (1Y): Ar ₂ -S-Ar ₃ -Ar ₁ -A ₁ -H

In addition, it is presumed that in addition to the above points, the fact that the acid diffusion control agent has a betaine structure also contributes to the improvement of LWR performance and CDU performance. As an acid diffusion control agent having the same mechanism of acid diffusion control (the mechanism of neutralization of the acid generator X) as that of the compound represented by the general formula (1), for example, a triphenylphosphonium salt is known. When such an acid diffusion control agent is used, it is difficult to plasticize a resist film when an acid diffusion control agent with a betaine structure is used. Therefore, it is considered that the resist film after exposure is not easily dissolved unevenly during 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. 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 includes a resin (hereinafter, also referred to as "resin (A)"). As the resin (A), for example, a resin (AX1), a resin (AX2), or the like can be used, and among them, the resin (AX1) is preferable.

(Resin (AX1)) Resin (AX1) is a resin (hereinafter, also referred to as "acid decomposition") having a group (hereinafter, also referred to as "acid-decomposable group") that has increased polarity due to decomposition by the action of an acid. Sex resin ".). When the composition of the present invention contains a resin (AX1), the pattern formed is usually a positive pattern when an alkali developer is used as a developer, and a negative pattern when an organic developer is used as a developer.

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

As the resin (AX1), a known resin can be appropriately used. For example, paragraphs <0055> to <0191> of U.S. Patent Application Publication No. 2016 / 0274458A1, paragraphs <0035> to <0085> of U.S. Patent Application Publication No. 2015 / 0004544A1, and U.S. Patent Application Publication No. 2016 / 0147150A1 can be used. Known resins disclosed in paragraphs <0045> to <0090> of the specification are suitably used as the resin (AX1).

The acid-decomposable group preferably has a structure in which a polar group is protected by a group (a leaving group) that is decomposed and decomposed by the action of an acid. Examples of the polar group include a carboxyl group, a phenolic hydroxyl group, a fluorinated alcohol group, a sulfonic acid group, a sulfonamido group, a sulfonamido group, (alkylsulfonyl group) (alkylcarbonyl) methylene group, ( Alkylsulfonyl) (alkylcarbonyl) fluorenimine, bis (alkylcarbonyl) methylene, bis (alkylcarbonyl) fluorenimine, bis (alkylsulfonyl) methylene, bis (Alkylsulfonyl) sulfonylimino, tris (alkylcarbonyl) methylene, and tri (alkylsulfonyl) methylene acid groups (dissociated in a 2.38 mass% tetramethylammonium hydroxide aqueous solution) Groups) and alcoholic hydroxyl groups.

In addition, the alcoholic hydroxyl group is a hydroxyl group bonded to a hydrocarbon group, and refers to a hydroxyl group other than a hydroxyl group (phenolic hydroxyl group) directly bonded to an aromatic ring, and is substituted by an electron-withdrawing group such as a fluorine atom at the alpha position of the hydroxyl group. Except for group alcohols (for example, 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 a carboxyl group, a phenolic hydroxyl group, a fluorinated alcohol group (preferably a hexafluoroisopropanol group), and a sulfonic acid group.

A preferable group as the acid-decomposable group is a group in which a hydrogen atom of such a group is replaced with a group (leaving group) which is released by the action of an acid. Examples of the group (leaving group) to be released by the action of an acid include -C (R ₃₆ ) (R ₃₇ ) (R ₃₈ ), -C (R ₃₆ ) (R ₃₇ ) (OR ₃₉ ), and- C (R ₀₁ ) (R ₀₂ ) (OR ₃₉ ) and so on. In the formula, R ₃₆ to R ₃₉ each independently represent an alkyl group, a cycloalkyl group, an aryl group, an aralkyl group, or an alkenyl group. R ₃₆ and R ₃₇ may be bonded to each other to form a ring. R ₀₁ and R ₀₂ each independently represent a hydrogen atom, an alkyl group, a cycloalkyl group, an aryl group, an aralkyl group, or an alkenyl group.

As the alkyl group represented by R ₃₆ to R ₃₉ , R ₀₁ and R ₀₂ , an alkyl group having 1 to 8 carbon atoms is preferred, and examples thereof include methyl, ethyl, propyl, n-butyl, and secondary butyl. Base, hexyl and octyl. The cycloalkyl group represented by R ₃₆ to R ₃₉ , R _01, and R ₀₂ may be monocyclic or polycyclic. The monocyclic cycloalkyl group is preferably a cycloalkyl group having 3 to 8 carbon atoms, and examples thereof include cyclopropyl, cyclobutyl, cyclopentyl, cyclohexyl, and cyclooctyl. The polycyclic cycloalkyl group is preferably a cycloalkyl group having 6 to 20 carbon atoms. Examples thereof include adamantyl, norbornyl, isofluorenyl, fluorenyl, dicyclopentyl, α-fluorenyl, Tricyclodecyl, tetracyclododecyl and androstanyl. In addition, at least one carbon atom in the cycloalkyl group may be substituted with a hetero atom such as an oxygen atom. As the aryl group represented by R ₃₆ to R ₃₉ , R ₀₁ and R ₀₂ , an aryl group having 6 to 10 carbon atoms is preferred, and examples thereof include a phenyl group, a naphthyl group, and an anthryl group. The aralkyl group represented by R ₃₆ to R ₃₉ , R ₀₁ and R ₀₂ is preferably an aralkyl group having 7 to 12 carbon atoms, and examples thereof include benzyl, phenethyl, and naphthylmethyl. The alkenyl group represented by R ₃₆ to R ₃₉ , R ₀₁ and R ₀₂ is preferably an alkenyl group having 2 to 8 carbon atoms, and examples thereof include vinyl, allyl, butenyl, and cyclohexenyl. As the ring formed by bonding R ₃₆ and R _{37 to} each other, a cycloalkyl group (monocyclic or polycyclic) is preferred. As the cycloalkyl group, monocyclic cycloalkyl groups such as cyclopentyl and cyclohexyl, or polycyclic cycloalkyl groups such as norbornyl, tetracyclodecyl, tetracyclododecyl, and adamantyl are preferred.

As the acid-decomposable group, a cumylester group, an enol ester group, an acetal ester group, or a tertiary alkyl ester group is preferable, and an acetal ester 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.

[Chemical Formula 2]

In the general formula (AI), Xa ₁ represents a hydrogen atom, a halogen atom, or a monovalent organic group. T represents a single bond or a divalent linking group. Rx ₁ to Rx ₃ each independently represent an alkyl group or a cycloalkyl group. Any two of Rx ₁ to Rx ₃ may be bonded 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-, -O-Rt-, and the like. In the 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 linear alkylene group having 1 to 5 carbon atoms, and -CH ₂ -,-(CH ₂ ) _2- , or-(CH ₂ ) ₃ -is more preferable. As T, a single bond is more preferred.

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 is preferably a carbon number of 1 to 4, and examples thereof include methyl, ethyl, propyl, methylol, and trifluoromethyl. As the alkyl group of Xa ₁ , a methyl group is preferred.

The alkyl group represented by Rx ₁ , Rx ₂ and Rx ₃ may be linear or branched, and methyl, ethyl, n-propyl, isopropyl, n-butyl, isobutyl or Tertiary butyl and the like are preferred. The number of carbon atoms of the alkyl group is preferably from 1 to 10, more preferably from 1 to 5, and even more preferably from 1 to 3. Among the alkyl groups represented by Rx ₁ , Rx ₂ and Rx ₃ , a part of the carbon-carbon bond may be a double bond. As the cycloalkyl group represented by Rx ₁ , Rx ₂ and Rx ₃ , monocyclic cycloalkyl or norbornyl such as cyclopentyl and cyclohexyl, tetracyclodecyl, tetracyclododecyl, adamantyl, etc. Polycyclic cycloalkyl is preferred.

As the ring structure formed by the two bonds of Rx ₁ , Rx ₂ and Rx ₃ , cyclopentane ring, cyclohexyl ring, cycloheptane ring, cyclooctane ring and other monocyclic naphthene rings or norbornane rings, Polycyclic cycloalkyl rings such as tetracyclodecane ring, tetracyclododecane ring and adamantane ring are preferred. Among them, a cyclopentane ring, a cyclohexyl ring or an adamantane ring is more preferable. As the ring structure formed by the two bonds of Rx ₁ , Rx ₂ and Rx ₃ , the structures shown below are also preferable.

[Chemical Formula 3]

Specific examples of the monomer corresponding to the repeating unit represented by the general formula (AI) are given below, but the present invention is not limited to these specific examples. Specific examples corresponding to the following general formula (AI) in the Xa ₁ is a methyl group, Xa is a hydrogen atom can be optionally _1, a halogen atom or a monovalent organic group substituted.

[Chemical Formula 4]

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

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

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

The content of repeating units with acid-decomposable groups contained in resin (AX1) (total of multiple repeating units with acid-decomposable groups) is 10 to 90 moles relative to all repeating units of resin (AX1) % Is preferable, 20 to 80 mol% is more preferable, and 30 to 70 mol% is further 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.

As a lactone structure or a sultone structure, it is only necessary to have a lactone structure or a sultone structure, and a 5- to 7-membered cyclic lactone structure or a 5- to 7-membered sultone structure is preferable. Among them, those with 5 to 7 membered cyclic lactone structures condensed with other ring structures in the form of forming a bicyclic structure or a spiro ring structure or with 5 to 7 members of cyclic sultone structure condensed with other structures in the form of a bicyclic structure or a spirocyclic structure. A ring structure is more preferred. The resin (AX1) has a lactone structure represented by any one of the following general formulae (LC1-1) to (LC1-21) or a resin represented by the following general formulae (SL1-1) to (SL1-3) Any repeating unit of the sultone structure is further preferred. The lactone structure or the sultone structure may be directly bonded to the main chain. Preferred structures include the general formula (LC1-1), general formula (LC1-4), general formula (LC1-5), general formula (LC1-8), general formula (LC1-16), or A lactone structure represented by the general formula (LC1-21) or a sultone structure represented by the general formula (SL1-1).

[Chemical Formula 5]

The lactone structural part or the sultone structural part may or may not have a substituent (Rb ₂ ). Preferred substituents (Rb ₂ ) include alkyl groups having 1 to 8 carbon atoms, cycloalkyl groups having 4 to 7 carbon atoms, alkoxy groups having 1 to 8 carbon atoms, and alkoxy groups having 2 to 8 carbon atoms. A carbonyl group, a carboxyl group, a halogen atom, a hydroxyl group, a cyano group, and an acid-decomposable group are preferably an alkyl group having 1 to 4 carbon atoms, a cyano group, or an acid-decomposable group. n ₂ represents an integer of 0 to 4. When n ₂ is 2 or more, a plurality of substituents (Rb ₂ ) may be the same or different. In addition, a plurality of substituents (Rb ₂ ) may be bonded to each other to form a ring.

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

[Chemical Formula 6]

In the above general formula (III), A represents an ester bond (a group represented by -COO-) or an amido bond (a group represented by -CONH-). n is the repetition number of the structure represented by -R ₀ -Z-, and represents an integer of 0 to 5, 0 or 1 is preferable, and 0 is more preferable. When n is 0, -R ₀ -Z- does not exist, and it becomes a single bond. R ₀ represents an alkylene group, a cycloalkylene group, or a combination thereof. When plural R ₀ are present, each R ₀ independently represents an alkylene group, a cycloalkylene group, or a combination thereof. Z represents a single bond, an ether bond, an ester bond, a amide bond, a urethane bond, or a urea bond. When a plurality of Z are present, each of Z independently represents a single bond, an ether bond, an ester bond, a 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).

[Chemical Formula 7]

In the 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 each independently represents a substituent. A represents a single bond or a divalent linking group. Z represents an atomic group that forms a monocyclic structure or a polycyclic structure together with the group represented by -OC (= O) -O- in the formula.

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

The resin (AX1) may have one type of repeating unit selected from the group consisting of a lactone structure, a sultone structure, and a carbonate structure, or it may have two or more types in combination.

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) are given below, but the present invention is not limited to this. 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 methyl groups, and R ₇ and R _A ¹ can be arbitrarily substituted with a hydrogen atom, a halogen atom, or Monovalent organic group substitution.

[Chemical Formula 8]

In addition to the above monomers, the monomers shown below are also preferably used as a raw material for the resin (AX1).

[Chemical Formula 9]

Content of at least one repeating unit selected from the group including a lactone structure, a sultone structure and a carbonate structure included in the resin (AX1) (having a content selected from the group consisting of a lactone structure, a sultone structure and a carbonic acid At least one repeating unit in the salt structure group is a total of a plurality of repeating units.) 5 to 70 mol% is preferred, and 10 to 65 mol% is more preferred to all repeating units in the resin (AX1). 20 to 60 mol% is further preferred.

It is preferable that the resin (AX1) has a repeating unit having a polar group. Examples of the polar group include a hydroxyl group, a cyano group, a carboxyl group, and a fluorinated alcohol group. As the repeating unit having a polar group, a repeating unit having an alicyclic hydrocarbon structure substituted with a polar group is preferable. Moreover, it is preferable that the repeating unit which has a polar group does not have an acid-decomposable group. As the alicyclic hydrocarbon structure in the alicyclic hydrocarbon structure substituted with a polar group, adamantyl or norbornyl is preferable.

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

[Chemical Formula 10]

In addition, specific examples of the repeating unit having a polar group include the repeating units disclosed in paragraphs <0415> to <0433> of the specification of US Patent Application Publication No. 2016 / 0070167A1. The resin (AX1) may have one type of repeating unit having a polar group alone, or may have two or more types in combination. The content of the repeating unit having a polar group is preferably 5 to 50 mol%, more preferably 5 to 48 mol%, and 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 which does not have any of an acid-decomposable group and a polar group. It is preferable that the repeating unit which does not have any of an acid-decomposable group and a polar group has an alicyclic hydrocarbon structure. Examples of the repeating unit which does not have any of an acid-decomposable group and a polar group include repeating units described in paragraphs <0236> to <0237> of US Patent Application Publication 2016 / 0026083A1. A preferred example of a monomer corresponding to a repeating unit which does not have any of an acid-decomposable group and a polar group is shown below.

[Chemical Formula 11]

In addition, specific examples of the repeating unit which does not have any of an acid-decomposable group and a polar group include the repeating unit disclosed in paragraph <0433> of the specification of US Patent Application Publication 2016 / 0070167A1. The resin (AX1) may have one type of repeating unit which does not have any of an acid-decomposable group and a polar group, or may have two or more types in combination. The content of the repeating unit without any of the acid-decomposable group and the polar group is preferably 5 to 40 mol%, and more preferably 5 to 30 mol%, relative to all the repeating units in the resin (AX1). 5 to 25 mole% is further preferred.

In addition to the above-mentioned repeating structural units, the resin (AX1) can adjust the dry etching resistance, the standard developer suitability, the substrate adhesion, the resist distribution, or the characteristics generally required for resists, that is, resolution, heat resistance, and sensitivity. Other purposes have various repeating structural units. Examples of such a repeating structural unit include, but are not limited to, a repeating structural unit corresponding to a predetermined unit.

Examples of the predetermined unit include one selected from acrylates, methacrylates, acrylamides, methacrylamides, allyl compounds, vinyl ethers, and vinyl esters. Compounds such as addition polymerizable unsaturated bonds. In addition, an addition polymerizable unsaturated compound that can be copolymerized with a monomer corresponding to the various repeating structural units described above can also be used. In order to adjust various properties, the molar ratio of each repeating structural unit in the resin (AX1) is appropriately set.

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

In the resin (AX1), all the repeating units are preferably composed of (meth) acrylate-based repeating units. In this case, those in which all repeating units are methacrylate-based repeating units, those in which all repeating units are acrylate-based repeating units, and all repeating units derived from methacrylate-based repeating units and acrylate-based repeating units can be used. Either one of them is preferably 50 mol% or less with respect to all repeating units of the resin (AX1).

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

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

The resin (AX1) may be used singly or in combination of two or more kinds. In the composition of the present invention, the content of the resin (AX1) is usually 20.0% by mass or more, more preferably 40.0% by mass or more, more preferably 60.0% by mass or more, and 80.0% by mass or more relative to the total solid content. Better. The upper limit is not particularly limited, and is preferably 99.5 mass% or less, more preferably 99.0 mass% or less, and still more preferably 97.0 mass% or less.

(Resin (AX2)) The resin (AX2) is an alkali-soluble resin having a phenolic hydroxyl group. When the composition of the present invention contains a resin (AX2), the composition of the present invention contains a crosslinking agent (G) described later together with the resin (AX2). The crosslinking agent (G) may be in a form of being supported on a resin (AX2). When the composition of the present invention contains a resin (AX2), the pattern usually formed becomes a negative pattern. As the resin (AX2), it is preferable to have a repeating unit having a phenolic hydroxyl group. The resin (AX2) may have the acid-decomposable group.

As the repeating unit having a phenolic hydroxyl group that the resin (AX2) has, a repeating unit represented by the following general formula (II) is preferred.

[Chemical Formula 12]

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

The divalent linking group represented by B 'has the same meaning as that of T in the general formula (AI), and preferred embodiments thereof are also the same. As the aromatic ring group represented by Ar ', a benzene ring is preferred. 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.

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

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

<Acid generator (B)> The composition of the present invention includes a compound (hereinafter, also referred to as "acid generator (B)") that generates an acid by irradiation with actinic rays or radiation. The acid generator (B) referred to herein corresponds to an acid generator (the above-mentioned acid generator) which is generally used to initiate a deprotection reaction (deprotection reaction of an acid-decomposable resin) of a resin component or to initiate a cross-linking reaction of a resin component. Agent X) and the acid generator (B) do not include the compound represented by the general formula (1). As the acid generator (B), a compound that generates an organic acid by irradiation with actinic rays or radiation is preferred. Examples thereof include a sulfonium salt compound, an iodide salt compound, a diazonium salt compound, a sulfonium salt compound, a fluorenimine sulfonate compound, an oxime sulfonate compound, a diazonium compound, a dihydrazone compound, and an o-nitrobenzyl group. Sulfonate compound.

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

[Chemical Formula 13]

In the general formula (ZI), R ₂₀₁ , R _202, and R ₂₀₃ each independently represent an organic group. The carbon number of the organic group as R ₂₀₁ , R ₂₀₂ and R ₂₀₃ is usually 1 to 30, and 1 to 20 is preferable. In addition, two of R ₂₀₁ to R ₂₀₃ may be bonded to form a ring structure, and the ring may include an oxygen atom, a sulfur atom, an ester bond, a amide bond, or a carbonyl group. Examples of the group formed by the two bonds of R ₂₀₁ to R ₂₀₃ include alkylene (such as butyl and pentayl) and -CH ₂ -CH ₂ -O-CH ₂ -CH ₂ -. Z ^- represents an anion.

Preferred embodiments of the cation in the general formula (ZI) include the corresponding ones of the compound (ZI-1), compound (ZI-2), compound (ZI-3), and compound (ZI-4) described later. Group. The acid generator (B) may be a compound having a plurality of structures represented by the general formula (ZI). For example, R represents a general formula of (ZI) of compound ₂₀₁ ~ R ₂₀₃ and at least one of the other compounds represented by the general formula (ZI) is R ₂₀₁ ~ R ₂₀₃ may be at least one single bond by having Or a compound having a structure in which a linking group is bonded.

First, the compound (ZI-1) will be described. The compound (ZI-1) is an arylfluorene compound in which at least one of R ₂₀₁ to R ₂₀₃ of the general formula (ZI) is an aryl group, that is, a compound in which arylfluorene is a cation. In the arylfluorene compound, all of R ₂₀₁ to R ₂₀₃ may be an aryl group, or a part of R ₂₀₁ to R ₂₀₃ may be an aryl group, and the remaining portion may be an alkyl group or a cycloalkyl group. Examples of the arylfluorene compound include a triarylfluorene compound, a diarylalkylfluorene compound, an aryldialkylfluorene compound, a diarylcycloalkylfluorene compound, and an arylbicycloalkylfluorene compound.

As the aryl group contained in the arylfluorene compound, a phenyl group or a naphthyl group is preferable, and a phenyl group is more preferable. The aryl group may be an aryl group having a heterocyclic structure including an oxygen atom, a nitrogen atom, or a sulfur atom. Examples of the heterocyclic structure include a pyrrole residue, a furan residue, a thiophene residue, an indole residue, a benzofuran residue, and a benzothiophene residue. When the arylfluorene compound has two or more aryl groups, the two or more aryl groups may be the same or different. Aryl hydrazone compounds have a linear or alkyl group having 1 to 15 carbon atoms, a branched alkyl group having 3 to 15 carbon atoms, or a cycloalkyl group having 3 to 15 carbon atoms as required. Preferred examples include methyl, ethyl, propyl, n-butyl, secondary butyl, tertiary butyl, cyclopropyl, cyclobutyl, and cyclohexyl.

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

Next, the compound (ZI-2) will be described. In the compound (ZI-2), R ₂₀₁ to R ₂₀₃ in the formula (ZI) are each independently a compound representing an organic group having no aromatic ring. Here, the aromatic ring also includes an aromatic ring containing a hetero atom. The number of carbons of the organic group having no aromatic ring as R ₂₀₁ to R ₂₀₃ is usually 1 to 30, and the number of carbons is preferably 1 to 20. R ₂₀₁ to R ₂₀₃ are each preferably an alkyl group, a cycloalkyl group, an allyl group, or a vinyl group. A linear or branched 2-oxoalkyl group, a 2-oxocycloalkyl group, or an alkane group is preferred. Oxocarbonylmethyl is more preferred, and linear or branched 2-oxoalkyl is more preferred.

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

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

[Chemical Formula 14]

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

Any two or more of R _1c to R _5c , R _5c and R _6c , R _6c and R _7c , R _5c and R _x and R _x and R _y may be bonded to each other to form a ring structure, and the ring structures may be independent of each other Ground contains an oxygen atom, a sulfur atom, a keto group, an ester bond, or an amidine bond. Examples of the ring structure include an aromatic or non-aromatic hydrocarbon ring, an aromatic or non-aromatic hetero ring, and a polycyclic condensed ring formed by combining two or more of these rings. Examples of the ring structure include a 3 to 10 member ring, a 4 to 8 member ring is more preferable, and a 5 or 6 member ring is more preferable.

_Examples of any two or more of R _1c to R _5c and the groups formed by bonding R _6c and R _7c and R _x and R _y include butyl and pentyl. As the group formed by bonding R _5c and R _6c and R _5c and R _x , a single bond or an alkylene group is preferred. Examples of the alkylene group include a methylene group and an ethylene group. Zc ^- represents an anion.

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

[Chemical Formula 15]

In the general formula (ZI-4), l represents an integer of 0 to 2. r represents an integer from 0 to 8. R ₁₃ represents a group having a hydrogen atom, a fluorine atom, a hydroxyl group, an alkyl group, a cycloalkyl group, an alkoxy group, an alkoxycarbonyl group, or 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 a plurality of R ₁₄ are present, they each independently represent the aforementioned group such as a hydroxyl group. R ₁₅ each independently represents an alkyl group, a cycloalkyl group, or a naphthyl group. These groups may have a substituent. Two R ₁₅ may be bonded to each other to form a ring. When two R ₁₅ are bonded to each other to form a ring, a hetero atom such as an oxygen atom or a nitrogen atom may be contained in the ring skeleton. In one aspect, it is preferable that two R ₁₅ are alkylene groups, which are bonded 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. As the alkyl group, methyl, ethyl, n-butyl or tertiary butyl is preferred.

Next, general formulae (ZII) and (ZIII) will be described. In the general formulae (ZII) and (ZIII), R ₂₀₄ to R ₂₀₇ each independently represent an aryl group, an alkyl group, or a cycloalkyl group. As the aryl group represented by R ₂₀₄ to R ₂₀₇ , a phenyl group or a naphthyl group is preferable, and a phenyl group is more preferable. The aryl group represented by R ₂₀₄ to R ₂₀₇ may be an aryl group having a heterocyclic structure having an oxygen atom, a nitrogen atom, a sulfur atom, 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 and a branched alkyl group having 3 to 10 carbon atoms (for example, methyl, ethyl, and propyl) , Butyl, pentyl, etc.) or a cycloalkyl group having 3 to 10 carbon atoms (for example, cyclopentyl, cyclohexyl, norbornyl, etc.) are preferred.

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

General formula (ZI) in the Z ^-, of the general formula (ZII) of Z ^-, of the general formula (ZI-3) in Zc ^- and the general formula (ZI-4) in the Z ^-, represented by the following general formula The anion represented by (3) is more preferred.

[Chemical Formula 16]

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

Xf represents a fluorine atom or an alkyl group substituted with at least one fluorine atom. The carbon number of the alkyl group is preferably 1 to 10, and more preferably 1 to 4. As the alkyl group substituted with at least one fluorine atom, a perfluoroalkyl group is preferred. 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 Xf of both is a fluorine atom.

R ₄ and R ₅ each independently represent a hydrogen atom, a fluorine atom, an alkyl group, or an alkyl group substituted with at least one fluorine atom. When plural R ₄ and R ₅ exist, R ₄ and R ₅ may be the same or different, respectively. The alkyl group represented by R ₄ and R ₅ may have a substituent, and the number of carbon atoms is preferably 1 to 4. R ₄ and R _{5 are} preferably a hydrogen atom. Specific examples and preferable aspects of the alkyl group substituted with at least one fluorine atom are the same as specific examples and preferable aspects 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 -COO-(-C (= O) -O-), -OCO-, -CONH-, -NHCO-, -CO-, -O-, -S- , -SO-, -SO _2- , alkylene (preferably carbon number 1 to 6), cycloalkylene (preferably carbon number 3 to 15), alkylene (preferably carbon number 2 to 6) and combining these plural divalent linking groups. Among them, -COO-, -OCO-, -CONH-, -NHCO-, -CO-, -O-, -SO _2- , -COO-aralkyl-, -OCO-aralkyl-, Alkylene- or -NHCO-alkylene- is more preferred, -COO-, -OCO-, -CONH-, -SO _2- , -COO-alkylene- or -OCO-alkylene- is more preferred good.

W represents an organic group containing a cyclic structure. Among them, a cyclic organic group is preferred. Examples of the cyclic organic group include an alicyclic group, an aryl group, and a heterocyclic group. The alicyclic group may be monocyclic or polycyclic. Examples of the monocyclic alicyclic group include monocyclic cycloalkyl groups such as cyclopentyl, cyclohexyl, and cyclooctyl. Examples of the polycyclic alicyclic group include polycyclic cycloalkyl groups such as norbornyl, tricyclodecyl, tetracyclodecyl, tetracyclododecyl, and adamantyl. Among them, alicyclic groups having a large volume structure of 7 or more, such as norbornyl, tricyclodecyl, tetracyclodecyl, tetracyclododecyl, and adamantyl, are preferred.

Aryl may be monocyclic or polycyclic. Examples of the aryl group include a phenyl group, a naphthyl group, a phenanthryl group, and an anthryl group. The heterocyclic group may be monocyclic or polycyclic. Polycyclics are more capable of suppressing the diffusion of acids. The heterocyclic group may be aromatic or non-aromatic. Examples of the aromatic heterocyclic ring include a furan ring, a thiophene ring, a benzofuran ring, a benzothiophene ring, a dibenzofuran ring, a dibenzothiophene ring, and a pyridine ring. Examples of the heterocyclic ring having no aromaticity include a tetrahydropiperan ring, a lactone ring, a sultone ring, and a decahydroisoquinoline ring. Examples of the lactone ring and the sultone ring include the lactone structure and the sultone structure exemplified in the aforementioned resin. As the hetero ring in the heterocyclic group, a furan ring, a thiophene ring, a pyridine ring, or a decahydroisoquinoline ring is particularly preferred.

The cyclic organic group may have a substituent. Examples of the substituent include an alkyl group (which may be linear or branched, and preferably having 1 to 12 carbon atoms), a cycloalkyl group (which may be a monocyclic ring, a polycyclic ring, or a spiro ring) Any one of them is preferably 3 to 20 carbons), aryl (6 to 14 carbons is preferred), hydroxyl, alkoxy, ester, amido, carbamate, and urea , Thioether group, sulfonamide group and sulfonate group. In addition, the carbon constituting the cyclic organic group (carbon contributing to ring formation) may be a 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) qW or SO ₃ ^-- CF ₂ -CH ( CF ₃ ) -OCO- (L) q'-W is more preferred. Here, L, q, and W are the same as those in the general formula (3). q 'represents an integer from 0 to 10.

In one aspect, the general formula (ZI) in the Z ^-, of the general formula (ZII) of Z ^-, of the general formula (ZI-3) in Zc ^- and the general formula (ZI-4) in the Z ^-, Anions represented by the following general formula (4) are also preferable.

[Chemical Formula 17]

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

General formula (ZI) in the Z ^-, of the general formula (ZII) of Z ^-, of the general formula (ZI-3) in Zc ^- and the general formula (ZI-4) in the Z ^-, represented by the following general formula The anion represented by (5) is also preferable.

[Chemical Formula 18]

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

General formula (ZI) in the Z ^-, of the general formula (ZII) of Z ^-, of the general formula (ZI-3) in Zc ^- and the general formula (ZI-4) in the Z ^- anion of benzenesulfonic acid may be, A benzenesulfonate anion substituted with a branched alkyl group or a cycloalkyl group is preferred.

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

[Chemical Formula 19]

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 that may be further included include a fluorine atom and a hydroxyl group.

n represents an integer of 0 or more. As n, 1 to 4 are preferable, 2 to 3 are more preferable, and 3 is further 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 fluorenylene group, a fluorenyl group, a sulfonate group, an ester group, and a combination of two or more of these groups.

B represents a hydrocarbon group.

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

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

[Chemical Formula 20]

Comparisons of the anion Z ^- in the general formula (ZI), the anion Z ^- in the general formula (ZII), Zc ^{-in the} general formula (ZI-3), and Z ^- in the general formula (ZI-4) are shown below. Good example.

[Chemical Formula 21]

Any of the above-mentioned cations and anions can be used in combination as an acid generator (B).

The acid generator (B) may be in the form of a low-molecular compound, or may be in the form of being incorporated into a part of a polymer. The form of the low-molecular compound and the form combined with a part of the polymer may be used in combination. The form in which the acid generator (B) is a low-molecular compound is preferred. 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 even more preferably 1,000 or less. When the acid generator (B) is incorporated into a part of the polymer, it may be incorporated into a part of the resin (A), or may be incorporated into a resin different from the resin (A). The acid generator (B) may be used singly or in combination of two or more kinds. In the composition, based on the total solid content of the composition, the content of the acid generator (B) (the total amount when there are a plurality of species) is preferably 0.1 to 20.0% by mass, and more preferably 0.5 to 15.0% by mass. 1.0 to 15.0% by mass is more preferable. When the acid generator contains a compound represented by the general formula (ZI-3) or (ZI-4), the content of the acid generator contained in the composition is based on the total solid content of the composition (there is a plurality of The total amount at the time of seeding) is preferably 5 to 35% by mass, and more preferably 7 to 30% by mass.

In addition, the acid dissociation constant pKa of the acid generated by decomposing the acid generator (B) by actinic radiation or radiation is smaller than the pKa of the acid generated from the compound represented by the following general formula (1): Better. As the acid generator (B) is decomposed by irradiation with actinic rays or radiation, the acid dissociation constant pKa of the acid produced by this is preferably -1.00 or less, more preferably -1.50 or less, and -2.00 or less is more good. The lower limit 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 this specification, the acid dissociation constant pKa represents the acid dissociation constant pKa in an aqueous solution, and is, for example, a chemical handbook (II) (Revised 4th Edition, 1993, edited by the Japan Chemical Society, Maruzen Inc.) In the description, the lower the value, the higher the acid strength. Specifically, the acid dissociation constant pKa in the aqueous solution can be actually measured by measuring the acid dissociation constant at 25 ° C. using an infinitely diluted aqueous solution, and the following software package 1 can be used to calculate the basis for Hammett The value of a database of substituent constants and well-known literature values. All pKa values described in this specification represent values obtained by calculation using the software package. Software Suite 1: Advanced Chemistry Development (ACD / Labs) Software V8.14 for Solaris (1994-2007 ACD / Labs)

<Acid diffusion control agent> The composition of this invention contains an acid diffusion control agent. The acid diffusion control agent captures an acid generated from the acid generator (B) and the like upon exposure, and functions as an inhibitor to suppress the reaction of the acid-decomposable resin in the unexposed portion due to the excess generation of acid. The composition of the present invention may contain at least a compound represented by the general formula (1) as an acid diffusion controlling agent, and may include other acid diffusion preventing agents within a range that does not inhibit the effect of the present invention. In addition, a compound represented by the general formula (1) will be described below as an acid diffusion control agent (C), and another acid diffusion preventing agent will be described as an acid diffusion control agent (D).

(Acid Diffusion Control Agent (C)) Hereinafter, a compound represented by the general formula (1) will be described. <Compounds represented by general formula (1)>

[Chemical Formula 22]

In the above formula, Ar ₁ , Ar ₂ and Ar ₃ each independently represent an aromatic hydrocarbon group. A ₁ S ⁺ and substituted in the ortho position of the bonded carbon atoms in the Ar _1, and represents ^{_{-L 1 -CO 2 -, -L 2}} -SO 3 - or ^{_{-L 3 -X 1 -N - -Y 1}} . L ₁ , L ₂ and L ₃ each independently represent a single bond or a divalent linking group. X ₁ represents -SO ₂ -or -CO-. Y ₁ represents -SO ₂ -R _A or -CO-R _B. R _A and R _B each independently represent a monovalent substituent. In addition, Ar ₁ , Ar ₂ and Ar ₃ may further have a substituent, and the substituents may be bonded to each other to form a ring.

The aromatic hydrocarbon group represented by Ar ₁ , Ar _2, and Ar ₃ may be any of a monocyclic structure (monocyclic aromatic hydrocarbon group) and a polycyclic structure (polycyclic aromatic hydrocarbon group). The carbon number of the aromatic hydrocarbon group is not particularly limited, but 5 to 18 is preferable, and 5 to 10 is more preferable. Specific examples of the aromatic hydrocarbon group include aryl (phenyl, tolyl, xylyl, etc.), naphthyl, anthracenyl, phenanthryl, indenyl, naphthobutenyl, fluorenyl, and fluorenyl Wait. As the aromatic hydrocarbon group represented by Ar ₁ , Ar _2, and Ar ₃ , a monocyclic aromatic hydrocarbon group is more preferable, and a phenyl group is more preferable from the viewpoint that the LWR performance and CDU performance of the formed pattern are more excellent.

Ar ₁ , Ar ₂ and Ar ₃ may further have a substituent. The kind of the substituent is not particularly limited, and examples thereof include the groups exemplified in the substituent group T described above. As the substituent, a non-aromatic substituent (in addition, the "non-aromatic substituent" in this specification means a substituent which does not exhibit aromaticity, and examples thereof include a substituent having no aromatic ring. ) Is preferred, and the alkyl group (can be any of linear, branched, and cyclic. The number of carbons is preferably 1 to 20, more preferably 1 to 10, and further preferably 1 to 6. ), Fluoroalkyl (represents an alkyl group substituted with at least one fluorine atom. The carbon number is preferably 1 to 10, and more preferably 1 to 4. The alkyl group substituted with at least one fluorine atom is a perfluoroalkyl group. It is preferable.), A halogen atom (for example, a fluorine atom, a chlorine atom, a bromine atom, an iodine atom, etc.), a thioalkyl group (which may be linear, branched, or cyclic) Carbon number is preferably from 1 to 20, more preferably from 1 to 10, and even more preferably from 1 to 6.) or alkoxy (can be any of linear, branched, and cyclic) One. The carbon number is preferably from 1 to 20, more preferably from 1 to 10, and even more preferably from 1 to 6.) is more preferred.

Regarding the substituents substituted with Ar ₁ , Ar ₂ and Ar ₃ , the substituents may be bonded to each other to form a ring. The ring may be any of aromatic and non-aromatic properties, but non-aromatic properties are preferred from the viewpoint that the formed pattern has better LWR performance and CDU performance. In addition, the ring may further have a substituent (for example, examples thereof in the substituent group T).

As the compound represented by the general formula (1), from the standpoint that the LWR performance and CDU performance of the formed pattern are more excellent, any one or more of Ar ₁ , Ar _2, and Ar ₃ are unsubstituted monocyclic rings. An aromatic hydrocarbon group is preferred (in addition, Ar ₁ indicates that it does not have a substituent other than A ₁ ). It is more preferable that any two or more of Ar ₁ , Ar _2, and Ar ₃ be a monocyclic aromatic hydrocarbon group. Ar ₁ It is more preferable that Ar ₂ and Ar ₃ are monocyclic aromatic hydrocarbon groups.

A ₁ S ⁺ and substituted in the ortho position of the bonded carbon atoms in the Ar _1, and represents ^{_{-L 1 -CO 2 -, -L 2}} -SO 3 - or ^{_{-L 3 -X 1 -N - -Y 1}} . Here, "in the S ⁺ and Ar ₁ bonded to ortho carbon atoms of the substituent" represents a sum of carbon atoms bonded ortho position in Ar _1, A ₁ is expressed in the general formula (1) in a sulfonium cation Bit substitution. In other words, in Ar ₁ , A _{1 is} substituted with a carbon atom adjacent to the carbon atom at the bonding position of the sulfonium cation specified in the general formula (1).

L ₁ , L _2, and L ₃ each independently represent a single bond or a divalent linking group. From the viewpoint of better LWR performance and CDU performance of the formed pattern, a single bond is preferred. The divalent linking group represented by L ₁ , L _2, and L ₃ is not particularly limited, and examples thereof include -O-, -CO-, and divalent hydrocarbon groups (for example, alkylene, alkylene, Alkynyl and arylene) and two or more groups combining these. As the divalent linking group represented by L ₁ , L _2, and L ₃ , among them, from the viewpoint that LWR performance and CDU performance are more excellent, -O-, -CO-, and an alkylene group having 1 to 10 carbon atoms , An alkenyl group having 2 to 10 carbon atoms, an alkynyl group having 2 to 10 carbon atoms, and a combination of two or more of these groups are preferred, -O-, -CO-, and 1 to 6 carbon atoms An alkylene group and two or more groups in which these are combined are more preferred, an alkylene group having 1 to 6 carbon atoms is more preferred, and an alkylene group having 1 to 3 carbon atoms is particularly preferred. In addition, it is preferable that the atom at the bonding position with Ar ₁ in L ₁ , L _2, and L ₃ is an atom other than an oxygen atom. For example, even when the divalent linking group represented by L ₁ , L _2, and L ₃ contains -O- (oxygen atom), an atom other than an oxygen atom (for example, a carbon atom) is bonded to Ar ₁ as described above. Is better.

As A ₁ , -L ₁ -CO ₂ ^- or -L ₃ -X ₁ -N ^-- Y ₁ is preferable from the viewpoint that the formed pattern has better LWR performance and CDU performance.

X ₁ represents -SO ₂ -or -CO-. Y ₁ represents -SO ₂ -R _A or -CO-R _B.

R _A and R _B each independently represent a monovalent substituent. The monovalent substituent represented by R _A and R _B is not particularly limited, and examples thereof include the groups exemplified in the above-mentioned substituent group T. As the monovalent substituent represented by R _A and R _B , an alkyl group (which may be any of linear, branched, and cyclic. The number of carbons is preferably 1 to 20, and 1 to 10 is preferred. More preferably, 1 to 6 are further preferred, and 1 to 3 are particularly preferred.), Alkenyl (can be any of linear, branched, and cyclic. Carbon number of 2 to 20 is preferred , 2 to 10 is more preferred, and 2 to 6 is more preferred.) Or alkynyl (which may be any of linear, branched, and cyclic. The number of carbons is preferably 2 to 20, and 2 to 2 10 is more preferred, and 2 to 6 are more preferred.) Is more preferred, alkyl groups having 1 to 10 carbon atoms are more preferred, and alkyl groups having 1 to 6 carbon atoms are further preferred. The alkyl group, alkenyl group, and alkynyl group may further have a substituent (for example, those exemplified in the substituent group T).

From the viewpoint that the function as an acid diffusion control agent is more excellent, the pKa of the acid generated from the compound represented by the general formula (1) is preferably more than -2.00, more preferably 1.00 or more, and 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 from 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, and more preferably 2.00 or more . The upper limit value is not particularly limited, and is, for example, 10.0. As described above, the acid diffusion control agent, that is, the acid generated from the compound represented by the general formula (1) becomes a relatively weak acid with respect to the acid generated from the acid generator (B). As long as the difference between the pKa of the acid generated from 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 used as an acid diffusion control agent. Better function.

As the compound represented by the general formula (1), a compound represented by the following general formula (2) is preferable from the viewpoint that the LWR performance and CDU performance of the formed pattern are more excellent. The general formula (2) will be described below. (Compound represented by general formula (2))

[Chemical Formula 23]

In the above formulas, Ar _2, Ar ₃ and A ₁ in the general formula (1) Ar _2, Ar ₃ and A ₁ have the same meaning and preferred aspects are also the same.

R ₁ , R ₂ , R ₃ and R ₄ each independently represent a hydrogen atom or a non-aromatic substituent. The substituents represented by R ₁ , R ₂ , R _3, and R ₄ are not particularly limited as long as they are non-aromatic substituents. The alkyl group (which may be linear, branched, or cyclic) Either. The number of carbon atoms is preferably from 1 to 20, more preferably from 1 to 10, and even more preferably from 1 to 6.), fluoroalkyl (represents an alkyl group substituted with at least one fluorine atom. The number of carbons is from 1 to 10 is more preferable, and 1 to 4 is more preferable. In addition, an alkyl group substituted with at least one fluorine atom is preferably a perfluoroalkyl group.), A halogen atom (as the halogen atom, for example, a fluorine atom and a chlorine atom may be mentioned , Bromine atom, iodine atom, etc.), thioalkyl (can be any of linear, branched, and cyclic. The number of carbons is preferably 1 to 20, more preferably 1 to 10, 1 -6 is more preferred.) Or alkoxy (can be any of linear, branched, and cyclic. The number of carbons is preferably 1 to 20, more preferably 1 to 10, and 1 to 6 Is even better.) Is even better. R ₁ , R ₂ , R ₃ and R ₄ may be bonded to each other to form a ring. The ring is preferably non-aromatic. In addition, the ring may further have a substituent (for example, examples thereof in the substituent group T). Among them, from the viewpoint that the formed pattern has better LWR performance and CDU performance, it is preferable that R ₁ , R ₂ , R _3, and R ₄ are bonded to each other to form a ring structure.

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 any of aromatic and non-aromatic properties, but non-aromatic properties are preferred from the viewpoint that the formed pattern has better LWR performance and CDU performance. In addition, the ring may further have a substituent (for example, examples thereof in the substituent group T).

As the compound represented by the general formula (2), from the viewpoint that the LWR performance and the CDU performance of the formed pattern are more excellent, R ₁ to R ₄ are all hydrogen atoms or at least one of Ar ₂ and Ar ₃ is Substituted monocyclic aromatic hydrocarbon groups are preferred. Among them, from the viewpoint that the formed pattern has better LWR performance and CDU performance, R ₁ to R ₄ are all hydrogen atoms, and one of Ar ₂ and Ar ₃ is an unsubstituted monocyclic aromatic hydrocarbon group, or Ar ₂ and Ar ₃ are both unsubstituted monocyclic aromatic hydrocarbon groups, or R ₁ to R ₄ are all hydrogen atoms, and Ar ₂ and Ar ₃ are both unsubstituted monocyclic aromatic hydrocarbon groups.

The compound represented by the said General formula (1) can be synthesize | combined by a well-known method, for example.

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

[Chemical Formula 24]

The compound represented by the general formula (1) may be used singly or in combination of two or more kinds. In the composition of the present invention, based on the total solid content of the composition, the content of the compound represented by the general formula (1) (the total amount in the case of plural types) is preferably 0.1 to 10% by mass, and 0.5 to 8.0. The mass% is better. 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 by mass ratio. For example, it is 1/99 to 99/1, 90/10 to 30/70 is more preferable, and 85/15 to 40/60 is more preferable.

(Acid Diffusion Control Agent (D)) The composition of the present invention may include, in a range not interfering with the effects of the present invention, the acid diffusion control agent (C) (a compound represented by the general formula (1) corresponds to the compound). Another acid diffusion control agent (hereinafter, "acid diffusion control agent (D)"). Examples of the acid diffusion controlling agent (D) include a basic compound (DA), a basic compound (DB) capable of reducing or disappearing basicity due to actinic radiation or radiation, and relatively weak acids with respect to the acid generator. An onium salt (DC), a low-molecular compound (DD) having a nitrogen atom and a group detached by the action of an acid, or an onium salt compound (DE) having a nitrogen atom in the cation portion are used as an acid diffusion control agent. In the composition of this invention, a well-known acid-diffusion control agent can be used suitably. For example, paragraphs <0627> to <0664> of U.S. Patent Application Publication No. 2016 / 0070167A1, paragraphs <0095> to <0187> of U.S. Patent Application Publication No. 2015 / 0004544A1, and U.S. Patent Application Publication No. 2016 / 0237190A1 can be used. The well-known compounds disclosed in paragraphs <0403> to <0423> and paragraphs <0259> to <0328> of US Patent Application Publication No. 2016 / 0274458A1 are preferably used as acid diffusion control agents (D).

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

[Chemical Formula 25]

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

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

As the basic compound (DA), guanidine, aminopyrrolidine, pyrazole, pyrazoline, piperazine, aminomorpholine, aminoalkylmorpholine, or piperidine, etc. are preferred, and have an imidazole structure. Acridine bicyclic structure, onium hydroxide structure, onium carboxylic acid structure, trialkylamine structure, aniline structure or pyridine structure compound, alkylamine derivative having hydroxyl and / or ether linkage or having hydroxyl and / or ether linkage Of these, aniline derivatives are more preferred.

Basic compounds (DB) whose basicity is reduced or disappeared by irradiation with actinic rays or radiation (hereinafter, also referred to as "compounds (DB)") have proton-accepting functional groups and are activated by actinic rays or A compound which is decomposed by irradiation of radiation, thereby reducing or disappearing the proton acceptor property or changing the proton acceptor property to an acidic property.

The proton acceptor functional group is a group capable of electrostatic interaction with a proton or a functional group having an electron, for example, a functional group having a giant ring structure such as a cyclic polyether or having a functional group which does not work on π conjugation A functional group of a nitrogen atom that does not share an electron pair. The nitrogen atom having a non-shared electron pair which does not contribute to the π conjugation is, for example, a nitrogen atom having a partial structure represented by the following formula.

[Chemical Formula 26]

Preferred partial structures of the proton accepting functional group include, for example, a crown ether structure, an aza crown ether structure, a 1-3 amine structure, a pyridine structure, an imidazole structure, and a pyridine structure.

The compound (DB) produces a compound that is decomposed by irradiation with actinic rays or radiation, whereby the proton acceptor property is reduced, disappears, or becomes protonic from the proton acceptor property. Here, the reduction, disappearance, or change from proton acceptor to acidity of a proton acceptor is a change in proton acceptor caused by the addition of a proton acceptor functional group to a proton. Specifically, it means that the When a compound (DB) of an acceptor functional group generates a proton adduct, the equilibrium constant in the chemical equilibrium decreases. The proton acceptor property can be confirmed by performing pH measurement.

The compound (DB) is decomposed by irradiation with actinic rays or radiation, and the acid dissociation constant pKa of the compound produced thereby satisfies pKa <-1, preferably -13 <pKa <-1, and -13 <PKa <-3 is further preferred.

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

In the composition of the present invention, an onium salt (DC), which is a relatively weak acid with respect to the acid generator, can be used as the acid diffusion control agent. When an acid generator is used in combination with an onium salt that generates a relatively weak acid relative to the acid generated from the acid generator, if the acid generated from the acid generator by actinic radiation or radiation is The conflict of the onium salts of the weak acid anions of the reaction produces an onium salt having a strong acid anion which releases a weak acid by salt exchange. In this process, the strong acid is replaced with a weak acid with a lower catalyst energy. Therefore, it is clear that the acid is inactivated and the acid diffusion control can be performed.

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

[Chemical Formula 27]

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 carbons which may have a substituent (wherein the carbon adjacent to S, a fluorine atom is an unsubstituted group), R ⁵² is an organic group, Y ³ is a linear, branched, or cyclic alkylene or aryl group, Rf is a hydrocarbon group containing a fluorine atom, and M ^{+ is} each independently an ammonium cation, a phosphonium cation, or an iodine cation.

Preferable examples of the sulfonium cation or iodine cation represented by M ⁺ include a sulfonium cation exemplified in the general formula (ZI) and an iodine cation exemplified in the general formula (ZII).

A low-molecular compound (DD) (hereinafter, also referred to as a "compound (DD)") having a nitrogen atom and a group detached by the action of an acid is a group having a nitrogen atom detached by the action of an acid An amine derivative is preferred. As the group to be removed by the action of an acid, an acetal group, a carbonate group, a urethane group, a tertiary ether group, a tertiary hydroxyl group, or a hemiamine acetal ether group is preferable, and the urethane group or Hemiamine acetal ether groups are more preferred. The molecular weight of the compound (DD) is preferably from 100 to 1,000, more preferably from 100 to 700, and even more preferably from 100 to 500. The compound (DD) may have a urethane group having a protective group on a nitrogen atom. The protective group constituting the urethane group is represented by the following general formula (d-1).

[Chemical Formula 28]

In the general formula (d-1), Rb each independently represents a hydrogen atom, an alkyl group (preferably 1 to 10 carbon atoms), a cycloalkyl group (preferably 3 to 30 carbon atoms), and an aryl group (preferably Is 3 to 30 carbons), aralkyl (preferably 1 to 10 carbons) or alkoxyalkyl (preferably 1 to 10 carbons). Rb may also be bonded to each other to form a ring. Rb may be connected to each other to form a ring. The alkyl group, cycloalkyl group, aryl group, and aralkyl group represented by Rb may be independently independently functional groups such as a hydroxyl group, a cyano group, an amino group, a pyrrolidinyl group, a piperidinyl group, a morpholinyl group, and an oxo group. Oxygen or halogen atom substitution. The same applies to the alkoxyalkyl group represented by Rb.

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

It is preferable that the compound (DD) has a structure represented by the following general formula (6).

[Chemical Formula 29]

In the general formula (6), l represents an integer of 0 to 2, m represents an integer of 1 to 3, and satisfies l + m = 3. Ra represents a hydrogen atom, an alkyl group, a cycloalkyl group, an aryl group, or an aralkyl group. When l is 2, the two Ras may be the same or different, and the two Ras may be connected to each other to form a heterocyclic ring with the nitrogen atom in the formula. The heterocyclic ring may contain heteroatoms other than the nitrogen atom in the formula. Rb has the same meaning as Rb in the general formula (d-1), and 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 may be independently substituted with the same group as the aforementioned group. The aforementioned group is a group in which an alkyl group, a cycloalkyl group, an aryl group, and an aralkyl group as Rb may be substituted.

Specific examples of the alkyl group, cycloalkyl group, aryl group, and aralkyl group of the Ra (these groups may be substituted by the above-mentioned groups) include the same groups as the specific examples described above with respect to Rb. Specific examples of the particularly preferred compound (DD) in the present invention include, but are not limited to, those disclosed in paragraph <0475> of the specification of US Patent Application Publication No. 2012 / 0135348A1.

The onium salt compound (DE) (hereinafter, also referred to as "compound (DE)") having a nitrogen atom in the cation part is preferably a compound having a basic site containing a nitrogen atom in the cation part. The basic site is preferably an amine group, and the aliphatic amine group is more preferred. It is further preferred that all atoms adjacent to the nitrogen atom in the basic site are hydrogen atoms or carbon atoms. From the standpoint of improving basicity, it is preferable that the electronically seekable functional group (such as a carbonyl group, a sulfonyl group, a cyano group, and a halogen atom) is not directly bonded to a nitrogen atom. Preferred specific examples of the compound (DE) include, but are not limited to, compounds disclosed in paragraph <0203> of the specification of US Patent Application Publication No. 2015 / 0309408A1.

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

[Chemical Formula 30] [Chemical Formula 31]

In the composition of the present invention, the acid diffusion control agent (D) may be used alone or in combination of two or more. When the acid diffusion control agent (D) is contained in the composition, the content of the acid diffusion control agent (D) (the total amount in the case of plural types) is preferably 0.1 to 10.0% by mass based on the total solid content of the composition. , More preferably 0.1 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 of the surface of the photosensitized or radiation-sensitive film. Thereby, development characteristics can be improved, outgassing can be suppressed, follow-up of the liquid immersion liquid during liquid immersion exposure, and defects of liquid immersion can be reduced. The hydrophobic resin (E) is preferably designed to be biased on the surface of the resist film, but unlike the surfactant, it is not necessary to have a hydrophilic group in the molecule, and it can uniformly mix polar and non-polar substances Does not work.

From the viewpoint of bias toward the surface layer of the film, the hydrophobic resin (E) is one selected from the group consisting of "fluorine atom", "silicon atom", and "CH ₃ partial structure contained in side chain portion of resin". A resin of at least one repeating unit is preferred. When the hydrophobic resin (E) contains a fluorine atom and / or a silicon atom, the above-mentioned fluorine atom and / or silicon atom in the hydrophobic resin (E) may be contained in the main chain of the resin or may be contained in a side chain.

When the hydrophobic resin (E) contains a fluorine atom, as the partial structure having a fluorine atom, a resin containing an alkyl group having a fluorine atom, a cycloalkyl group having a fluorine atom, or an aryl group having a fluorine atom is preferred.

It is preferable that the hydrophobic resin (E) 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 conversion group.) (Z) A group which is decomposed by the action of an acid group

Examples of the acid group (x) include a phenolic hydroxyl group, a carboxylic acid group, a fluorinated alcohol group, a sulfonic acid group, a sulfoamido group, a sulfoimino group, and (alkylsulfonyl) (alkylcarbonyl) Methylene, (alkylsulfonyl) (alkylcarbonyl) fluorenimine, bis (alkylcarbonyl) methylene, bis (alkylcarbonyl) fluorenimine, bis (alkylsulfonyl) Methylene, bis (alkylsulfonyl) fluorenimine, tris (alkylcarbonyl) methylene and tris (alkylsulfonyl) methylene, etc. As the acid group, a fluorinated alcohol group (preferably hexafluoroisopropanol), a sulfonylimino group or a bis (alkylcarbonyl) methylene group is preferred.

Examples of the group (y) whose solubility in the alkali developer is increased by decomposition by the action of the alkali developer, include, for example, a lactone group, a carboxylic acid ester group (-COO-), and an acid anhydride group (-C (O ) OC (O)-), acid ammonium (-NHCONH-), carboxylic acid thioester (-COS-), carbonate (-OC (O) O-), sulfate (-OSO ₂ O-) and a sulfonate group (-SO ₂ O-) and the like, and a lactone group or a carboxylate group (-COO-) are preferred. Examples of repeating units containing these groups include repeating units in which the groups are directly bonded to the main chain of the resin, and examples thereof include repeating units derived from acrylate and methacrylate. In the repeating unit, the groups may be bonded to the resin's main chain by a linking group. Alternatively, the repeating unit is used when polymerizing a polymerization initiator or a chain transfer agent having such groups, and can be introduced into a terminal of a resin. Examples of the repeating unit having a lactone group include the same as the repeating unit having a lactone structure described in the item of the resin (AX1).

The content of the repeating unit (y) having a group (y) having an increased solubility in the alkali developing solution by decomposition by the action of the alkali developing solution is 1 to 100 mole% relative to all the repeating units in the hydrophobic resin (E). Preferably, 3 to 98 mol% is more preferred, and 5 to 95 mol% is even more preferred.

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

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

On the other hand, especially when the hydrophobic resin (E) includes a CH ₃ partial structure in a side chain portion, it is also preferable that the hydrophobic resin (E) does not substantially include a fluorine atom and a silicon atom. Moreover, it is preferable that the hydrophobic resin (E) consists essentially of repeating units (consisting only of atoms selected from a carbon atom, an oxygen atom, a hydrogen atom, a nitrogen atom, and a sulfur atom).

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

The total content of the residual monomers 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 the hydrophobic resin (E), a known resin can be appropriately selected and used alone or as a mixture thereof. For example, the known resins disclosed in paragraphs <0451> to <0704> of US Patent Application Publication No. 2015 / 0168830A1 and paragraphs <0340> to <0356> of US Patent Application Publication No. 2016 / 0274458A1 can be preferably used. Used as a hydrophobic resin (E). In addition, the repeating units disclosed in paragraphs <0177> to <0258> of US Patent Application Publication No. 2016 / 0237190A1 are also preferred 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.

[Chemical Formula 32]

[Chemical Formula 33]

The hydrophobic resin (E) may be used singly or in combination of two or more kinds. From the viewpoint of considering both the liquid immersion liquid followability and the development characteristics in liquid immersion exposure, it is preferable to use a mixture of two or more types of hydrophobic resins (E) having different surface energies. 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 based on the total solid content in the composition.

<Solvent (F)> The composition of the present invention may contain a solvent. In the composition of the present invention, a known resist solvent can be appropriately used. For example, paragraphs <0665> to <0670> of U.S. Patent Application Publication 2016 / 0070167A1, paragraphs <0210> to <0235> of U.S. Patent Application Publication 2015 / 0004544A1 can be preferably used, and U.S. Patent Application Publication 2016 / 0237190A1, paragraphs <0424> to <0426>, and well-known solvents disclosed in paragraphs <0357> to <0366> of US Patent Application Publication 2016 / 0274458A1. Examples of the solvent that can be used in preparing the composition include alkylene glycol monoalkyl ether carboxylic acid esters, alkylene glycol monoalkyl ether carboxylic acid esters, alkyl lactate esters, and alkyl alkoxypropionate alkyl groups. Esters, cyclic lactones (preferably 4 to 10 carbons), monoketone compounds that may have rings (preferably 4 to 10 carbons), alkylene carbonates, alkyl alkoxyacetates, and acetone Organic solvents such as acid alkyl esters.

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

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

<Surfactant (H)> The composition of the present invention may contain a surfactant. When a 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, especially 220 nm or less is used, a pattern with low adhesion and development defects can be obtained with good sensitivity and resolution. Examples of the fluorine-based and / or silicon-based surfactants include the surfactants described in paragraph <0276> of the specification of US Patent Application Publication No. 2008/0248425. In addition, other surfactants other than fluorine-based and / or silicon-based surfactants described in paragraph <0280> of the specification of US Patent Application Publication No. 2008/0248425 can also be used.

These surfactants may be used individually by 1 type, and may use 2 or more types together. When the composition of the present invention contains a surfactant, the content of the surfactant relative to the total solid content of the composition is preferably 0.0001 to 2.0% by mass, and more preferably 0.0005 to 1.0% by mass. On the other hand, by setting the content of the surfactant to the total solid content of the composition to be 10 ppm or more, the surface bias of the hydrophobic resin (E) is improved. Thereby, the surface of the photosensitized radiation- or radiation-sensitive film can be made more hydrophobic, and the water followability during liquid immersion exposure can be improved.

(Other Additives) The composition of the present invention may further include 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.

<Preparation method> Generally, the solid content concentration of the composition of the present invention is preferably 1.0 to 10% by mass, more preferably 2.0 to 5.7% by mass, and even more preferably 2.0 to 5.3% by mass. The solid content concentration is a mass percentage of the mass of the resist component other than the solvent with respect to the total mass of the composition.

In addition, from the viewpoint of improving the resolution, the film thickness of the photosensitized radioactive or radiation-sensitive film composed of the composition of the present invention is preferably 90 nm or less, and more preferably 85 nm or less. Such a film thickness can be set by setting the solid content concentration in the composition to an appropriate range so as to have a suitable viscosity and to improve the coatability or film-forming properties.

Regarding the composition of the present invention, the above-mentioned components are dissolved in a predetermined organic solvent, preferably in the above-mentioned mixed solvent, filtered through a filter, and then coated and used on a predetermined support (substrate). The pore size of the filter used for filter filtration is preferably 0.1 μm or less, more preferably 0.05 μm or less, and 0.03 μm or less is more preferable. The filter is preferably made of polytetrafluoroethylene, polyethylene or nylon. In filter filtration, for example, disclosed in Japanese Patent Application Laid-Open No. 2002-062667 (Japanese Patent Application Laid-Open No. 2002-062667), circulating filtering may be performed, or a plurality of filters may be connected in series or in parallel to perform filtering. The composition can be filtered multiple times. Furthermore, the composition may be subjected to a degassing treatment and the like before and after the filtration by the filter.

<Use> The composition of the present invention relates to a photosensitized radioactive or radiation-sensitive resin composition that changes its properties by reacting with actinic radiation or radiation. More specifically, the composition of the present invention relates to a semiconductor manufacturing process such as IC (Integrated Circuit), manufacturing of a circuit board such as a liquid crystal or a thermal head, manufacturing of a mold structure for imprinting, and other photosensitivity. Photoresistive or radiation-sensitive resin composition in an etching process or in the manufacture of 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, a MEMS (Micro Electro Mechanical Systems), and the like.

[Pattern forming method] The present invention also relates to a pattern forming method using the above-mentioned photosensitive radiation- or radiation-sensitive resin composition. The pattern forming method of the present invention will be described below. The photosensitized radioactive or radiation-sensitive film of the present invention will be described together with the description of the pattern forming method.

The pattern forming method of the present invention includes: (i) a process (resistance) for forming a resist film (photosensitive radioactive or radiation-sensitive film) on a support by using the above-mentioned photosensitive radioactive or radiation-sensitive resin composition; (Film formation process), (ii) a process for exposing the resist film (irradiating actinic rays or radiation) (exposure process), and (iii) a process for developing the exposed resist film using a developing solution ( Development process).

The pattern forming method of the present invention is not particularly limited as long as it includes the processes (i) to (iii), and may further include the following processes. In the pattern forming method of the present invention, the exposure method in the (ii) exposure process may be liquid immersion exposure. It is preferable that the pattern forming method of the present invention has (iv) a pre-bake (PB) process before (ii) the exposure process. The pattern forming method of the present invention preferably has (v) a Post Exposure Bake (PEB) process after (ii) the exposure process and (iii) before the development process. The pattern forming method of the present invention may have a plurality of (ii) exposure processes. The pattern forming method of the present invention may have a plurality of (iv) pre-baking processes. The pattern forming method of the present invention may have a plurality of (v) post-exposure heating processes.

In the pattern forming method of the present invention, the above-mentioned (i) film-forming process, (ii) exposure process, and (iii) development process can be performed by a generally known method. If necessary, a resist underlayer film (for example, SOG (Spin On Glass), SOC (Spin On Carbon), and antireflection film) may be formed between the resist film and the support. ). As a material constituting the resist underlayer film, a known organic-based or inorganic-based material can be appropriately used. A protective film (top coat) may be formed on the resist film. As a protective film, a well-known material can be used suitably. For example, US Patent Application Publication No. 2007/0178407, US Patent Application Publication No. 2008/0085466, US Patent Application Publication No. 2007/0275326, and US Patent Application Publication No. 2016/0299432 can be preferably used. The composition for forming a protective film disclosed in US Patent Application Publication No. 2013/0244438 and International Patent Application Publication No. 2016 / 157988A. As a composition for forming a protective film, it is preferable to include the said acid diffusion control agent. A protective film may be formed on the upper layer of the resist film containing the above-mentioned hydrophobic resin.

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

Regarding the heating temperature, in any of (iv) the pre-baking process and (v) the post-exposure heating process, 70 to 130 ° C. is more preferred, and 80 to 120 ° C. is more preferred. Regarding the heating time, in any of (iv) the pre-baking process and (v) the post-exposure heating process, 30 to 300 seconds is preferable, 30 to 180 seconds is more preferable, and 30 to 90 seconds is further Better. The heating may be performed using a member provided in the exposure device and the developing device, or may be performed using a heating plate or the like.

The wavelength of the light source used in the exposure process is not limited, and examples thereof include infrared light, visible light, ultraviolet light, extreme ultraviolet light, extreme ultraviolet light (EUV), X-rays, and electron beams. The medium and far ultraviolet light is preferred, and its wavelength is preferably below 250 nm, more preferably below 220 nm, and even more preferably between 1 and 200 nm. Specifically, it is KrF excimer laser (248nm), ArF excimer laser (193nm), F ₂ excimer laser (157nm), X-ray, EUV (13nm) or electron beam, etc., KrF excimer laser , ArF excimer laser, EUV or electron beam is preferred.

In the (iii) development process, the developer may be an alkali developer or a developer containing an organic solvent (hereinafter, also referred to as an organic developer).

As the alkali developing solution, a quaternary ammonium salt represented by tetramethylammonium hydroxide is generally used. In addition, an alkaline aqueous solution such as an inorganic base, a 1-3 amine, an alcohol amine, and a cyclic amine can also be used. Furthermore, the alkali developing solution 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 development time 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 formed.

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

Examples of the ketone-based solvent include 1-octanone, 2-octanone, 1-nonanone, 2-nonanone, acetone, 2-heptanone (methylpentyl ketone), 4-heptanone, 1- Hexanone, 2-hexanone, diisobutyl ketone, cyclohexanone, methylcyclohexanone, phenylacetone, methyl ethyl ketone, methyl isobutyl ketone, acetoacetone, acetone acetone, ionone , Diacetone alcohol, acetamethanol, acetophenone, methylnaphthone, isophorone and propylene carbonate.

Examples of the ester-based solvent include methyl acetate, butyl acetate, ethyl acetate, isopropyl acetate, pentyl acetate, isoamyl acetate, pentyl acetate, propylene glycol monomethyl ether acetate, and ethylene glycol Monoethyl ether acetate, diethylene glycol monobutyl ether acetate, diethylene glycol monoethyl ether acetate, ethyl-3-ethoxypropionate, 3-methoxybutyl acetate , 3-methyl-3-methoxybutyl acetate, methyl formate, ethyl formate, butyl formate, propyl formate, ethyl lactate, butyl lactate, propyl lactate, butyl butyrate, Methyl 2-hydroxyisobutyrate, isoamyl acetate, isobutyl isobutyrate and butyl propionate.

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

The above-mentioned solvents may be mixed in a plurality of types, or may be mixed with a solvent or water other than the above-mentioned solvents. The moisture content of the developer as a whole is preferably less than 50% by mass, more preferably less than 20% by mass, even more preferably less than 10% by mass, and more preferably 0% by mass or more and less than 5% by mass, which contains substantially no moisture. Especially good. The content of the organic solvent with respect to the organic developer is preferably 50 to 100% by mass, more preferably 80 to 100% by mass, even more preferably 90 to 100% by mass, and 95 to 100%. The mass% is particularly good.

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

The content of the surfactant relative to the total amount of the developing solution 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.

The organic developer may contain the acid diffusion control agent.

Examples of the development method include a method of immersing a substrate in a tank filled with a developer for a certain period of time (immersion method), and a method of raising the developer by surface tension and leaving the substrate on the surface for a certain period of time (liquid coating method) ), The method of spraying the developer solution on the surface of the substrate (spray method) or the method of continuously ejecting the developer solution onto the substrate rotating at a certain speed while scanning the developer ejection nozzle at a certain speed (dynamic distribution method), etc.

A process of developing using an alkaline aqueous solution (alkali developing process) and a process of developing using a developing solution containing an organic solvent (organic solvent developing process) may be combined. Thereby, a pattern can be formed only by dissolving a region with an intermediate-level exposure intensity, so that a finer pattern can be formed.

It is preferable to have a process (rinsing process) using a washing solution after the (iii) developing process.

As the rinsing liquid used in the rinsing process after the development process using the alkali developing solution, for example, pure water can be used. Pure water may contain a suitable amount of a surfactant. At this time, after the development process or the rinsing process, a treatment for removing the developing solution or the rinsing solution attached to the pattern by a supercritical fluid may be added. Further, in order to remove the moisture remaining in the pattern, a heat treatment may be performed after the treatment by a rinsing treatment or a treatment with a supercritical fluid.

The developing solution used in the developing process after the developing process using a developing solution containing an organic solvent is not particularly limited as long as it does not dissolve the pattern, and a solution containing a common organic solvent can be used. As the washing liquid, a washing liquid containing at least one organic solvent selected from the group consisting of a hydrocarbon-based solvent, a ketone-based solvent, an ester-based solvent, an alcohol-based solvent, an amidine-based solvent, and an ether-based solvent is preferably used. Specific examples of the hydrocarbon-based solvent, the ketone-based solvent, the ester-based solvent, the alcohol-based solvent, the amidine-based solvent, and the ether-based solvent are the same as those described in the developer containing an organic solvent. As the rinsing liquid used in the rinsing process at this time, a rinsing liquid containing monovalent alcohol is more preferable.

Examples of the monovalent alcohol used in the washing process include linear, branched, or cyclic monovalent alcohols. Specific examples include 1-butanol, 2-butanol, 3-methyl-1-butanol, tertiary butanol, 1-pentanol, 2-pentanol, 1-hexanol, and 4-methyl alcohol. 2-Pentanol, 1-heptanol, 1-octanol, 2-hexanol, cyclopentanol, 2-heptanol, 2-octanol, 3-hexanol, 3-heptanol, 3-octanol , 4-octanol and methyl isobutyl methanol. Examples of the monovalent 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 methanol and so on.

A plurality of components may be mixed, and they may be used in combination with an organic solvent other than the above. The water content in the washing liquid is preferably 10% by mass or less, more preferably 5% by mass or less, and even more preferably 3% by mass or less. By setting the water content to 10% by mass or less, good developing characteristics can be obtained.

The rinse solution may contain a suitable amount of a surfactant. In the rinsing process, a substrate that is developed using an organic developer is rinsed with a rinse solution containing an organic solvent. The method of the cleaning treatment is not particularly limited, and examples thereof include a method of continuously spraying a washing solution on a substrate rotating at a constant speed (spin coating method), and a method of immersing a substrate in a tank filled with a developer for a predetermined time (immersion Method) or a method of spraying a developer solution on the substrate surface (spray method). Among them, it is preferable to perform a cleaning process by a spin coating method, and then rotate the substrate at a rotation speed of 2,000 to 4,000 rpm after the cleaning, thereby removing the rinse liquid from the substrate. It is also preferable to have a heating process (Post Bake) after the rinsing process. The developing process and the developing solution remaining between the patterns and inside the patterns are removed by the heating process. In the heating process after the rinsing process, 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, and 30 seconds to 90 seconds is more preferable.

Various materials (for example, a resist solvent, a developing solution, a developing solution, a composition for forming an antireflection film, or a top layer) used in the actinic radiation- or radiation-sensitive resin composition of the present invention and the pattern forming method of the present invention It is preferable that the composition for forming a coating layer does not contain impurities such as metal components, isomers, and residual monomers. As for the content of such impurities contained in the above-mentioned various materials, 1 ppm or less is preferable, 100 ppt or less is more preferable, 10 ppt or less is more preferable, and it is particularly preferable not to include substantially (below the detection limit of the measurement device).

Examples of a method for removing impurities such as metals from the various materials include filtration using a filter. The pore size of the filter is preferably 10 nm or less, more preferably 5 nm or less, and 3 nm or less. The material of the filter is preferably a filter made of polytetrafluoroethylene, polyethylene, or nylon. The filter can also be cleaned with an organic solvent in advance. In the filtration process, multiple types of filters can be used in series or in parallel. When using multiple filters, filters with different pore sizes and / or materials can be used in combination. In addition, various materials can be filtered multiple times, and the process of filtering multiple times can also be a cycle filtering process. As the filter, it is preferable to reduce the amount of the eluted matter disclosed in Japanese Patent Application Publication No. 2016-201426 (Japanese Patent Application Laid-Open No. 2016-201426). In addition to filter filtration, impurities can be removed by adsorbent materials, or filters can be used in combination with adsorbent materials. As the adsorbent, a known adsorbent can be used, and for example, an inorganic adsorbent such as silica gel or zeolite, or an organic adsorbent such as activated carbon can be used. Examples of the metal adsorbent include those disclosed in Japanese Patent Application Publication No. 2016-206500 (Japanese Patent Application Laid-Open No. 2016-206500). In addition, as a method for reducing impurities such as metals contained in the various materials mentioned above, there may be selected a raw material having a small metal content as a raw material constituting the various materials, filtering the raw material constituting the various materials by filtration, or filtering Teflon (Registered trademark) A method such as lining the device and performing distillation under conditions that minimize contamination. In order to reduce impurities such as metals to the ppt level, it is preferable to perform glass lining treatment throughout the entire manufacturing process of the manufacturing equipment for various materials (resin, photoacid generator, etc.) that synthesize a resist component. The preferable conditions in the filtration of the raw materials constituting various materials are the same as those described above.

In order to prevent contamination of impurities, it is preferable to store the above-mentioned various materials in containers described in US Patent Application Publication No. 2015/0227049, Japanese Patent Application Publication No. 2015-123351 (Japanese Patent Application Laid-Open No. 2015-123351) and the like .

A method for improving the surface roughness of a pattern can be applied to a pattern formed by the pattern forming method of the present invention. As a method for improving the surface roughness of a pattern, for example, a method of treating a pattern with a plasma containing a hydrogen gas disclosed in the specification of US Patent Application Publication No. 2015/0104957 can be mentioned. In addition, Japanese Patent Application Publication No. 2004-235468 (Japanese Patent Application Laid-Open No. 2004-235468), US Patent Application Publication No. 2010/0020297, Proc. Of SPIE Vol. 8328 83280N-1 "EUV Resist Curing" can be applied. "Method for LWR Reduction and Etch Selectivity Enhancement". The pattern formed by the above method can be used, for example, as a core for a spacer process disclosed in Japanese Patent Application Laid-Open No. 1991-270227 (Japanese Patent Application Laid-Open No. 3-270227) and US Patent Application Laid-Open No. 2013/0209941.材 (Core).

[Method for Manufacturing Electronic Component] The present invention also relates to a method for manufacturing an electronic component including the pattern forming method described above. The electronic component manufactured by the method for manufacturing an electronic component of the present invention can be preferably mounted on electrical and electronic equipment (for example, home appliances, OA (Office Automation: Office Automation) -related equipment, media-related equipment, optical equipment, and communication equipment, etc.) .

[Compound] The present invention also relates to a compound represented by the general formula (1) and a compound represented by the general formula (2). Specific aspects of the compound represented by the general formula (1) and the compound represented by the general formula (2) are as described above. [Example]

Hereinafter, the present invention will be described in more detail based on examples. The materials, usage amounts, proportions, processing contents, processing steps, and the like shown in the following examples can be appropriately changed without departing from the gist of the present invention. Therefore, the scope of the present invention should not be interpreted restrictively by the examples shown below.

[Preparation of the photosensitive radiation- or radiation-sensitive resin composition] Various components contained in the photosensitive radiation- 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. In addition, the weight average molecular weight (Mw) and the dispersion (Mw / Mn) of the resins A1 to A6 were measured by GPC (carrier: tetrahydrofuran (THF)) (in terms of polystyrene conversion). The composition ratio (mole% ratio) of the resin was measured by ¹³ C-NMR (nuclear magnetic resonance).

[Chemical Formula 34]

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

[Chemical Formula 35]

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

[Table 1]

<Acid Diffusion Control Agent> (Compound (C) represented by General Formula (1)) The structure of the compound (Compounds C1 to C18) represented by General Formula (1) shown in Table 3 is shown below. A synthesis example of the compound C1 is shown as one example.

<< Synthesis Example 1: Synthesis of Compound C1 >> After ethyl 2-iodobenzoate (3.3 g) was dissolved in THF (20 mL) placed in a container, the internal temperature was cooled to -10 ° C. Next, isopropyl magnesium chloride-lithium chloride complex (THF solution, 11.9 g) was added dropwise to the cooled mixed solution so that the internal temperature did not exceed 0 ° C, and the mixture was stirred at -10 ° C for 30 minutes (Reaction liquid 1). ). After diphenylsulfene (3.2 g) was dissolved in THF (20 mL) placed in a container, the internal temperature was cooled to -10 ° C. Next, trifluoromethanesulfonic anhydride (3.4 g) was added dropwise to the cooled mixed solution so that the internal temperature did not exceed 0 ° C, and the mixture was stirred at 0 ° C for 30 minutes (Reaction Liquid 2). Next, after the reaction solution 1 was dropped into the container containing the reaction solution 2 so that the internal temperature did not exceed 0 ° C, the reaction solution was allowed to react at room temperature for 12 hours. Dichloromethane (100 mL) and distilled water (100 mL) were added to the obtained reaction liquid, and liquid separation was performed. Then, the extracted organic layer was washed 4 times with distilled water (50 mL), and then the solvent was distilled off. Furthermore, the obtained residue was purified by a column to obtain a purified product. The purified product obtained by the above process was dissolved in dichloromethane (16 mL), and then 0.2 mol / L sodium hydroxide (16 mL) was further added, and the mixture was allowed to react at 40 ° C. for 4 hours. The obtained reaction solution was separated, and the aqueous layer was extracted five times with dichloromethane (15 mL), and then the solvent was distilled off. After the obtained solid was washed with diisopropyl ether (5 mL), the solvent was removed and dried to obtain C1 (0.26 g).

In addition, the same operations as in the synthesis example of the compound C1 described above were performed to synthesize compounds C2 to C24 described later.

[Chemical Formula 36]

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

[Chemical Formula 37]

(PKa of Acid Diffusion Control Agent) Table 2 shows the pKa of acids generated from compounds C1 to C24 and the pKa of acids generated from compounds D1 to D4. The pKa was measured by the method described above.

[Table 2]

<Preparation of a photosensitive radiation- 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 obtained mixed liquid was filtered in the order of a polyethylene filter having a pore diameter of 50 nm, a nylon filter having a pore diameter of 10 nm, and a polyethylene filter having a pore diameter of 5 nm. Radiation- or radiation-sensitive resin composition. In the photosensitized or radiation-sensitive resin composition, the solid content means all components except the solvent (F). In the examples and comparative examples, the obtained actinic radiation- or radiation-sensitive resin compositions were used.

[Pattern formation and various evaluations] <Pattern formation 1: ArF liquid immersion exposure, organic solvent development> An organic antireflection film-forming composition ARC29SR (manufactured by Nissan Chemical Corporation) was coated on a silicon wafer and heated at 205 ° C. An anti-reflection film with a thickness of 95 nm was formed in 60 seconds. The obtained anti-reflection film was coated with the actinic radiation- or radiation-sensitive resin composition of the examples and comparative examples, and heated at 100 ° C for 60 seconds (PB: Prebake) to form a film. 85nm thick resist film. Using ArF excimer laser liquid immersion scanner (manufactured by ASML; XT1700i, NA1.20, C-Quad, outer sigma 0.900, inner sigma 0.812, XY deflection), and a 1: 1 line and space pattern with a line width of 44nm A 6% half-tone mask was used to expose the resist film on the silicon wafer obtained in the above steps. As the liquid immersion liquid, ultrapure water was used. After that, the exposed resist film was heated at 105 ° C. (PEB: Post Exposure Bake) for 60 seconds, and then developed using a negative-type developing solution (organic developing solution, butyl acetate) for 30 seconds by a liquid coating method. Furthermore, the rinse solution (methyl isobutyl methanol (MIBC)) was used for 30 seconds by the overlying method. Next, the silicon wafer was spin-dried at 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 1: 1 line and space pattern of 44 nm was observed from the upper part of the pattern using a line width measurement scanning electron microscope (S-8840, manufactured by Hitachi, Ltd.). At this time, the line width was measured at 50 points for a range of 2 μm of the edge in the longitudinal direction of the line pattern, and the standard deviation (3σ) of the measurement deviation of the measured line width was calculated. The smaller the value of the standard deviation (3σ), the better the pattern's LWR performance. In addition, the evaluation of LWR performance was performed based on the following five-stage benchmark. The evaluation results are shown in Table 3.

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

<Pattern formation 2: ArF liquid immersion exposure, organic solvent development> An organic antireflection film ARC29SR (manufactured by Brewer) was coated on a silicon wafer, and baked at 205 ° C for 60 seconds, thereby forming a 98 nm film thickness. An anti-reflection film was coated thereon with the actinic radiation or radiation-sensitive resin composition of the examples and comparative examples, and baked at 100 ° C for 60 seconds, thereby forming a resist film having a thickness of 90 nm. . The ArF excimer laser liquid immersion scanner (manufactured by ASML; XT1700i, NA (numerical aperture) 1.20, C-Quad, outer sigma 0.98, inner sigma 0.89, XY deflection) was used to form the resistance obtained by the above steps. On the wafer of the resist film, a contact hole pattern with a diameter of 45 nm was exposed through a 6% half-tone mask. The exposure amount to the above-mentioned pattern size is set as the optimal exposure amount. Ultra-pure water was used as the liquid immersion liquid. After that, the PEB temperature was set to 90 ° C., and then developed with an organic developing solution, that is, butyl acetate for 30 seconds, and spin-dried to obtain a hole pattern.

<Performance evaluation: CDU performance (nm)> In one exposure of the above-mentioned optimal exposure (E _opt ) exposure, in an area of 20 places spaced at a distance of 1 μm from each other, an arbitrary 25 pieces are measured for each area (that is, , A total of 500 holes), to determine the standard deviation (σ), and calculated 3σ. The smaller the value, the smaller the deviation in size and the better the performance. In addition, CDU performance was evaluated based on the following five-stage benchmarks. The evaluation results are shown in Table 3.

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

In Table 3, the content (% by mass) of each component represents the content relative to the total solid content. In Table 3, "pKa (B)" corresponds to the pKa of the acid generated from the acid generator (B) (compounds B1 to B10) (same as disclosed in Table 1). In Table 3, "pKa (A1)" and "pKa (A2)" correspond to the pKa of the acid generated from the compound (compounds C1 to C24) represented by the general formula (1) and the diffusion from the comparative acid, respectively. The pKa of the acid produced by the control agent (compounds D1 to D4) (same as disclosed in Table 2).

[table 3]

From the results in Table 3, it was confirmed that the pattern of the formed photoresistance or radiation-sensitive resin composition according to the examples was excellent in both LWR and CDU. Moreover, it is confirmed from the comparison of Examples ₁ , ₄ , ₁₀ and ₁₂ that at least one of Ar ₁ , Ar ₂ and Ar ₃ among the compounds represented by the general formula (1) is an unsubstituted monocyclic aromatic In the case of a hydrocarbon group (in other words, in the compound represented by the general formula (2), R ₁ to R ₄ are all hydrogen atoms or when at least one of Ar ₂ and Ar ₃ is an unsubstituted monocyclic aromatic hydrocarbon (Example 1 , 4 and 10 and Example 12)), the LWR and CDU of the formed pattern are all more excellent.

Moreover, it is confirmed from the comparison of Examples ₁ , ₄ , ₁₀ and ₁₂ that at least two of Ar ₁ , Ar ₂ and Ar ₃ among the compounds represented by the general formula (1) are unsubstituted monocyclic aromatics. In the case of a group hydrocarbon group (in other words, in the compound represented by the general formula (2), R ₁ to R ₄ are all hydrogen atoms and one of Ar ₂ and Ar ₃ is an unsubstituted monocyclic aromatic hydrocarbon group, or Ar ₂ and When Ar ₃ is an unsubstituted monocyclic aromatic hydrocarbon group, or when R ₁ to R ₄ are all hydrogen atoms, and Ar ₂ and Ar ₃ are both unsubstituted monocyclic aromatic hydrocarbon groups (Examples 1 and 4 and implementation) Comparison of Examples 10 and 12)), the LWR and CDU of the formed pattern are more excellent.

Moreover, it is confirmed from the comparison between Example 1 and Examples 13 and 14 that, in the compound represented by the general formula (1), when L ₁ to L ₃ are single bonds, both the LWR and the CDU of the formed pattern are more excellent. Further, it is confirmed from the comparison of Examples 1, 2 and 15 to 18 that in the compound represented by the general formula (1), A ₁ is -L ₁ -CO ₂ ^- or -L ₃ -X ₁ -N ^-- Y _{At 1} , the LWR and CDU of the formed pattern are both more excellent.

In addition, it was confirmed from the comparison between Example 1 and Examples 19 and 20 that when the compound represented by the general formula (1) is the compound represented by the general formula (2), both the LWR and the CDU of the pattern formed are more Excellent.

Moreover, it is confirmed from the comparison between Example 21 and Example 22 that, in the compound represented by the general formula (1), when Ar ₁ has a non-aromatic substituent, both the LWR and the CDU of the formed pattern are more excellent.

On the other hand, the actinic radiation- or radiation-sensitive resin composition of the comparative example failed to satisfy the desired requirements.

Claims (15)

An actinic radiation- or radiation-sensitive resin composition comprising: a resin; an acid generator that generates an acid upon irradiation with actinic radiation or radiation; and an acid diffusion control agent comprising the following: A compound represented by the general formula (1), In the above formula, Ar ₁ , Ar ₂ and Ar ₃ each independently represent an aromatic hydrocarbon group, and A ₁ is substituted at the ortho position of the carbon atom bonded to S ⁺ on Ar ₁ and represents -L ₁ -CO ₂ ^- ,- L ₂ -SO ₃ ^- or -L ₃ -X ₁ -N ^-- Y ₁ , L ₁ , L ₂ and L ₃ each independently represent a single bond or a divalent linking group, and X ₁ represents -SO ₂ -or -CO-, Y ₁ represents -SO ₂ -R _A or -CO-R _B , R _A and R _B each independently represent a monovalent substituent, and Ar ₁ , Ar ₂ and Ar ₃ may further have a substituent The substituents may be bonded to each other to form a ring. The photosensitive radiation- or radiation-sensitive resin composition according to item 1 of the scope of the patent application, wherein the compound represented by the general formula (1) is a compound represented by the following general formula (2), In the above formula, Ar ₂ and Ar ₃ each independently represent a monocyclic aromatic hydrocarbon group, R ₁ , R ₂ , R ₃ and R ₄ each independently represent a hydrogen atom or a non-aromatic substituent, and A ₁ represents -L ^{_{1 -CO 2 -, -L 2 -SO}} 3 - or ^{_{-L 3 -X 1 -N - -Y 1}} , L 1, L 2 and L ₃ each independently represent a single bond or a divalent linking group, X ₁ represents -SO ₂ -or -CO-, Y ₁ represents -SO ₂ -R _A or -CO-R _B , R _A and R _B each independently represent a monovalent substituent, and Ar ₂ and Ar ₃ may be It further has a substituent, and these substituents may be bonded to each other to form a ring. The photosensitized or radiation-sensitive resin composition according to item 2 of the scope of patent application, wherein R ₁ to R ₄ are all hydrogen atoms or at least one of Ar ₂ and Ar ₃ is an unsubstituted monocyclic aromatic Group of hydrocarbon groups. The photosensitive radiation- or radiation-sensitive resin composition according to item 2 of the scope of patent application, wherein R ₁ to R ₄ are all hydrogen atoms and one of Ar ₂ and Ar ₃ is an unsubstituted monocyclic aromatic The hydrocarbon group, or Ar ₂ and Ar ₃ are both unsubstituted monocyclic aromatic hydrocarbon groups, or R ₁ to R ₄ are all hydrogen atoms, and Ar ₂ and Ar ₃ are both unsubstituted monocyclic aromatic hydrocarbon groups. The photosensitive radiation- or radiation-sensitive resin composition according to any one of claims 1 to 4 of the scope of patent application, wherein A ₁ is -L ₁ -CO ₂ ^- or -L ₃ -X ₁ -N ^- -Y _1. The photosensitive radiation- or radiation-sensitive resin composition according to item 5 of the scope of the patent application, wherein L ₁ and L ₃ are single bonds. A resist film formed using the photosensitized radiation- or radiation-sensitive resin composition described in any one of claims 1 to 6 of the scope of patent application. A pattern forming method, comprising: a resist film forming process using the photosensitized radioactive or radiation-sensitive resin composition described in any one of claims 1 to 6 of the patent application scope; an exposure process, Exposing the resist film; and a developing process, developing the exposed resist film using a developing solution. A method for manufacturing an electronic component includes the pattern forming method described in item 8 of the scope of patent application. A compound represented by the following general formula (1), wherein In the above formula, Ar ₁ , Ar ₂ and Ar ₃ each independently represent an aromatic hydrocarbon group, and A ₁ is substituted at the ortho position of the carbon atom bonded to S ⁺ on Ar ₁ and represents -L ₁ -CO ₂ ^- ,- L ₂ -SO ₃ ^- or -L ₃ -X ₁ -N ^-- Y ₁ , L ₁ , L ₂ and L ₃ each independently represent a single bond or a divalent linking group, and X ₁ represents -SO ₂ -or -CO-, Y ₁ represents -SO ₂ -R _A or -CO-R _B , and R _A and R _B each independently represent a monovalent substituent, wherein L ₁ , L _2, and L ₃ are the same as Ar ₁ The atom at the bonding position is not an oxygen atom, and 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. A compound represented by the following general formula (2), wherein In the above formula, Ar ₂ and Ar ₃ each independently represent a monocyclic aromatic hydrocarbon group, R ₁ , R ₂ , R ₃ and R ₄ each independently represent a hydrogen atom or a non-aromatic substituent, and A ₁ represents -L ^{_{1 -CO 2 -, -L 2 -SO}} 3 - or ^{_{-L 3 -X 1 -N - -Y 1}} , L 1, L 2 and L ₃ each independently represent a single bond or a divalent linking group, X ₁ represents -SO ₂ -or -CO-, Y ₁ represents -SO ₂ -R _A or -CO-R _B , R _A and R _B each independently represent a monovalent substituent, wherein L ₁ , L ₂ and The atom at the bonding position with Ar ₁ in L ₃ is not an oxygen atom, and 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 item 11 of the scope of patent application, wherein R ₁ to R ₄ are all hydrogen atoms or at least one of Ar ₂ and Ar ₃ is an unsubstituted monocyclic aromatic hydrocarbon group. The compound according to item 11 of the scope of patent application, wherein R ₁ to R ₄ are all hydrogen atoms and one of Ar ₂ and Ar ₃ is an unsubstituted monocyclic aromatic hydrocarbon group, or both Ar ₂ and Ar ₃ are An unsubstituted monocyclic aromatic hydrocarbon group, or R ₁ to R ₄ are all hydrogen atoms, and Ar ₂ and Ar ₃ are both unsubstituted monocyclic aromatic hydrocarbon groups. The compound as described in any one of claims 10 to 13 in the scope of patent application, wherein A ₁ is -L ₁ -CO ₂ ^- or -L ₃ -X ₁ -N ^-- Y ₁ . The compound as described in claim 14 in the scope of patent application, wherein L ₁ and L ₃ are single bonds.