TW202012467A - Actinic light sensitive or radiation sensitive resin composition, resist film, pattern forming method, and method for producing electronic device - Google Patents

Abstract

Provided is an actinic light sensitive or radiation sensitive resin composition that has excellent resolution and that enables the formation of a pattern having excellent LWR. Also provided are a resist film, a pattern forming method, and a method for producing an electronic device. This actinic light sensitive or radiation sensitive resin composition contains a resin and a photoacid generator. The resin contains a repeating unit containing a partial structure represented by formula (2) and at least one repeating unit selected from the group consisting of a repeating unit containing a group having a polarity that is increased by the action of an acid, a repeating unit represented by general formula (1-1), and a repeating unit represented by formula (1-2).

Description

Photosensitive or radiation-sensitive resin composition, resist film, pattern forming method, manufacturing method of electronic device

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

In the manufacturing process of semiconductor devices such as IC (Integrated Circuit) and LSI (Large Scale Integrated Circuit), the use of photolithography or radiation sensitive resin composition lithography Perform microfabrication. As a method of lithography, a method in which a resist film is formed by sensitizing radiation or radiation-sensitive resin composition, and then the obtained film is exposed and then developed. For example, Patent Document 1 discloses a radiation-sensitive resin composition including a resin, the resin including: a repeating unit including a group (acid-decomposable group) whose polarity is increased by the action of an acid; and having a ring The carbonate structure serves as a repeating unit of the partial structure. [Prior Technical Literature] [Patent Literature]

[Patent Document 1] Japanese Patent Application Publication No. 2010-160348

The present inventors have studied the radiation-sensitive linear resin composition described in Patent Document 1, and have clarified the LWR (Line Width Roughness: line width) which is not compatible with the resolution and the pattern formed at the recently required level. Roughness).

Therefore, an object of the present invention is to provide a sensitized radiation or radiation-sensitive resin composition having excellent resolution and excellent LWR of the formed pattern. In addition, an object of the present invention is to provide a resist film, a pattern forming method, and a method of manufacturing an electronic device.

The inventors found that the above-mentioned problems can be solved by the following structure.

[1] A sensitized radioactive or radiation-sensitive resin composition comprising a resin and a photoacid generator, wherein The above resin contains: Repeating units containing groups with increased polarity by the action of acid; At least one kind of repeating unit selected from the group consisting of repeating units represented by the following general formula (1-1) and repeating units represented by the following general formula (1-2); and The repeating unit includes a partial structure represented by the general formula (2) described later. Among them, the above resin includes a repeating unit including a group whose polarity is increased by the action of the above acid, a repeating unit represented by the above general formula (1-1), a repeating unit represented by the above general formula (1-2), and When a repeating unit other than a repeating unit having a partial structure represented by the general formula (2) is included, the repeating unit does not substantially include a repeating unit including a lactone structure. [2] The sensitized radiation or radiation sensitive resin composition as described in [1], wherein The partial structure represented by the general formula (2) is one or more types selected from the group including the general formula (3) to the general formula (8) described later. [3] The sensitized radiation or radiation sensitive resin composition as described in [2], wherein The partial structure represented by the above general formula (2) is one or more kinds selected from the group including the above general formula (5) and the above general formula (8). [4] The sensitized radiation or radiation sensitive resin composition according to any one of [1] to [3], wherein The content of the repeating unit including the partial structure represented by the above general formula (2) is 5 to 40 mol% relative to all the repeating units in the above resin. [5] The sensitized radiation or radiation sensitive resin composition according to any one of [1] to [4], wherein The content of the repeating unit containing the partial structure represented by the above general formula (2) is greater than that selected from the group including the repeating unit represented by the above general formula (1-1) and the repeating unit represented by the above general formula (1-2) The content of at least one or more repeating units in the group. [6] The sensitized radiation or radiation sensitive resin composition according to any one of [1] to [5], wherein The above resin further includes a repeating unit including a ring structure directly bonded to the main chain. [7] The sensitized radiation or radiation sensitive resin composition according to any one of [1] to [6], which is a negative resist composition developed using a developer containing an organic solvent. [8] A resist film formed of the photosensitive radiation-sensitive or radiation-sensitive resin composition according to any one of [1] to [7]. [9] A pattern forming method, including: In the resist film forming process, the photosensitive film composition according to any one of [1] to [7] is used to form a resist film; An exposure process to expose the above resist film; and In the development process, the exposed resist film is developed using a developing solution. [10] A method of manufacturing an electronic device, including the pattern forming method described in [9]. [Effect of the invention]

According to the present invention, it is possible to provide a sensitized radiation or radiation-sensitive resin composition having excellent resolution and excellent LWR of the formed pattern. In addition, according to the present invention, a resist film, a pattern forming method, and an electronic device manufacturing method can be provided.

An example of the form for implementing the present invention will be described below. In addition, in this specification, the numerical range represented by "-" means the range which includes the numerical value described before and after "-" as a lower limit and an upper limit. In addition, in the label of the group (atomic group) in this specification, the label which is not marked as substituted or unsubstituted includes the group which does not have a substituent and the group which has a substituent. For example, "alkyl" means not only an unsubstituted alkyl group (unsubstituted alkyl group) but also a substituted alkyl group (substituted alkyl group). The “(meth)acrylic group” in this specification is a general term including an acrylic group and a methacrylic group, and means “at least one of an acrylic group and a methacrylic group”. Similarly, "(meth)acrylic acid" means "at least one of acrylic acid and methacrylic acid". In this specification, the weight-average molecular weight (Mw), number-average molecular weight (Mn), and degree of dispersion (also known as molecular weight distribution) (Mw/Mn) of the resin are based on GPC (Gel Permeation Chromatography) equipment ( HLC-8120GPC manufactured by TOSOH CORPORATION) and based on GPC measurement (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, the detector: Refractive index detector (Refractive Index Detector) is defined by the conversion value of polystyrene. 1Å is 1×10 ^-10 m.

[Photosensitive or radiosensitive resin composition] As one of the characteristic points of the sensitized radiation-sensitive or radiation-sensitive resin composition (hereinafter, also referred to as "composition") of the present invention, the aspect including a resin is included. The resin includes: (A) A repeating unit of a group (hereinafter, also referred to as "acid-decomposable group") increased by the action of an acid; (B) is selected from the group including the repeating unit represented by the general formula (1-1) described below and At least one or more repeating units in the group of repeating units represented by general formula (1-2) (hereinafter, also referred to as "specific repeating unit 1"); and (C) includes the general formula (2) described later Part of the repeating unit structure (hereinafter, also referred to as "specific repeating unit 2"). The above resin contains the specific repeating unit 1 and the specific repeating unit 2, and thus has excellent compatibility with the photoacid generator. As a result, in the resist film, the distribution of the acid generated from the photoacid generator during exposure becomes more uniform, and the LWR of the formed pattern is excellent. In addition, the resin includes the specific repeating unit 1 and the specific repeating unit 2, and thus has excellent solubility in the developer, and as a result, has excellent resolution. In particular, the above resin is excellent in solubility in a developer containing an organic solvent. Therefore, the above composition can be used as a negative resist composition developed using a developer containing an organic solvent.

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

〔Resin (A)〕 The composition of the present invention contains a resin (hereinafter, also referred to as "resin (A)"). The resin (A) includes: a repeating unit including a group (acid-decomposable group) whose polarity is increased by the action of an acid; selected from the group including a repeating unit represented by the general formula (1-1) described below and a general formula described later (1-2) At least one or more repeating units (specific repeating unit 1) in the group of repeating units represented; and repeating units (specific repeating unit 2) including a partial structure represented by the general formula (2) described later. That is, the resin (A) is a resin that is decomposed by the action of an acid and has increased polarity (hereinafter, also referred to as "acid-decomposable resin."). When the composition of the present invention contains a resin (A), the formed pattern generally becomes a positive pattern when an alkaline developer is used as a developer, and a negative pattern when an organic developer is used as a developer.

<Repeating unit containing acid-decomposable group> The resin (A) includes a repeating unit containing an acid-decomposable group. The acid-decomposable group preferably has a structure in which the polar group is protected by a group (detached group) that is decomposed and decomposed by the action of an acid. Examples of polar groups include carboxyl groups, phenolic hydroxyl groups, fluorinated alcohol groups, sulfonic acid groups, sulfonamide groups, sulfonylimide groups, (alkylsulfonyl) (alkylcarbonyl) methylene groups, ( (Alkylsulfonyl) (alkylcarbonyl) amide imino, bis (alkylcarbonyl) methylene, bis (alkylcarbonyl) amide imino, bis (alkylsulfonyl) methylene, bis (Alkylsulfonyl) amide imino, tri(alkylcarbonyl)methylene and tri(alkylsulfonyl)methylene and other acidic groups (in 2.38% by mass aqueous tetramethylammonium hydroxide solution Dissociated groups), and alcoholic hydroxyl groups.

In addition, the alcoholic hydroxyl group refers to a hydroxyl group bonded to a hydrocarbon group other than the hydroxyl group (phenolic hydroxyl group) directly bonded to the aromatic ring, and as the hydroxyl group, the alpha position is substituted with an electron-withdrawing group such as a fluorine atom at the α position Except for radicals (for example, hexafluoroisopropanol, etc.). As the alcoholic hydroxyl group, a hydroxyl group having a pKa (acid dissociation constant) of 12 or more and 20 or less is preferable.

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

A preferable group as an acid-decomposable group is a group in which the hydrogen atom of these groups is replaced by a group (leaving group) that is desorbed by the action of an acid. Examples of the group (leaving group) 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 ) etc. 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 second butyl Base, hexyl and octyl. The cycloalkyl groups represented by R ₃₆ to R ₃₉ , R ₀₁ and R ₀₂ may be monocyclic or polycyclic. As the monocyclic cycloalkyl group, a C3-C8 cycloalkyl group is preferred, and examples thereof include cyclopropyl, cyclobutyl, cyclopentyl, cyclohexyl, and cyclooctyl. As the polycyclic cycloalkyl group, a cycloalkyl group having 6 to 20 carbon atoms is preferred, for example, adamantyl group, norbornyl group, isobornyl group, camphenyl group, dicyclopentyl group, α-pinenyl group, tris Cyclodecyl, tetracyclododecyl group, androstanyl group, etc. 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 16 carbon atoms is preferred, and examples thereof include a phenyl group, a naphthyl group and an anthracenyl 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 a vinyl group, an allyl group, a butenyl group and a cyclohexenyl group. The ring system cycloalkyl (monocyclic or polycyclic) formed by bonding R ₃₆ and R _{37 to} each other is preferred. As the cycloalkyl group, monocyclic cycloalkyl groups such as cyclopentyl group and cyclohexyl group or polycyclic cycloalkyl groups such as norbornyl group, tetracyclodecyl group, tetracyclododecyl group and adamantyl group are preferred.

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

As the repeating unit containing an acid-decomposable group, the resin (A) preferably contains a repeating unit represented by the following general formula (AI).

[Chemical Formula 1]

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 form a ring structure.

Examples of the divalent linking group represented by T include alkylene, aryl, -COO-Rt-, -O-Rt-, and the like. In the formula, Rt represents an alkylene group, cycloalkylene group or aryl group. T series single bond or -COO-Rt- is preferred. Rt-based chain alkylene groups having 1 to 5 carbon atoms are preferred, and -CH ₂ -, -(CH ₂ ) ₂ -or -(CH ₂ ) ₃ -are more preferred. As T, a single bond is better.

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

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

As a ring structure formed by two bonds in Rx ₁ , Rx ₂ and Rx ₃ , a monocyclic cycloalkane ring such as cyclopentyl ring, cyclohexyl ring, cycloheptyl ring, cyclooctane ring, or norbranche Polycyclic cycloalkyl rings such as alkane ring, tetracyclodecane ring, tetracyclododecane ring, and adamantane ring are preferred. Among them, cyclopentyl ring, cyclohexyl ring or adamantane ring is more preferable. The ring structure formed by bonding two of Rx ₁ , Rx ₂ and Rx ₃ is also preferably the structure shown below.

[Chemical Formula 2]

Specific examples of monomers corresponding to repeating units represented by the general formula (AI) are listed below, but the present invention is not limited to these specific examples. Specific examples conform to the following general formula (AI) in the case of methyl lines Xa _1, Xa can be optionally substituted with _one hydrogen atom, a halogen atom or a monovalent organic group.

[Chemical Formula 3]

It is also preferable that the resin (A) contains the repeating unit described in paragraphs <0336> to <0369> of US Patent Application Publication No. 2016/0070167A1 as a repeating unit containing an acid-decomposable group.

In addition, the resin (A) may have a repeating unit described in paragraphs <0363> to <0364> of US Patent Application Publication 2016/0070167A1, which contains a group that is decomposed by the action of an acid to generate an alcoholic hydroxyl group as Repeating units containing acid-decomposable groups.

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

The content of the repeating unit containing an acid-decomposable group contained in the resin (A) is 10 to 10 to all the repeating units of the resin (A) (the total of repeating units containing an acid-decomposable group is plural). 90 mol% is more preferable, 20 to 80 mol% is more preferable, and 30 to 70 mol% is more preferable.

<Specific repeating unit 1> The resin (A) contains at least one kind of repeating unit (specific repeating unit) selected from the group consisting of a repeating unit represented by the general formula (1-1) described later and a repeating unit represented by the general formula (1-2) described later 1). Hereinafter, the repeating unit represented by the general formula (1-1) and the repeating unit represented by the general formula (1-2) will be described.

(Repeating unit represented by general formula (1-1))

[Chemical Formula 4]

In the general formula (1-1), Z ¹ represents a hydrogen atom or a monovalent substituent. The monovalent substituent represented by Z ¹ is not particularly limited, and examples thereof include alkyl groups, alkoxy groups, and halogen atoms. Examples of the alkyl group include an alkyl group having 1 to 20 carbon atoms (may be any of linear, branched, and cyclic.). The carbon number of the alkyl group is preferably 1-10, more preferably 1-6, and even more preferably 1-3. The above-mentioned alkyl group may further have a substituent. Examples of the substituent include halogen atoms and hydroxyl groups. Examples of the alkoxy group include an alkoxy group having 1 to 20 carbon atoms (may be any of linear, branched, and cyclic.). The carbon number of the alkoxy group is preferably 1-10, more preferably 1-6, and even more preferably 1-3. The alkoxy group may further have a substituent. Examples of halogen atoms include fluorine atoms, chlorine atoms, bromine atoms, and iodine atoms.

Among them, Z ¹ is preferably a hydrogen atom or an alkyl group.

X ¹ represents an oxygen atom or a sulfur atom. Among them, X ¹ is preferably an oxygen atom.

R ¹ represents a (n+1)-valent hydrocarbon group having one or more fluorine atoms. In addition, R ¹ corresponds to a linking group that connects n hydroxyl groups and X ¹ that are clearly shown in the general formula (1-1). n represents an integer of 1 or more. The upper limit of n is not particularly limited, and is 20, for example. As n, 1-10 is preferable, 1-5 is more preferable, 1-3 is still more preferable, 1 or 2 is especially preferable, and 2 is most preferable. In addition, the (n+1)-valent hydrocarbon group represented by R ¹ having one or more fluorine atoms may further have a substituent (for example, as exemplified in the substituent group T shown below). 〈<Substituent group>> Examples of the substituent group T include halogen atoms such as fluorine atom, chlorine atom, bromine atom and iodine atom; alkoxy groups such as methoxy group, ethoxy group and third butoxy group; phenoxy Aryloxy groups such as phenyl and p-tolyloxy; alkoxycarbonyl groups such as methoxycarbonyl, butoxycarbonyl and phenoxycarbonyl; acetyloxy, propyloxy and benzoyloxy etc. ; Acyl, benzoyl, isobutyl, acryloyl, methacryloyl, and methoxaloyl; acyl and other alkylthio groups such as methylthio and third butylthio; phenylthio and Arylthio groups such as p-tolylthio; alkyl; cycloalkyl; aryl; heteroaryl; hydroxy; carboxyl; formyl; sulfo; cyano; alkylaminocarbonyl; arylaminocarbonyl; sulfo Acylamino; silyl; amine; monoalkylamino; dialkylamino; arylamino; and combinations of these.

The (n+1)-valent hydrocarbon group represented by R ¹ having one or more fluorine atoms is not particularly limited, and examples thereof include the following. In addition, the case where R ¹ is a divalent hydrocarbon group having one or more fluorine atoms and a trivalent or more hydrocarbon group having one or more fluorine atoms will be described below.

·Divalent hydrocarbon group with one or more fluorine atoms Examples of the divalent hydrocarbon group include a divalent aliphatic hydrocarbon group and a divalent aromatic hydrocarbon group. That is, examples of the divalent hydrocarbon group having one or more fluorine atoms include a divalent aliphatic hydrocarbon group having one or more fluorine atoms and a divalent aromatic hydrocarbon group having one or more fluorine atoms.

The divalent aliphatic hydrocarbon group may be any of linear, branched, and cyclic, and examples thereof include alkylene groups having 1 to 20 carbon atoms (preferably alkylene groups having 1 to 10 carbon atoms). ), an alkenyl group having 2 to 20 carbon atoms (preferably an alkenyl group having 2 to 10 carbon atoms) and an alkynyl group having 2 to 20 carbon atoms (preferably an alkynyl group having 2 to 10 carbon atoms). In addition, as the carbon number of the above-mentioned divalent aromatic hydrocarbon group, 6 to 20 is preferable, 6 to 14 is more preferable, and 6 to 10 is even more preferable. For example, phenylene can be cited.

Examples of the divalent hydrocarbon group represented by R ¹ having one or more fluorine atoms include groups represented by the following formulas (M1) to (M3). In the following formula (M1), L ²⁰¹ represents a divalent aliphatic hydrocarbon group having one or more fluorine atoms or a divalent aromatic hydrocarbon group having one or more fluorine atoms. In the following formula (M2), L ²⁰² represents a divalent aromatic hydrocarbon group or a cyclic divalent aliphatic hydrocarbon group, and L ²⁰³ represents a linear or branched divalent aliphatic hydrocarbon group. Among them, one or more of L ²⁰² and L ²⁰³ have one or more fluorine atoms. In the following formula (M3), L ²⁰⁴ represents a single bond, a divalent aliphatic hydrocarbon group or a divalent aromatic hydrocarbon group, and L ²⁰⁵ represents a linear or branched divalent aliphatic hydrocarbon group. Among them, one or more of L ²⁰⁴ and L ²⁰⁵ have one or more fluorine atoms. R ^A and R ^B each independently represent a hydrogen atom or a monovalent substituent (as the substituent, for example, those exemplified in the above substituent group T can be cited, and an alkyl group having 1 to 20 carbon atoms is preferred. The alkyl group may be It further has a substituent.).

As specific examples of the above-mentioned divalent aliphatic hydrocarbon group and the above-mentioned divalent aromatic hydrocarbon group in formulas (M1) to (M3), the above-mentioned ones can be mentioned. In addition, the divalent aliphatic hydrocarbon group and the divalent aromatic hydrocarbon group may further have a substituent (for example, those exemplified in the substituent group T). In the above formula (M1) to the above formula (M3), one of * represents the bonding position with the above X ¹ , and the other of * represents the hydroxyl group clearly expressed in the general formula (1-1) (wherein, n =1) The bonding position.

In the above formula (M2) and the above formula (M3), the linear or branched divalent aliphatic hydrocarbon group represented by L ²⁰³ and L ²⁰⁵ is a linear or branched chain having one or more fluorine atoms The divalent aliphatic hydrocarbon group in the form is preferable, and -CH ₂ -C(CF ₃ ) ₂ -or -C(CF ₃ ) ₂ -is more preferable.

When R ^{1 is} represented by the above formula (M2), the L ²⁰² side is the bonding position with X ¹ , and the L ²⁰³ side is the bonding with the hydroxyl group (where n=1) clearly shown in the general formula (1-1) The location is better. In addition, when R ^{1 is} represented by the above formula (M3), the L ²⁰⁴ side is a bonding position with X ¹ , and the L ²⁰⁵ side is a bonding position with a hydroxyl group shown in the general formula (1-1).

[Chemical Formula 5]

·A hydrocarbon group with more than 3 valences of one or more fluorine atoms Examples of the above-mentioned trivalent or higher hydrocarbon group include trivalent or more aliphatic hydrocarbon groups and trivalent or more aromatic hydrocarbon groups. That is, examples of the trivalent or higher hydrocarbon group having one or more fluorine atoms include trivalent or more aliphatic hydrocarbon groups having one or more fluorine atoms and trivalent or more aromatic groups having one or more fluorine atoms Hydrocarbyl.

Examples of the trivalent or higher hydrocarbon group having one or more fluorine atoms represented by R ¹ include groups represented by the following formula (M4) to formula (M8). In the following formula (M4), L ³⁰¹ to L ³⁰³ each independently represent a single bond, a divalent aliphatic hydrocarbon group, or a divalent aromatic hydrocarbon group. Among them, one or more of L ³⁰¹ to L ³⁰³ contain a fluorine atom. In the above formula (M4), R ^C represents a hydrogen atom or a monovalent substituent (as the substituent, for example, those exemplified in the above substituent group T can be cited, and an alkyl group having 1 to 20 carbon atoms is preferred. It may further have a substituent.).

In the following formula (M5), L ³⁰⁴ to L ³⁰⁶ each independently represent a single bond or a divalent aliphatic hydrocarbon group. Among them, at least one of L ³⁰⁴ to L ³⁰⁶ contains a fluorine atom.

In the following formula (M6), L ³⁰⁷ to L ³⁰⁹ each independently represent a single bond or a divalent aliphatic hydrocarbon group. Among them, at least one of L ³⁰⁷ to L ³⁰⁹ contains a fluorine atom.

In the following formula (M7), L ³¹⁰ to L ³¹³ each independently represent a single bond, a divalent aliphatic hydrocarbon group, or a divalent aromatic hydrocarbon group. Among them, at least one of L ³¹⁰ to L ³¹³ contains a fluorine atom.

In the following formula (M8), L ³¹⁴ to L ³²⁰ each independently represent a single bond, a divalent aliphatic hydrocarbon group, or a divalent aromatic hydrocarbon group. Among them, one or more of L ³¹⁴ to L ³²⁰ contain a fluorine atom. r represents an integer of 1-10, the integer of 1-3 is more preferable, and 1 or 2 is more preferable.

As specific examples of the divalent aliphatic hydrocarbon group and the divalent aromatic hydrocarbon group in the formulas (M4) to (M8), the above-mentioned ones can be mentioned. In addition, the divalent aliphatic hydrocarbon group and the divalent aromatic hydrocarbon group may further have a substituent (for example, those exemplified in the substituent group T). In the following formula (M4) to the above formula (M8), one of the plurality of * represents the bonding position to the above X ¹ , and the residual part of * represents the hydroxyl group clearly expressed in the general formula (1-1) Bonding position.

In the following formula (M5), L ³⁰⁴ represents a single bond, and L ³⁰⁵ and L ³⁰⁶ represent a linear or branched divalent aliphatic hydrocarbon group having one or more fluorine atoms. Regarding L ³⁰⁵ and L ³⁰⁶ , -CH ₂ -C(CF ₃ ) ₂ -or -C(CF ₃ ) ₂ -is more preferable. In addition, when R ^{1 is} represented by the above formula (M5), the L ³⁰⁴ side is the bonding position with X ¹ , and the L ³⁰⁵ and L ³⁰⁶ sides are the same as the hydroxyl group clearly shown in the general formula (1-1) (where, n= 2) The bonding position is better.

In the above formula (M6), L ³⁰⁷ represents a single bond, and L ³⁰⁸ and L ³⁰⁹ represent a linear or branched divalent aliphatic hydrocarbon group having one or more fluorine atoms. Regarding L ³⁰⁸ and L ³⁰⁹ , -CH ₂ -C(CF ₃ ) ₂ -or -C(CF ₃ ) ₂ -is more preferable. In addition, when R ^{1 is} represented by the following formula (M6), the L ³⁰⁷ side is the bonding position with X ¹ , and the L ³⁰⁸ and L ³⁰⁹ sides are the same as the hydroxy group clearly shown in the general formula (1-1) (where, n =2) The bonding position is better.

[Chemical Formula 6]

Hereinafter, specific examples of the repeating unit represented by the general formula (1-1) are exemplified, but not limited thereto.

[Chemical Formula 7]

(Repeating unit represented by general formula (1-2))

[Chemical Formula 8]

In the general formula (1-2), Z ² represents a hydrogen atom or a monovalent substituent. Represented by a Z ² 1 The monovalent substituent in the general formula (1-1) by the same meanings of the substituents Z 1 represents ^a monovalent, the preferred aspects are also the same.

X ² represents an oxygen atom or a sulfur atom. Among them, X ² is preferably an oxygen atom.

R ² represents an alkylene group having 1 to 10 carbon atoms. The alkylene group represented by the above R ² may be any of linear, branched, and cyclic, preferably having 1 to 6 carbon atoms, and more preferably 1 to 4 carbon atoms. In addition, the above-mentioned alkylene group may further have a substituent (for example, those exemplified in the above-mentioned substituent group T).

R ³ represents a monovalent substituent. The monovalent substituent represented by R ³ is not particularly limited, and an alkyl group, -SO ₂ -alkyl group, alkoxy group, or acetyl group is preferred. Examples of the alkyl group in the alkyl group and -SO ₂ -alkyl group include an alkyl group having 1 to 20 carbon atoms (any one of linear, branched, and cyclic.). The carbon number of the alkyl group is preferably 1-10, more preferably 1-6, and even more preferably 1-3. The above-mentioned alkyl group may further have a substituent (for example, those exemplified in the above-mentioned substituent group T, and a fluorine atom is preferable.). Examples of the alkoxy group include an alkoxy group having 1 to 20 carbon atoms (may be any of linear, branched, and cyclic.). The carbon number of the alkoxy group is preferably 1-10, more preferably 1-6, and even more preferably 1-3. The above-mentioned alkoxy group may further have a substituent (for example, those exemplified in the above-mentioned substituent group T, and a fluorine atom is preferable.). Examples of the acyl group include an alkylcarbonyl group having 1 to 20 carbon atoms (which may be linear, branched, or cyclic.). The number of carbon atoms in the alkylcarbonyl group is preferably 1-10, more preferably 1-6, and even more preferably 1-3. The above-mentioned alkylcarbonyl group may further have a substituent (for example, those exemplified in the above-mentioned substituent group T, and a fluorine atom is preferred.). As a monovalent substituent represented by R ³ , from the viewpoint that the resolution of the above composition is more excellent and/or that the LWR of the formed pattern is more excellent, -SO ₂ -alkyl or -CO -An alkyl group is preferable, and -SO ₂ -alkyl group having 1 to 4 carbon atoms or -CO-alkyl group having 1 to 4 carbon atoms is more preferable. In addition, the above-mentioned alkyl group may be substituted with a fluorine atom.

Hereinafter, specific examples of the repeating unit represented by the general formula (1-2) are exemplified, but not limited thereto.

[Chemical Formula 9]

The resin (A) may contain one kind of specific repeating unit 1 alone, or may contain two or more kinds at the same time.

The content of the specific repeating unit 1 contained in the resin (A) (in the case where a plurality of repeating units including the specific repeating unit 1 are present, the total) is 5 to 30 moles relative to all the repeating units of the resin (A) % Is better, 10-25 mol% is more preferable, and 10-20 mol% is even more preferable.

<Specific repeating unit 2> The resin (A) includes a repeating unit (specific repeating unit 2) including a partial structure represented by the general formula (2) described later. Hereinafter, the specific repeating unit 2 will be described.

[Chemical Formula 10]

In the general formula (2), Y ¹ represents an oxygen atom or -C(R ^X1 ) ₂ -. Y ² represents a carbonyl group or a sulfonyl group. Y ³ represents an oxygen atom, -NR ^X2 -or -C(R ^X3 ) ₂ -. In addition, as a combination of Y ¹ , Y ² and Y ³ , when Y ² represents a carbonyl group, as a combination of Y ¹ and Y ³ (Y ¹ , Y ³ ), (oxygen atom, oxygen atom), (oxygen atom, -NR ^X2 -) or (-C(R ^X1 ) ₂ -, -NR ^X2 -) are preferred.

R ^X1 , R ^X2 and R ^X3 each independently represent a hydrogen atom or a monovalent substituent. The monovalent substituent represented by R ^X1 , R ^X2 and R ^X3 is not particularly limited, and examples thereof include the groups exemplified in the above substituent group T, and among them, an alkyl group having 1 to 20 carbon atoms (may be It is any of linear, branched and cyclic.). The carbon number of the alkyl group is preferably 1-10, more preferably 1-6, and even more preferably 1-3. The above-mentioned alkyl group may further have a substituent (for example, the group exemplified in the above-mentioned substituent group T). As R ^X1 , R ^X2 and R ^X3 , a hydrogen atom is preferred. In addition, a plurality of R ^X1 and a plurality of R ^X3 may be the same or different.

W ¹ includes at least Y ^{1 indicated} in the above general formula (2), Y ^{2 indicated in the} above general formula (2), and Y ³ indicated in the above general formula (2), indicating 5 which may have a substituent ~ 7-member ring. Among them, W ¹ does not constitute a lactone ring. The 5- to 7-membered ring represented by W ¹ is preferably non-aromatic. The atoms constituting W ¹ other than the above Y ¹ , Y ² and Y ³ may be carbon atoms or heteroatoms. Examples of heteroatoms include oxygen atoms, nitrogen atoms, and sulfur atoms, represented by -Y ^X1 -, -N(Ra)-, -C(=Y ^X2 )-, -CON(Rb)-, -C(=Y ^X3 ) Y ^X4 -or the combination of these groups is preferably included. Y ^X1 to Y ^X4 each independently represent an oxygen atom or a sulfur atom, and an oxygen atom is preferred. t represents an integer of 1-3. Ra, Rb, and Rc each independently represent a hydrogen atom or an alkyl group having 1 to 10 carbon atoms. As the 5- to 7-membered ring represented by W ¹ , among them, the atom-based carbon atoms other than Y ¹ , Y ² and Y ³ constituting the ring are preferred. In addition, as the 5- to 7-membered ring represented by W ¹ , a 5-membered ring or a 6-membered ring is preferred. In addition, the 5- to 7-membered ring represented by W ¹ can form a polycyclic structure by bonding with other alicyclic rings and/or heteroalicyclic rings. In addition, in the case of a multi-ring structure, it may be a spiral ring structure. In addition, in the alicyclic ring and the heteroalicyclic ring, the carbon constituting the ring (carbon that contributes to ring formation) may be a carbonyl carbon. Examples of the alicyclic ring include monocyclic naphthenes such as cyclopentane, cyclohexane, and cyclooctane, norbornene, tricyclodecane, tetracyclodecane, tetracyclododecane, and adamantane. Polycyclic naphthenes. In addition, in the monocyclic and polycyclic naphthenes exemplified as the above-mentioned specific examples, the carbon constituting the ring (the carbon contributing to the formation of the ring) may be replaced by a carbonyl carbon.

Examples of the heteroalicyclic ring include a furan ring and a lactone ring.

The substituent that W ¹ may have is not particularly limited, and examples thereof include the groups exemplified in the above substituent group T. Specific examples of the substituent include an alkyl group having 1 to 20 carbon atoms (may be any of linear, branched, and cyclic.). The carbon number of the alkyl group is preferably 1-10, more preferably 1-6, and even more preferably 1-3. The above-mentioned alkyl group may further have a substituent (for example, the group exemplified in the above-mentioned substituent group T).

The partial structure represented by the above general formula (2) is preferably one or more types selected from the group including general formula (3) to general formula (8). [Chemical Formula 11]

In the general formula (3), W ² contains at least one oxygen atom, one nitrogen atom, and one carbon atom, and represents a 5- to 7-membered ring which may have a substituent. The 5- to 7-membered ring which may have a substituent represented by W ² has the same meaning as W ¹ in the general formula (2), and the preferred aspects are also the same. R ⁴ represents a hydrogen atom or a monovalent substituent. The monovalent substituent represented by R ⁴ has the same meaning as the monovalent substituent represented by R ^X1 , R ^X2 and R ^X3 in the general formula (2), and the preferred aspects are also the same.

In the general formula (4), W ³ contains at least one nitrogen atom and two carbon atoms, and represents a 5- to 7-membered ring which may have a substituent. The 5- to 7-membered ring which may have a substituent represented by W ³ has the same meaning as W ¹ in the general formula (2), and the preferred aspects are also the same. R ⁵ , R ⁶ and R ⁷ each independently represent a hydrogen atom or a monovalent substituent. The monovalent substituent represented by R ⁵ , R ⁶ and R ⁷ has the same meaning as the monovalent substituent represented by R ^X1 , R ^X2 and R ^X3 in the above general formula (2), and the preferred form is also the same.

In the general formula (5), W ⁴ represents a 5- to 7-membered ring that contains at least one carbon atom and two oxygen atoms and may have a substituent. The 5- to 7-membered ring which may have a substituent represented by W ⁴ has the same meaning as W ¹ in the general formula (2), and the preferred aspects are also the same. As W ⁴ , a five-membered ring is preferred.

In the general formula (6), W ⁵ represents a 5- to 7-membered ring that contains at least one nitrogen atom, one sulfur atom, and one carbon atom, and may have a substituent. The 5- to 7-membered ring which may have a substituent represented by W ⁵ has the same meaning as W ¹ in the general formula (2), and the preferred aspects are also the same. R ⁸ , R ⁹ and R ¹⁰ each independently represent a hydrogen atom or a monovalent substituent. The monovalent substituent represented by R ⁸ , R ⁹ and R ¹⁰ has the same meaning as the monovalent substituent represented by R ^X1 , R ^X2 and R ^X3 in the above general formula (2), and the preferred form is also the same.

In the general formula (7), W ⁶ represents a 5- to 7-membered ring that contains at least one oxygen atom, one sulfur atom, and one carbon atom, and may have a substituent. The 5- to 7-membered ring which may have a substituent represented by W ⁶ has the same meaning as W ¹ in the general formula (2), and the preferred aspects are also the same. R ¹¹ and R ¹² each independently represent a hydrogen atom or a monovalent substituent. The monovalent substituent represented by R ¹¹ and R ¹² has the same meaning as the monovalent substituent represented by R ^X1 , R ^X2 and R ^X3 in the above general formula (2), and the preferred aspects are also the same.

In the general formula (8), W ⁷ represents a 5- to 7-membered ring containing at least 1 sulfur atom and 2 carbon atoms, and may have a substituent. The 5- to 7-membered ring which may have a substituent represented by W ⁷ has the same meaning as W ¹ in the general formula (2), and the preferred aspects are also the same. R ¹³ , R ¹⁴ , R ¹⁵ and R ¹⁶ each independently represent a hydrogen atom or a monovalent substituent. The monovalent substituent represented by R ¹³ , R ¹⁴ , R ¹⁵ and R ¹⁶ has the same meaning as the monovalent substituent represented by R ^X1 , R ^X2 and R ^X3 in the above general formula (2), preferably The same is true.

From the viewpoint that the LWR of the formed pattern is more excellent, the general formula (3) to the general formula (8) are selected from the group including the general formula (4), the general formula (5), and the general formula (8) One or more of them are preferred, and one or more selected from the group including general formula (5) and general formula (8) is more preferred, and general formula (5) is further preferred.

Examples of the specific repeating unit 2 include repeating units represented by the following general formulas (9) to (13).

[Chemical Formula 12]

[Chemical Formula 13]

In the general formula (9), R ¹⁷ represents a hydrogen atom or a monovalent substituent. The monovalent substituent represented by R ¹⁷ has the same meaning as the monovalent substituent represented by Z ¹ in the general formula (1-1), and the preferred aspects are also the same. L ^A represents a divalent linking group. The divalent linking group represented by L ^A is not particularly limited, and examples include -CO-, -O-, -NH-, and divalent aliphatic hydrocarbon groups (which may be linear, branched, or cyclic) Any one of them.) and a divalent linking group formed by combining these pluralities. In addition, as the divalent aliphatic hydrocarbon group, an alkylene group having 1 to 6 carbon atoms, an alkynyl group having 2 to 6 carbon atoms, or an alkenyl group having 2 to 6 carbon atoms is preferable. The divalent aliphatic hydrocarbon group may further have a substituent (for example, the groups exemplified in the above-mentioned substituent group T.). Examples of the divalent linking group represented by L ^A include -COO- and -COO-2 valent aliphatic hydrocarbon groups-and -CO-. R ¹⁸ represents a monovalent group including a partial structure represented by the above general formula (2). R ¹⁸ may be a monovalent group formed by removing one hydrogen atom from the partial structure represented by the above general formula (2), or may include a partial structure represented by the general formula (2) and other alicyclic rings A monovalent group of a polycyclic structure formed by bonding and/or heteroalicyclic rings to each other. In addition, the polycyclic structure formed by bonding a part of the structure represented by the general formula (2) to another alicyclic ring and/or heteroalicyclic ring is as described above.

In the general formula (10), R ¹⁹ represents a hydrogen atom or a monovalent substituent. The monovalent substituent represented by R ¹⁹ has the same meaning as the monovalent substituent represented by Z ¹ in the general formula (1-1), and the preferred aspects are also the same. Y ² and Y ³ are the same as in the general formula the meaning of Y ² and Y ³ (2). R ²⁰ to R ²³ each independently represent a hydrogen atom or a monovalent substituent. The monovalent substituent represented by R ²⁰ to R ²³ has the same meaning as the substituent that W ¹ in the general formula (2) may have, and the preferred aspects are also the same. When m1 represents 2 or 3, a plurality of R ²⁰ to R ²³ may be the same or different. m1 is an integer of 1-3, and 1 or 2 is preferable.

In the general formula (11), R ²⁴ represents a hydrogen atom or a monovalent substituent. The monovalent substituent represented by R ²⁴ has the same meaning as the monovalent substituent represented by Z ¹ in the general formula (1-1), and the preferred aspects are also the same. R ²⁵ and R ²⁶ each independently represent a hydrogen atom or a monovalent substituent. The monovalent substituent represented by R ²⁵ and R ²⁶ has the same meaning as the substituent that W ¹ in the general formula (2) may have, and the preferred aspects are also the same. When m2 represents 2, a plurality of R ²⁵ and R ²⁶ may be the same or different. m2 represents 1 or 2, with 1 being preferred. X ^A3 represents -CO- or -C(R ^T1 ) ₂ -. The above R ^T1 each independently represents a hydrogen atom or a monovalent substituent. The monovalent substituent represented by R ^T1 has the same meaning as the substituent that W ¹ in the general formula (2) may have, and the preferred aspects are also the same. L ^B represents a divalent linking group. The divalent linking group represented by L ^B is not particularly limited, and examples thereof include -CO-, -O-, -NH-, and divalent aliphatic hydrocarbon groups (which may be linear, branched, or cyclic) Any one of them.) and a bivalent linking group formed by combining these pluralities. In addition, as the divalent aliphatic hydrocarbon group, an alkylene group having 1 to 6 carbon atoms, an alkynyl group having 2 to 6 carbon atoms, or an alkenyl group having 2 to 6 carbon atoms is preferable. The divalent aliphatic hydrocarbon group may further have a substituent (for example, the groups exemplified in the above-mentioned substituent group T.). Represents the divalent linking group of L ^B, a divalent aliphatic hydrocarbon group is preferred. R ²⁷ has the same meaning as R ¹⁸ in the above general formula (9), and the preferred aspects are also the same.

In the general formula (12), R ²⁸ represents a hydrogen atom or a monovalent substituent. The monovalent substituent represented by R ²⁸ has the same meaning as the monovalent substituent represented by Z ¹ in the general formula (1-1), and the preferred aspects are also the same. R ²⁹ to R ³² each independently represent a hydrogen atom or a monovalent substituent. The monovalent substituent represented by R ²⁹ to R ³² has the same meaning as the substituent that W ¹ in the general formula (2) may have, and the preferred aspects are also the same. When m3 represents 2, a plurality of R ²⁹ and R ³⁰ may be the same or different. When m4 represents 2, a plurality of R ³¹ and R ³² may be the same or different. m3 represents 1 or 2, with 1 being preferred. m4 represents an integer of 0 to 2, with 0 or 1 being preferred. Y ^1, Y ² and Y ³ are Y in the general formula (2) is ^1, Y ² and Y ³ are the same meaning. X ^A4 represents -CO-, -C(R ^T1 ) ₂ -, -NR ^T2 -or -O-. Each of R ^T1 and R ^T2 independently represents a hydrogen atom or a monovalent substituent. The monovalent substituent represented by R ^T1 and R ^T2 has the same meaning as the substituent that W ¹ in the general formula (2) may have, and the preferred aspects are also the same.

In the general formula (13), R ³³ represents a hydrogen atom or a monovalent substituent. The monovalent substituent represented by R ³³ has the same meaning as the monovalent substituent represented by Z ¹ in the above general formula (1-1), and the preferred aspects are also the same. R ³⁴ to R ³⁹ each independently represent a hydrogen atom or a monovalent substituent. The monovalent substituent represented by R ³⁴ to R ³⁹ has the same meaning as the substituent that W ¹ in the general formula (2) may have, and the preferred aspects are also the same. X ^A5 , X ^A6 and X ^A7 represent -CO-, -C(R ^T1 ) ₂ -, -NR ^T2 -or -O-. Each of R ^T1 and R ^T2 independently represents a hydrogen atom or a monovalent substituent. The monovalent substituent represented by R ^T1 and R ^T2 has the same meaning as the substituent that W ¹ in the general formula (2) may have, and the preferred aspects are also the same. Among them, X ^A5 represents -CO-, and X ^A6 and X ^A7 represent -O- in the general formula (13). Y ^1, Y ² and Y ³ are Y in the general formula (2) is ^1, Y ² and Y ³ are the same meaning.

Hereinafter, a specific example of the repeating unit 2 is illustrated, but it is not limited to this.

[Chemical Formula 14]

[Chemical Formula 15]

The resin (A) may contain one kind of specific repeating unit 2 alone, or may contain two or more kinds at the same time.

The content of the specific repeating unit 2 contained in the resin (A) (in the case where a plurality of repeating units including the specific repeating unit 2 are present, the total) is 5 to 40 moles relative to all the repeating units of the resin (A) % Is better, 10-40 mole% is more preferable, and 10-30 mole% is even more preferable.

In addition, from the viewpoint that the LWR of the formed pattern is more excellent, the content of the repeating unit 2 in the resin (A) (when there are a plurality of repeating units including the specific repeating unit 2 is the total) is greater than the repeating unit The content of 1 (when there are a plurality of repeating units including the specific repeating unit 1 is the total) is preferable.

<Other repeating units> The resin (A) may contain other repeating units than the repeating unit containing an acid-decomposable group, the specific repeating unit 1 and the specific repeating unit 2. However, when the resin (A) contains the above-mentioned other repeating units, the above-mentioned other repeating units do not substantially include repeating units containing a lactone structure. Here, "substantially does not include a repeating unit containing a lactone structure" means that the content of the repeating unit containing a lactone structure in the resin (A) is 5 mol% or less with respect to all the repeating units of the resin (A) , 3 mol% or less is preferred, 1 mol% or less is further preferred, and 0 mol% is particularly preferred.

From the viewpoint that the resolution of the above composition is more excellent and/or that the LWR of the formed pattern is more excellent, the resin (A) contains a repeating unit containing a ring structure directly bonded to the main chain as the other repeating unit is Better.

Examples of the repeating unit including a ring structure directly bonded to the main chain include a repeating unit represented by the general formula (D) or the general formula (E). In addition, the repeating unit represented by the general formula (D) or the general formula (E) does not include the specific repeating unit 2. (Repeating unit represented by general formula (D))

[Chemical Formula 16]

In formula (D), "Cyclic" means a group that forms a main chain with a cyclic structure. The number of constituent atoms of the ring is not particularly limited.

As specific examples of the repeating unit represented by the formula (D), the following repeating units may be mentioned.

[Chemical Formula 17]

In the above formula, R independently represents a hydrogen atom, an alkyl group, a cycloalkyl group, an aryl group, an aralkyl group, an alkenyl group, a hydroxyl group, an alkoxy group, an oxy group, a cyano group, a nitro group, an amine group, a halogen atom , Ester group (-OCOR'' or -COOR'': R'' is a C 1-20 alkyl group or fluorinated alkyl group) or a carboxyl group. In addition, the alkyl group, the cycloalkyl group, the aryl group, the aralkyl group, and the alkenyl group may each have a substituent. In addition, the hydrogen atom bonded to the carbon atom in the group represented by R may be replaced by a fluorine atom or an iodine atom. In the above formula, R′ independently represents an alkyl group, a cycloalkyl group, an aryl group, an aralkyl group, an alkenyl group, a hydroxyl group, an alkoxy group, an oxy group, a cyano group, a nitro group, an amine group, a halogen atom, an ester Group (-OCOR'' or -COOR'': R'' is an alkyl group having 1 to 20 carbon atoms or a fluorinated alkyl group) or a carboxyl group. In addition, the alkyl group, the cycloalkyl group, the aryl group, the aralkyl group, and the alkenyl group may each have a substituent. In addition, the hydrogen atom bonded to the carbon atom in the group represented by R'may be substituted with a fluorine atom or an iodine atom. m represents an integer of 0 or more. The upper limit of m is not particularly limited, but is usually 2 or less, and more often 1 or less.

(Repeating unit represented by formula (E))

[Chemical Formula 18]

In formula (E), Re independently represents a hydrogen atom or an organic group. Examples of the organic group include alkyl groups, cycloalkyl groups, aryl groups, aralkyl groups, and alkenyl groups which may have substituents. "Cyclic" is a cyclic group containing carbon atoms in the main chain. The number of atoms contained in the cyclic group is not particularly limited.

As specific examples of the repeating unit represented by formula (E), the following repeating units may be mentioned.

[Chemical Formula 19]

In the above formula, R'independently represents a hydrogen atom, an alkyl group, a cycloalkyl group, an aryl group, an aralkyl group and an alkenyl group, a hydroxyl group, an alkoxy group, an oxy group, a cyano group, a nitro group, an amine group, a halogen Atom, ester group (-OCOR'' or -COOR'': R'' is C1-C20 alkyl group or fluorinated alkyl group) or carboxyl group. In addition, the alkyl group, the cycloalkyl group, the aryl group, the aralkyl group, and the alkenyl group may each have a substituent. In addition, the hydrogen atom bonded to the carbon atom in the group represented by R'may be substituted with a fluorine atom or an iodine atom. m represents an integer of 0 or more. The upper limit of m is not particularly limited, but is usually 2 or less, and more often 1 or less.

The weight-average molecular weight of the resin (A) as a polystyrene conversion value measured by the GPC method is preferably 1,000 to 200,000, and more preferably 3,000 to 20,000. By setting the weight average molecular weight to 1,000 to 200,000, the deterioration of heat resistance and dry etching resistance can be prevented, and further the deterioration of developability and the deterioration of film formability due to the increase in viscosity can be prevented. On the other hand, the weight average molecular weight of the resin (A) is preferably 3,000 to 9,500 as the polystyrene conversion value measured by the GPC method. The degree of dispersion (molecular weight distribution) is usually 1 to 5, preferably 1 to 3, more preferably 1.2 to 3.0, and further preferably 1.2 to 2.0. The smaller the degree of dispersion, the better the resolution and the shape of the resist. Furthermore, the smoother the sidewalls of the resist pattern and the better the roughness.

In the resin (A), it is a matter of course that there are few impurities such as metals, and the content of residual monomer and oligomer components is also small. Specifically, the content of the residual monomer and oligomer components in the resin (A) is preferably 10% by mass or less, more preferably 5% by mass or less, and further preferably 1% by mass or less. In addition, the lower limit value is, for example, 0% by mass. By reducing the content of residual monomers and oligomer components in the resin (A), a composition with less foreign matters in the liquid and suppressed changes in sensitivity over time can be obtained.

The resin (A) can be synthesized according to a conventional method (for example, radical polymerization). For example, as a general synthesis method, a unified polymerization method in which a monomer species and an initiator are dissolved in a solvent and heated to thereby perform polymerization; and a monomer species is added dropwise to a heated solvent over 1 to 10 hours The addition polymerization method and the like are carried out with the solution of the initiator, and the addition polymerization method is preferable. Examples of the reaction solvent include ethers such as tetrahydrofuran, 1,4-dioxane, and diisopropyl ether; ketones such as methyl ethyl ketone and methyl isobutyl ketone; ester solvents such as ethyl acetate; dimethyl Acetylamine solvents such as methylformamide, dimethylacetamide, and N-methylpyrrolidone; the dissolution resist compositions such as propylene glycol monomethyl ether acetate, propylene glycol monomethyl ether, and cyclohexanone, which will be described later. Solvent, etc. Among them, it is preferable to use the same solvent as the solvent used for the resist composition for polymerization. This can suppress the generation of particles during storage.

The polymerization reaction is preferably carried out in an inert gas environment such as nitrogen and argon. As the polymerization initiator, a commercially available radical initiator (azo-based initiator, peroxide, etc.) can be used. As the radical initiator, an azo-based initiator is preferred, and an azo-based initiator having an ester group, a cyano group, a carboxyl group and the like is more preferred. Examples of such an azo-based initiator include azobisisobutyronitrile, azobisdimethylvaleronitrile, and dimethyl 2,2'-azobis(2-methylpropionate). The polymerization initiator may be any of batch addition and separate addition. In addition, the solid content concentration of the reaction liquid is preferably 5 to 50% by mass, and more preferably 10 to 45% by mass. The reaction temperature is usually 10 to 150°C, preferably 30 to 120°C, and more preferably 40 to 100°C. After the reaction is completed, the desired polymer is recovered by a method such as powder or solid recovery by pouring the reaction solution into a solvent. The recovered polymer is preferably purified. For purification, the following general methods can be applied: liquid-liquid extraction method that removes residual monomers or oligomer components by water washing and combination of appropriate solvents; purification method in the state of solution such as ultrafiltration that extracts and removes only those with a specific molecular weight or less ; Re-precipitation method to remove the residual monomers by solidifying the resin in the poor solvent by dropping the resin solution in the poor solvent; and using the poor solvent to clean the filtered resin slurry in the solid state, etc. Under the purification method and so on.

In the above composition, the content of the resin (A) is preferably 50 to 99.9% by mass relative to the total solid content of the composition, and more preferably 60 to 99.0% by mass. In addition, one kind of resin (A) may be used, or plural kinds may be used in combination.

<Photoacid generator (B)> The composition of the present invention contains a photoacid generator (hereinafter, also referred to as "photoacid generator (B)"). The photoacid generator is a compound that generates an acid by irradiation of actinic rays or radiation. As the photoacid generator (B), a compound that generates an acid by irradiation with actinic rays or radiation is preferred. For example, osmium salt compounds, iodonium salt compounds, diazonium salt compounds, phosphonium salt compounds, amide imine sulfonate compounds, oxime sulfonate compounds, diazonium disulfonate compounds, dioxin compounds, and o-nitrobenzylsulfonate Acid compound.

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

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

[Chemical Formula 20]

In the above 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, preferably 1 to 20. In addition, two of R ₂₀₁ to R ₂₀₃ may be bonded to form a ring structure, and an oxygen atom, a sulfur atom, an ester bond, an amide bond, or a carbonyl group may be included in the ring. Examples of the group formed by bonding two of R ₂₀₁ to R ₂₀₃ include an alkylene group (for example, butyl group and pentyl group) and -CH ₂ -CH ₂ -O-CH ₂ -CH ₂ -. Z ^- represents an anion.

Preferred examples 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. In addition, the photoacid generator (B) may be a compound having a structure represented by a plurality of general formulas (ZI). For example, at least one of R ₂₀₁ to R ₂₀₃ having a compound represented by general formula (ZI) and at least one of R ₂₀₁ to R ₂₀₃ of another compound represented by general formula (ZI) may be through a single bond Or a compound that connects the structure of the bonding group.

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

As the aryl group included in the aryl um compound, phenyl or naphthyl is preferred, and phenyl is more preferred. The aryl group may be an aryl group containing a heterocyclic structure having an oxygen atom, a nitrogen atom or a sulfur atom. Examples of the heterocyclic structure include pyrrole residues, furan residues, thiophene residues, indole residues, benzofuran residues, and benzothiophene residues. When the aryl alkene compound has two or more aryl groups, the presence of two or more aryl groups may be the same or different. The alkyl group or cycloalkyl group which the aryl amide compound has as needed is a linear alkyl group having 1 to 15 carbon atoms, a branched alkyl group having 3 to 15 carbon atoms, or a cycloalkyl group having 3 to 15 carbon atoms. Preferably, for example, methyl, ethyl, propyl, n-butyl, second butyl, third butyl, cyclopropyl, cyclobutyl, cyclohexyl and the like can be mentioned.

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), and an aryl group. (For example, carbon number 6-14), an alkoxy group (for example, carbon number 1-15), a halogen atom, a hydroxyl group, or a thiophenyl 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) each independently represent a compound having no aromatic ring organic group. Among them, aromatic rings also include aromatic rings containing heteroatoms. The organic group not having an aromatic ring as R ₂₀₁ to R ₂₀₃ is generally 1 to 30 carbon atoms, and preferably 1 to 20 carbon atoms. R ₂₀₁ to R ₂₀₃ are preferably independently alkyl, cycloalkyl, allyl or vinyl, and linear or branched 2-oxoalkyl, 2-oxocycloalkyl or alkyl The oxycarbonylmethyl group is more preferred, and the linear or branched 2-oxoalkyl group is further preferred.

As the alkyl group and cycloalkyl group of R ₂₀₁ and 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, butyl Group or pentyl group) or a cycloalkyl group having 3 to 10 carbon atoms (for example, cyclopentyl group, cyclohexyl group, and norbornyl group) is preferred. R ₂₀₁ to R ₂₀₃ may be further substituted with a halogen atom, an alkoxy group (for example, C 1 to 5), 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 benzoylmethyl benzoyl salt structure.

[Chemical Formula 21]

In the general formula (ZI-3), R _1c to R _5c 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, Cycloalkylcarbonyloxy, halogen atom, hydroxyl, nitro, alkylthio or arylthio. 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 alkyl, cycloalkyl, 2-oxoalkyl, 2-oxocycloalkyl, alkoxycarbonylalkyl, allyl or vinyl.

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 form a ring structure, and the ring structure may be independent The ground contains an oxygen atom, a sulfur atom, a ketone group, an ester bond, or an amide bond. Examples of the ring structure include aromatic or non-aromatic hydrocarbon rings, aromatic or non-aromatic heterocycles, and polycyclic condensed rings formed by combining two or more such rings. Examples of the ring structure include 3 to 10 member rings, 4 to 8 member rings are preferred, and 5 or 6 member rings are more preferred.

Examples of the group formed by bonding two or more of R _1c to R _5c , R _6c and R _7c , and R _x and R _y include butylene 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 methylene group and ethylidene 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 22]

In the general formula (ZI-4), l represents an integer of 0 to 2. r represents an integer of 0-8. R ₁₃ represents a hydrogen atom, a fluorine atom, a hydroxyl group, an alkyl group, a cycloalkyl group, an alkoxy group, an alkoxycarbonyl group, or a group having a cycloalkyl group. These groups may have a substituent. R ₁₄ represents a hydroxyl group, an alkyl group, a cycloalkyl group, an alkoxy group, an alkoxycarbonyl group, an alkylcarbonyl group, an alkylsulfonyl group, a cycloalkylsulfonyl group, or a group having a cycloalkyl group. These groups may have a substituent. When there are a plurality of R ₁₄ , each of them independently represents the above-mentioned groups 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 included in the ring skeleton. In one aspect, two R ₁₅ are alkylene groups and are preferably 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 1-10. As the alkyl group, methyl, ethyl, n-butyl or tertiary butyl is preferred.

Next, the general formulas (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 , phenyl or naphthyl is preferred, and phenyl is more preferred. The aryl group represented by R ₂₀₄ to R ₂₀₇ may be an aryl group having a heterocyclic structure containing an oxygen atom, a nitrogen atom, or a sulfur atom. 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 (eg, methyl, ethyl, propyl) , Butyl, pentyl, etc.) or C3-C10 cycloalkyl (for example, cyclopentyl, cyclohexyl, norbornyl, etc.) is preferred.

The aryl group, alkyl group, and cycloalkyl group represented by R ₂₀₄ to R ₂₀₇ may each independently have a substituent. Examples of substituents that the aryl group, alkyl group, and cycloalkyl group represented by R ₂₀₄ and R ₂₀₇ may have include, for example, alkyl groups (for example, carbon number 1 to 15) and cycloalkyl groups (for example, carbon number 3 to 3). 15), an aryl group (for example, carbon number 6-15), an alkoxy group (for example, carbon number 1-15), a halogen atom, a hydroxyl group, a 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 (3) The indicated anion is preferred.

[Chemical Formula 23]

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

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 1-10, and more preferably 1-4. In addition, as the alkyl group substituted with at least one fluorine atom, a perfluoroalkyl group is preferred. Xf-based fluorine atoms or perfluoroalkyl groups having 1 to 4 carbon atoms are preferred, and fluorine atoms or CF ₃ are more preferred. In particular, both Xf-based fluorine atoms are further preferred.

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 R ₄ and R ₅ existence plural, R ₄ and R ₅ may be the same, also be different. The alkyl group represented by R ₄ and R ₅ may have a substituent, and preferably has 1 to 4 carbon atoms. R ₄ and R _{5 are} preferably hydrogen atoms. Specific examples and preferred aspects of the alkyl group substituted with at least one fluorine atom are the same as specific examples and preferred aspects of Xf in the general formula (3).

L represents a divalent linking group. When there are a plurality of L, L may be the same or different. Examples of the divalent linking group include -COO-(-C(=O)-O-), -OCO-, -CONH-, -NHCO-, -CO-, -O-, -S-, and- SO-, -SO ₂ -, alkylene group (preferably carbon number 1-6), cycloalkyl group (preferably carbon number 3-15), alkenyl group (preferably carbon number 2-6) And a bivalent linking group formed by combining these plural numbers. Among these, -COO-, -OCO-, -CONH-, -NHCO-, -CO-, -O-, -SO ₂ -, -COO-alkylene-, -OCO-alkylene-,- CONH-alkylene- or -NHCO-alkylene- is preferred, -COO-, -OCO-, -CONH-, -SO ₂ -, -COO-alkylene- or -OCO-alkylene- For better.

W represents an organic group containing a cyclic structure. Among these, cyclic organic groups are also preferred. Examples of cyclic organic groups include alicyclic groups, aryl groups, and heterocyclic groups. The alicyclic group may be monocyclic or polycyclic. Examples of monocyclic alicyclic groups 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 huge structure of 7 or more carbons such as norbornyl, tricyclodecyl, tetracyclodecyl, tetracyclododecyl, and adamantyl are preferred.

The aryl group may be monocyclic or polycyclic. Examples of the aryl group include phenyl, naphthyl, phenanthrenyl, and anthracenyl. The heterocyclic group may be monocyclic or polycyclic. The polycyclic type can further suppress the diffusion of acid. In addition, the heterocyclic group may or may not be aromatic. Examples of the aromatic heterocyclic ring include furan ring, thiophene ring, benzofuran ring, benzothiophene ring, dibenzofuran ring, dibenzothiophene ring and pyridine ring. Examples of the heterocyclic ring that does not have 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 heterocyclic ring in the heterocyclic group, a furan ring, a thiophene ring, a pyridine ring or a decahydroisoquinoline ring is particularly preferable.

The cyclic organic group may have a substituent. Examples of the substituent include an alkyl group (which may be linear or branched, preferably having 1 to 12 carbon atoms), and a cycloalkyl group (which may be monocyclic, polycyclic, or spirocyclic). Any one of C 3-20 is preferred), aryl (C 6-14 is preferred), hydroxy, alkoxy, ester, amide, urethane, urea, Thioether group, sulfonamide group and sulfonate group. In addition, the carbon constituting the cyclic organic group (carbon that contributes to ring formation) may be a carbonyl carbon.

As an 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 preferred. Here, L, q, and W are the same as the general formula (3). q'represents an integer of 0-10.

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 preferred.

[Chemical Formula 24]

In the general formula (4), X ^B1 and X ^B2 each independently represent a hydrogen atom or a monovalent organic group having no fluorine atom. X ^B1 and X ^B2 are preferably hydrogen atoms. X ^B3 and X ^B4 each independently represent a hydrogen atom or a monovalent organic group. Preferably, at least one of X ^B3 and X ^B4 is a fluorine atom or a monovalent organic group having a fluorine atom, and both X ^B3 and X ^B4 are a fluorine atom or a monovalent organic group having a fluorine atom. . It is further preferred that both X ^B3 and X ^B4 are alkyl groups substituted with fluorine. L, q and W are the same as 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 (5) The indicated anion is preferred.

[Chemical Formula 25]

In the general formula (5), Xa independently represents a fluorine atom or an alkyl group substituted with at least one fluorine atom. Xb independently represents a hydrogen atom or an organic group having no 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) in the Z ^-, of the general formula (ZI-3) in Zc ^- and the formula Z (ZI-4) ^- The acid may be an anion, A benzenesulfonic acid anion substituted with a branched alkyl group or 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 ^-, represented by the following general formula The aromatic sulfonic acid anion represented by (SA1) is also preferred.

[Chemical Formula 26]

In formula (SA1), Ar represents an aryl group, and may further have a substituent other than a sulfonic acid anion and a -(D-B) group. Examples of substituents that may be further included include fluorine atoms and hydroxyl groups.

n represents an integer of 0 or more. As n, 1-4 is preferable, 2-3 is more preferable, and 3 is still 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 sulylene group, a sulylene group, a sulfonate group, an ester group, and a group containing a combination of two or more of these.

B represents a hydrocarbon group.

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

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

[Chemical Formula 27]

The following shows the comparison of the anion Z ^- in the general formula (ZI), the anion Z ^- in the general formula (ZII), the Zc ^{-in the} general formula (ZI-3) and the Z ^- in the general formula (ZI-4) Good example.

[Chemical Formula 28]

The above-mentioned cation and anion can be arbitrarily combined and used as a photoacid generator (B).

The photoacid 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 the polymer. In addition, the form of the low-molecular compound and the form incorporated in a part of the polymer may be used together. The form of the photoacid generator (B) is a low-molecular compound, which is preferred. When the photoacid generator (B) is in the form of a low-molecular compound, the molecular weight is preferably 3,000 or less, more preferably 2,000 or less, and further preferably 1,000 or less. When the photoacid generator (B) is incorporated into a part of the polymer, it may be incorporated into a part of the aforementioned resin (A) or may be incorporated into a resin different from the resin (A). One type of photoacid generator (B) may be used alone, or two or more types may be used in combination. In the composition, the content of the photoacid generator (B) (in the case of plural types, the total) is based on the total solid content of the composition, preferably 0.1 to 35.0% by mass, and 0.5 to 25.0% by mass More preferably, 3.0 to 20.0% by mass is more preferable. When the photoacid generator contains the compound represented by the above general formula (ZI-3) or (ZI-4), the content of the photoacid generator contained in the composition (in the case of plural types, it is the total ) Based on the total solid content of the composition, 5 to 35% by mass is more preferable, and 7 to 30% by mass is more preferable.

<Acid Diffusion Control Agent (C)> The composition of the present invention may contain an acid diffusion control agent as long as the effect of the present invention is not hindered. The acid diffusion control agent (D) captures the acid generated from the acid generator during exposure, and functions as a quencher for suppressing the reaction of the acid-decomposable resin in the unexposed portion caused by the generated excess acid By. As the acid diffusion control agent (C), for example, a basic compound (CA), a basic compound (CB) whose basicity decreases or disappears due to irradiation of actinic rays or radiation, and a relative amount relative to the acid generator can be used As a weak acid onium salt (CC), a low-molecular compound (CD) having a nitrogen atom and a group detached by the action of an acid, or an onium salt compound (CE) having a nitrogen atom in the cation part, etc., as an acid diffusion control agent . In the composition of the present invention, a known acid diffusion control agent can be appropriately used. For example, paragraphs <0627> to <0664> of US Patent Application Publication 2016/0070167A1, paragraphs <0095> to <0187> of US Patent Application Publication 2015/0004544A1, and US Patent Application Publication 2016 can be preferably used The well-known compounds disclosed in paragraphs <0403> to <0423> of specification /0237190A1 and paragraphs <0259> to <0328> of U.S. Patent Application Publication 2016/0274458A1 serve as acid diffusion control agents (C).

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

[Chemical Formula 29]

In the general formulas (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 having 1 to 20 carbon atoms), and a cycloalkyl group (Preferably carbon number 3-20) or aryl group (carbon number 6-20). 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 formulas (A) and (E) may have a substituent, or may be unsubstituted. Regarding the above-mentioned alkyl group, as the alkyl group having a substituent, an aminoalkyl group having 1 to 20 carbon atoms, a hydroxyalkyl group having 1 to 20 carbon atoms, or a cyanoalkyl group having 1 to 20 carbon atoms is preferred. The alkyl groups in the general formulas (A) and (E) are preferably unsubstituted.

As the basic compound (CA), guanidine, aminopyrrolidine, pyrazole, pyrazoline, piperazine, aminopyrimidine, aminoalkyloxazoline, piperidine, etc. are preferred, having an imidazole structure, Compounds with diazabicyclic structure, onium hydroxide structure, onium carboxylate structure, trialkylamine structure, aniline structure or pyridine structure, alkylamine derivatives having hydroxyl and/or ether bonds or having hydroxyl and/or Aniline derivatives such as ether bonds are more preferred.

A basic compound (CB) whose basicity is reduced or disappeared by irradiation of actinic rays or radiation (hereinafter, also referred to as "compound (CB)") has a proton acceptor functional group and is actinic A compound that decomposes by irradiation of radiation or radiation, and the proton acceptor property decreases, disappears, or changes from the proton acceptor property to acidity.

The proton acceptor functional group refers to a functional group having a group or an electron capable of electrostatically interacting with a proton, for example, a functional group having a macrocyclic structure such as a cyclic polyether or having a common π-conjugated unshared group The functional group of the nitrogen atom where the electron does not work. A nitrogen atom having an unshared electron pair that is conjugated to π refers to, for example, a nitrogen atom having a partial structure represented by the following formula.

[Chemical Formula 30]

As a preferable partial structure of the proton acceptor functional group, for example, a crown ether structure, an aza crown ether structure, a primary to tertiary amine structure, a pyridine structure, an imidazole structure, a pyrazole structure, etc. may be mentioned.

The compound (CB) is a compound that is decomposed by actinic rays or radiation, and the proton acceptor property decreases, disappears, or changes from the proton acceptor property to acidity. Among them, the decrease or disappearance of proton acceptor property, or the change from proton acceptor property to acidity refers to the change of proton acceptor property caused by the addition of proton to proton acceptor functional group. When the proton acceptor functional compound (CB) and proton form a proton adduct, the equilibrium constant under its chemical equilibrium decreases. Proton acceptor properties can be confirmed by performing pH measurement.

By irradiation with actinic rays or radiation, the acid dissociation constant pKa of the compound produced by the decomposition of the compound (CB) is preferably pKa<-1, more preferably -13<pKa<-1, more preferably -13< pKa<-3 is further preferable.

The acid dissociation constant pKa refers to the acid dissociation constant pKa in an aqueous solution, for example, as defined in Chemical Handbook (II) (Revised 4th Edition, 1993, edited by the Chemical Society of Japan, Maruzen Company, Limited). The lower the value of the acid dissociation constant pKa, the greater 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. Alternatively, the following software package 1 can also be used to calculate the value of a database based on Hammett's substituent constants and known literature values by calculation. The values of pKa described in this manual are all values calculated by using the software package.

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

In the composition of the present invention, an onium salt (CC) that becomes a relatively weak acid relative to an acid generator can be used as an acid diffusion control agent. When an acid generator is used in combination with an onium salt that generates a relatively weak acid for the acid generated from the acid generator, if it is generated from the acid generator by irradiation with actinic rays or radiation The acid conflicts with the unreacted onium salt with weak acid anion, and the weak acid is released through salt exchange and the onium salt with strong acid anion is produced. In this process, the strong acid is exchanged for a weaker acid with a lower catalyst capacity. Therefore, in appearance, the acid is deactivated and the acid diffusion can be controlled.

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

[Chemical Formula 31]

In the formula, R ⁵¹ is a hydrocarbon group which may have a substituent, Z ^2c is a hydrocarbon group having 1 to 30 carbon atoms which may have a substituent (wherein, it is assumed that the carbon adjacent to S is not substituted with a fluorine atom), R ⁵² It 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} independently an ammonium cation, a cation, or a cation.

As preferred examples of the cations or cations represented by M ⁺ , the cations exemplified in the general formula (ZI) and the cations exemplified in the general formula (ZII) can be cited.

The onium salt (CC) which is relatively weaker than the acid generator may be a compound having a cation site and an anion site in the same molecule, and the cation site and anion site are linked by a covalent bond (hereinafter, also Called "Compound (CCA)".). The compound (CCA) is preferably a compound represented by any one of the following general formulas (C-1) to (C-3).

[Chemical Formula 32]

In the general formulae (C-1) to (C-3), R ₁ , R ₂ and R ₃ each independently represent a substituent having 1 or more carbon atoms. L ₁ represents a divalent linking group or single bond connecting the cationic site and the anionic site. -X ^- represents a group selected ^{_{-COO -, -SO 3 -, -SO}} 2 - and -N ^- in the anionic sites -R _4. R ₄ represents a carbonyl group (-C(=O)-), a sulfonyl group (-S(=O) ₂ -) and a sulfinyl group (-S(=O)- ) At least one monovalent substituent. R ₁ , R ₂ , R ₃ , R ₄ and L ₁ may be bonded to each other to form a ring structure. In addition, in the general formula (C-3), two of R ₁ to R ₃ together represent a divalent substituent, and may be bonded to the N atom by a double bond.

Examples of the substituents having 1 or more carbon atoms in R ₁ to R ₃ include alkyl groups, cycloalkyl groups, aryl groups, alkoxycarbonyl groups, cycloalkoxycarbonyl groups, aryloxycarbonyl groups, alkylaminocarbonyl groups, Cycloalkylaminocarbonyl and arylaminocarbonyl, etc. Among them, an alkyl group, a cycloalkyl group or an aryl group is preferred.

Examples of L ₁ as a divalent linking group include a linear or branched alkylene group, cycloalkylene group, aryl group, carbonyl group, ether bond, ester bond, amide bond, and urethane bond. , Urea bonds and groups formed by combining two or more of these. L _{1 is} preferably an alkylene group, an aryl group, an ether bond, an ester bond, or a combination of two or more of these groups.

A low-molecular compound (CD) having a nitrogen atom and having a group detached by the action of an acid (hereinafter, also referred to as "compound (CD)".) is a nitrogen atom that has been detached by the action of an acid Amine derivatives of the group are preferred. As a group to be detached by the action of an acid, an acetal group, a carbonate group, a carbamate group, a tertiary ester group, a tertiary hydroxyl group or a hemiacetal amine ether group is preferred, and a carbamate The group or hemiacetal ether group is more preferable. The molecular weight of the compound (CD) is preferably from 100 to 1,000, more preferably from 100 to 700, and even more preferably from 100 to 500. The compound (CD) may have a carbamate group having a protective group on the nitrogen atom. The protective group constituting the urethane group is represented by the following general formula (d-1).

[Chemical Formula 33]

In the general formula (d-1), R _b independently represents a hydrogen atom, an alkyl group (preferably having a carbon number of 1 to 10), a cycloalkyl group (preferably having a carbon number of 3 to 30), and an aryl group (compared to It is preferably a carbon number of 3 to 30), an aralkyl group (preferably a carbon number of 1 to 10) or an alkoxyalkyl group (preferably a carbon number of 1 to 10). R _b may also be connected to each other to form a ring. The alkyl group, cycloalkyl group, aryl group and aralkyl group represented by R _b may be independently substituted by functional groups such as hydroxy, cyano, amine, pyrrolidinyl, piperidinyl, porphyrinyl, and oxo , Alkoxy or halogen atom substitution. The same applies to the alkoxyalkyl group represented by R _b .

As R _b , a linear or branched alkyl group, a cycloalkyl group, or an aryl group is preferable, and a linear or branched alkyl group or a cycloalkyl group is more preferable. Examples of the ring formed by connecting two R _{b to} each other include alicyclic hydrocarbons, aromatic hydrocarbons, heterocyclic hydrocarbons, and derivatives thereof. As a specific structure of the group represented by the general formula (d-1), the structure disclosed in paragraph <0466> of US Patent Publication No. US2012/0135348A1 can be cited, but it is not limited thereto.

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

[Chemical Formula 34]

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. R _a 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 heterocycle together with the nitrogen atom in the formula. The heterocyclic ring may contain hetero atoms other than the nitrogen atom in the formula. The same as R _b in the general formula (d-1) in the meaning of R _b, preferred embodiments are also the same. In the general formula (6), the alkyl group, cycloalkyl group, aryl group, and aralkyl group independently of _Ra may be independently substituted with the same groups as the aforementioned groups. The aforementioned group is, as R The alkyl group, cycloalkyl group, aryl group and aralkyl group of _b may be substituted.

As the above R _a is alkyl, cycloalkyl, aryl and aralkyl groups (these groups may be substituted with the above group) Specific examples of R _b include the same specific examples of the groups for. As specific examples of the particularly preferred compound (CD) in the present invention, the compounds disclosed in paragraph <0475> of US Patent Application Publication No. 2012/0135348A1 can be cited, but it is not limited thereto.

An onium salt compound (CE) having a nitrogen atom in the cation portion (hereinafter, also referred to as "compound (CE)") is preferably a compound having a basic portion containing a nitrogen atom in the cation portion. The amine group of the basic site is preferable, and the aliphatic amine group is more preferable. All the atoms adjacent to the nitrogen atom in the basic site are all hydrogen atoms or carbon atoms. In addition, from the viewpoint of improving basicity, it is preferable that the electron-withdrawing functional group (carbonyl group, sulfonyl group, cyano group, halogen atom, etc.) not be directly bonded to the nitrogen atom. As a preferred specific example of the compound (CE), the compound disclosed in paragraph <0203> of US Patent Application Publication No. 2015/0309408A1 can be cited, but it is not limited thereto.

Hereinafter, preferred examples of the acid diffusion control agent (C) are shown.

[Chemical Formula 35]

[Chemical Formula 36]

In the composition of the present invention, the acid diffusion control agent (C) may be used alone or in combination of two or more. When the acid diffusion control agent (C) is included in the composition, the content of the acid diffusion control agent (C) (in the case of plural types, the total) is 0.1 to 10.0% by mass based on the total solid content of the composition Preferably, 0.1 to 5.0% by mass is more preferable.

<Hydrophobic resin (D)> The composition of the present invention may contain a hydrophobic resin (D). In addition, the hydrophobic resin (D) is preferably different from the resin (AX1) and the resin (AX2). The composition of the present invention contains a hydrophobic resin (D), whereby the static/dynamic contact angle on the surface of the photosensitizing radiation or radiation-sensitive film can be controlled. With this, it is possible to improve development characteristics, suppress outgassing, improve liquid immersion liquid followability in liquid immersion exposure, and reduce liquid immersion defects. The hydrophobic resin (D) is preferably designed in such a way that it is localized on the surface of the resist film, but unlike surfactants, it is not necessary to have a hydrophilic group in the molecule, and it can be uniformly mixed with polar/non-polar substances. kick in.

From the viewpoint of localization to the membrane surface layer, the hydrophobic resin (D) is selected from the group consisting of "fluorine atom", "silicon atom" and "CH ₃ part structure contained in the side chain part of the resin" At least one type of resin of repeating units is preferred. When the hydrophobic resin (D) contains fluorine atoms and/or silicon atoms, the above-mentioned fluorine atoms and/or silicon atoms in the hydrophobic resin (D) may be included in the main chain of the resin or may be included in the side chain.

When the hydrophobic resin (D) contains a fluorine atom, as a 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 (D) has at least one group selected from the group including the following (x) to (z). (X) Acid group (Y) A group that decomposes under the action of an alkali developer and increases its solubility in an alkali developer (hereinafter, also referred to as a polarity conversion group.) (Z) A group decomposed by the action of acid

Examples of the acid group (x) include a phenolic hydroxyl group, a carboxylic acid group, a fluorinated alcohol group, a sulfonic acid group, a sulfonamide group, a sulfonimide group, (alkylsulfonyl) (alkylcarbonyl) group Methyl, (alkylsulfonyl) (alkylcarbonyl) amide imino, bis (alkylcarbonyl) methylene, bis (alkylcarbonyl) amide imino, bis (alkylsulfonyl) imide Methyl, bis(alkylsulfonyl)imide, tri(alkylcarbonyl)methylene and tri(alkylsulfonyl)methylene, etc. As the acid group, a fluorinated alcohol group (preferably hexafluoroisopropanol group), a sulfonylimide group or a bis(alkylcarbonyl)methylene group is preferred.

Examples of the group (y) that decomposes by the action of the alkali developer and increases solubility in the alkali developer include lactone groups, carboxylate groups (-COO-), and acid anhydride groups (-C ( O) OC (O) -), acid imino group (-NHCONH-), carboxylic acid thioester group (-COS-), carbonate group (-OC (O) O-), sulfate group (-OSO ₂ O-) and sulfonate (-SO ₂ O-), etc., lactone or carboxylate (-COO-) is preferred. Examples of the repeating units containing these groups include repeating units in which these groups are directly bonded to the main chain of the resin, for example, repeating units based on acrylate and methacrylate. In the repeating unit, these groups may be bonded to the main chain of the resin via a linking group. Or, the repeating unit may be used when polymerizing a polymerization initiator or chain transfer agent having such groups, and introduced into the end of the resin. As the repeating unit having a lactone group, for example, the same repeating unit having the lactone structure described above in the section of resin (AX1) can be cited.

The content of the repeating unit (y) having a group (y) that is decomposed by the action of the alkali developer to increase the solubility to the alkali developer is 1 to 100 mol% relative to all repeating units in the hydrophobic resin (D) Preferably, 3 to 98 mol% is more preferable, and 5 to 95 mol% is still more preferable.

The repeating unit having a group (z) decomposed by the action of an acid in the hydrophobic resin (D) may be the same as the repeating unit having an acid-decomposable group exemplified in the resin (AX1). The repeating unit having a group (z) that is decomposed by the action of an acid may have at least any one of fluorine atoms and silicon atoms. The content of the repeating unit having a group (z) that is decomposed by the action of an acid is preferably 1 to 80 mol% relative to all the repeating units in the hydrophobic resin (D), and 10 to 80 mol% More preferably, 20 to 60 mol% is further preferable. The hydrophobic resin (D) may further have a repeating unit different from the repeating unit described above.

The repeating unit having a fluorine atom is preferably 10 to 100 mol%, and more preferably 30 to 100 mol% relative to all the repeating units in the hydrophobic resin (D). In addition, the repeating unit having silicon atoms is preferably 10 to 100 mol%, and more preferably 20 to 100 mol% relative to all the repeating units in the hydrophobic resin (D).

On the other hand, especially in the case where the hydrophobic resin (D) has a structure in which the CH ₃ moiety is included in the side chain portion, it is also preferable that the hydrophobic resin (D) does not substantially contain fluorine atoms and silicon atoms. In addition, it is preferable that the hydrophobic resin (D) consists essentially of only repeating units, and the repeating units consist of only atoms selected from carbon atoms, oxygen atoms, hydrogen atoms, nitrogen atoms, and sulfur atoms.

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

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

As the hydrophobic resin (D), a known resin can be appropriately selected and used alone or as a mixture of these. 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. It is used as a hydrophobic resin (D). In addition, the repeating units disclosed in paragraphs <0177> to <0258> of US Patent Application Publication 2016/0237190A1 are also preferred as the repeating units constituting the hydrophobic resin (D).

Hereinafter, preferred examples of the monomers corresponding to the repeating units constituting the hydrophobic resin (D) are shown.

[Chemical Formula 37]

[Chemical Formula 38]

One type of hydrophobic resin (D) may be used alone, or two or more types may be used in combination. From the viewpoint of taking into consideration both the followability of the liquid immersion liquid and the development characteristics in the liquid immersion exposure, it is preferable to mix and use two or more types of hydrophobic resins (D) having different surface energies. In the composition, the content of the hydrophobic resin (D) relative to the total solid content in the composition is preferably 0.01 to 10.0% by mass, and more preferably 0.05 to 8.0% by mass.

<Solvent (E)> The composition of the present invention may contain a solvent. In the composition of the present invention, a known resist solvent can be appropriately used. For example, paragraphs <0665> to <0670> of US Patent Application Publication 2016/0070167A1, paragraphs <0210> to <0235> of US Patent Application Publication 2015/0004544A1, and US Patent Application Publication 2016 can be preferably used. The well-known solvents disclosed in paragraphs <0424> to <0426> of the specification of /0237190A1 and paragraphs <0357> to <0366> of the specification of US Patent Application Publication 2016/0274458A1. Examples of the solvent that can be used when preparing the composition include alkylene glycol monoalkyl ether carboxylate, alkylene glycol monoalkyl ether, alkyl lactate, and alkoxypropionic acid alkyl. Ester, cyclic lactone (preferably carbon number 4-10), monoketone compound which may have a ring (preferably carbon number 4-10), alkylene carbonate, alkyl alkoxyacetate 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 not having a hydroxyl group in the structure are mixed can be used. As the solvent having a hydroxyl group and the solvent not having a hydroxyl group, the aforementioned exemplified compounds can be appropriately selected. As the solvent containing a hydroxyl group, alkylene glycol monoalkyl ethers or alkyl lactates are preferred. Propylene glycol monomethyl ether ( PGME), propylene glycol monoethyl ether (PGEE), methyl 2-hydroxyisobutyrate or ethyl lactate is preferred. Moreover, as a solvent having no hydroxyl group, alkylene glycol monoalkyl ether acetate, alkyl alkoxy propionate, monoketone compound which may have a ring, cyclic lactone, alkyl acetate, etc. Preferably, among these, propylene glycol monomethyl ether acetate (PGMEA), ethyl ethoxypropionate, 2-heptanone, γ-butyrolactone, cyclohexanone, cyclopentanone or butyl acetate are More preferably, propylene glycol monomethyl ether acetate, γ-butyrolactone, ethyl ethoxypropionate, cyclohexanone, cyclopentanone or 2-heptanone is still more preferable. 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 not having a hydroxyl group is 1/99 to 99/1, preferably 10/90 to 90/10, and more preferably 20/80 to 60/40. From the viewpoint of coating uniformity, a mixed solvent containing 50% by mass or more of a solvent having no hydroxyl group is preferred. The solvent preferably contains propylene glycol monomethyl ether acetate, and may be a single solvent of propylene glycol monomethyl ether acetate, or a mixed solvent of two or more types containing propylene glycol monomethyl ether acetate.

<Crosslinking agent (F)> The composition of the present invention may contain a compound that crosslinks the resin by the action of an acid (hereinafter, also referred to as a crosslinking agent (F).). As the crosslinking agent (F), a known compound can be appropriately used. For example, the well-known ones disclosed in paragraphs <0379> to <0431> of US Patent Application Publication 2016/0147154A1 and paragraphs <0064> to <0141> of US Patent Application Publication 2016/0282720A1 can be preferably used. The compound acts as a crosslinking agent (F). The crosslinking agent (F) is a compound having a crosslinkable group capable of crosslinking the resin. Examples of the crosslinkable group include hydroxymethyl, alkoxymethyl, acetylmethyl, and alkoxy. Methyl ether group, ethylene oxide ring and oxycyclobutane ring, etc. The crosslinkable group is preferably a methylol group, an alkoxymethyl group, an ethylene oxide ring or an oxetane ring. The crosslinking agent (F) is preferably a compound (including a resin) having two or more crosslinkable groups. The crosslinking agent (F) is a hydroxymethyl group or an alkoxymethyl group, a phenol derivative, a urea compound (a compound having a urea structure) or a melamine compound (a compound having a melamine structure) is more preferable. One type of crosslinking agent may be used alone, or two or more types may be used in combination. The content of the crosslinking agent (F) relative to the total solid content of the resist composition is preferably 1.0 to 50% by mass, preferably 3.0 to 40% by mass, and more preferably 5.0 to 30% by mass.

<Surface Active Agent (G)> The composition of the present invention may contain a surfactant. When a surfactant is included, a fluorine-based and/or silicon-based surfactant (specifically, a fluorine-based surfactant, a silicon-based surfactant, or a surfactant having both fluorine atoms and silicon atoms) is preferred good.

The composition of the present invention contains a surfactant, whereby when an exposure light source of 250 nm or less, especially 220 nm or less is used, a pattern with good sensitivity and resolution and less adhesion and development defects can be obtained. Examples of the fluorine-based and/or silicon-based surfactants include those described in paragraph <0276> of US Patent Application Publication No. 2008/0248425. In addition, surfactants other than fluorine-based and/or silicon-based surfactants described in paragraph <0280> of US Patent Application Publication No. 2008/0248425 can also be used.

One type of these surfactants may be used alone, or two or more types may be used in combination. When the composition of the present invention contains a surfactant, the content of the surfactant with respect 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, when the content of the surfactant is 10 ppm or more relative to the total solid content of the composition, the surface locality of the hydrophobic resin (D) is improved. Thereby, the surface of the photosensitizing radiation or radiation-sensitive film can be made more hydrophobic, thereby improving the water-followability during liquid immersion exposure.

(Other additives) The composition of the present invention may further contain other additives such as acid multiplication agents, dyes, plasticizers, photosensitizers, light absorbers, alkali-soluble resins, dissolution inhibitors and dissolution accelerators.

<Preparation method> The solid content concentration of the composition of the present invention is usually preferably 1.0 to 10% by mass, more preferably 2.0 to 5.7% by mass, and even more preferably 2.0 to 5.3% by mass. The solid content concentration refers to the mass percentage of the mass of the resist components other than the solvent relative to the total mass of the composition.

In addition, from the viewpoint of improving the resolution, the film thickness of the sensitizing radiation or radiation sensitive film including the composition of the present invention is preferably 90 nm or less, and more preferably 85 nm or less. By setting the solid content concentration in the composition to an appropriate range so as to have an appropriate viscosity, the coating properties or the film-forming properties can be improved, whereby the film thickness can be formed.

The composition of the present invention is obtained by dissolving the above-mentioned components in a predetermined organic solvent, preferably the above-mentioned mixed solvent, and performing filter filtration, and then applying it 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 further preferably 0.03 μm or less. In addition, when the solid content concentration of the composition is high (for example, 25% by mass or more), the pore size of the filter used for filter filtration is preferably 3 μm or less, more preferably 0.5 μm or less, and 0.3 μm or less It is further preferred. The filter is preferably made of polytetrafluoroethylene, polyethylene or nylon. In filter filtration, for example, as disclosed in Japanese Patent Application Publication No. 2002-062667 (Japanese Patent Application Laid-Open No. 2002-062667), it is possible to perform cyclic filtration, or it is possible to perform filtration by connecting a plurality of filters in series or in parallel. In addition, the composition can be filtered a plurality of times. Furthermore, before and after filtration by the filter, the composition may be subjected to degassing treatment or the like.

<Use> The composition of the present invention relates to a sensitized radiation or radiation-sensitive resin composition whose properties change by reacting with actinic rays or radiation. In more detail, the composition of the present invention relates to a semiconductor manufacturing process such as IC (Integrated Circuit), a circuit board manufacturing such as a liquid crystal or a thermal head, a mold structure for imprinting, and other photosensitive Photosensitive or radiation-sensitive resin composition in the etching process, lithographic printing plate, or acid-curable composition. In the present invention, the formed pattern can be used in etching processes, ion implantation processes, bump electrode formation processes, rewiring formation processes, 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 sensitized radiation or radiation sensitive resin composition. Hereinafter, the pattern forming method of the present invention will be described. In addition, the photosensitizing radiation 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 has the following processes: (I) The process (resist film formation process) of forming a resist film (photosensitive radiation or radiation-sensitive film) on the support by the above-mentioned photosensitive ray-sensitive or radiation-sensitive resin composition; (Ii) The process (exposure process) of exposing (irradiating actinic rays or radiation) to the above resist film; and (Iii) The process of developing the above-mentioned 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 of (i) to (iii) above, and may have the following processes. In the pattern forming method of the present invention, (ii) the exposure method in the exposure process may be immersion exposure. In the pattern forming method of the present invention, (ii) a process including (iv) a pre-heating (PB: PreBake) process before the exposure process is preferred. In the pattern forming method of the present invention, (ii) after the exposure process and (iii) before the development process includes (v) post-exposure heating (PEB: Post Exposure Bake) process is preferred. The pattern forming method of the present invention may include a plurality of (ii) exposure processes. The pattern forming method of the present invention may include multiple (iv) preheating processes. The pattern forming method of the present invention may include a plurality of (v) heating processes after exposure.

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

The support is not particularly limited, and it is possible to use substrates that are generally used in photolithographic processes such as photolithographic processes other than the manufacturing processes of semiconductors such as ICs and the manufacturing processes of circuit boards such as liquid crystals and thermal heads. Specific examples of the support include inorganic substrates such as silicon, SiO ₂ and SiN.

Regarding the heating temperature, in any of (iv) the preheating process and (v) the post-exposure heating process, 70 to 130°C is preferable, and 80 to 120°C is more preferable. Regarding the heating time, in either (iv) pre-heating process and (v) post-exposure heating process, 30 to 300 seconds is preferred, 30 to 180 seconds is more preferred, and 30 to 90 seconds It is further preferred. The heating can be performed by means provided in the exposure device and the developing device, and a hot plate or the like can also be used.

The wavelength of the light source used in the exposure process is not particularly limited, and examples thereof include infrared light, visible light, ultraviolet light, far ultraviolet light, extreme ultraviolet light (EUV), X-rays, and electron beams. Among these, far ultraviolet light is preferable, and its wavelength is preferably 250 nm or less, more preferably 220 nm or less, and further preferably 1 to 200 nm. Specifically, 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, it may be an alkali developer or a developer containing an organic solvent (hereinafter, also referred to as an organic developer.).

As the alkaline developing solution, quaternary ammonium salts typified by tetramethylammonium hydroxide can be generally used, and in addition, alkaline aqueous solutions such as inorganic bases, primary to tertiary amines, alcohol amines, and cyclic amines can be used. Furthermore, the alkali developer may contain alcohols and/or surfactants in appropriate amounts. The alkali concentration of the alkali developer is usually 0.1 to 20% by mass. The pH of the alkaline developer is usually 10 to 15. The time for developing with an alkaline developer is usually 10 to 300 seconds. The alkali concentration, pH, and development time of the alkali developer can be adjusted appropriately according to the formed pattern.

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

Examples of the ketone-based solvent include 1-octanone, 2-octanone, 1-nonanone, 2-nonanone, acetone, 2-heptanone (methyl amyl ketone), 4-heptanone, 1- Hexanone, 2-hexanone, diisobutyl ketone, cyclohexanone, methylcyclohexanone, phenylacetone, methyl ethyl ketone, methyl isobutyl ketone, acetone acetone, acetone acetone, ionone, Diacetone alcohol (diacetonylalcohol), acetone methanol, acetophenone, methyl naphthyl ketone, isophorone and propyl carbonate, etc.

Examples of the ester solvents include methyl acetate, butyl acetate, ethyl acetate, isopropyl acetate, pentyl acetate, isoamyl acetate, amyl acetate, and propylene glycol monomethyl ether. Acetate, ethylene glycol monoethyl ether acetate, diethylene glycol monobutyl ether acetate, diethylene glycol monoethyl ether acetate, ethyl-3-ethoxypropionate, 3-methoxy Butyl 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, amide-based solvent, ether-based solvent, and 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 plural or may be mixed with solvents other than the above or water. The water content of the entire developer is preferably less than 50% by mass, more preferably less than 20% by mass, even more preferably less than 10% by mass, and it is particularly preferable that it contains substantially no moisture. The content of the organic solvent with respect to the organic developing solution is preferably 50 to 100% by mass, more preferably 80 to 100% by mass, more preferably 90 to 100% by mass, 95 to 100 Quality% is particularly good.

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

The content of the surfactant relative to the total amount of the developer 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 above-mentioned acid diffusion control agent.

As a developing method, for example, a method of immersing the substrate in a tank filled with a developer for a certain period of time (immersion method); a method of depositing the developer on the surface of the substrate using surface tension and allowing it to stand for a certain period of time (coating method) ); The method of spraying developer on the surface of the substrate (spray method); or the method of scanning the developer ejection nozzle at a certain speed while continuously ejecting the developer onto the substrate rotating at a certain speed (dynamic distribution method), etc.

It is possible to combine the development process using an alkali aqueous solution (alkali development process) and the development process using an organic solvent-containing developing solution (organic solvent development process). With this, it is possible to form a pattern without dissolving only the region of the exposure intensity at an intermediate level, so that a finer pattern can be formed.

After (iii) the development process, a process (rinsing process) including washing with a rinse solution is preferred.

The rinse liquid used in the rinse process after the development process using an alkali developer can be, for example, pure water. Pure water may contain an appropriate amount of surfactant. In this case, after the development process or the rinsing process, a process of removing the developer or rinsing liquid adhering to the pattern by supercritical fluid may be added. Furthermore, in order to remove moisture remaining in the pattern, heat treatment may be performed after rinsing treatment or supercritical fluid treatment.

The rinsing liquid used in the rinsing process after the development process using a developer containing an organic solvent is not particularly limited as long as it does not dissolve the pattern, and a solution containing a normal organic solvent or the like can be used. As the rinsing liquid, it is preferable to use a rinsing liquid containing at least one organic solvent selected from the group consisting of hydrocarbon-based solvents, ketone-based solvents, ester-based solvents, alcohol-based solvents, amide-based solvents, and ether-based solvents. Specific examples of the hydrocarbon-based solvent, ketone-based solvent, ester-based solvent, alcohol-based solvent, amide-based solvent, and ether-based solvent include the same solvents 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 monohydric alcohol is more preferable.

Examples of the monohydric alcohol used in the washing process include linear, branched, or cyclic monohydric alcohols. Specifically, 1-butanol, 2-butanol, 3-methyl-1-butanol, third butanol, 1-pentanol, 2-pentanol, 1-hexanol, 4-methyl -2-pentanol, 1-heptanol, 1-octanol, 2-hexanol, cyclopentanol, 2-heptanol, 2-octanol, 3-hexanol, 3-heptanol, 3-octanol, 4-octanol and methyl isobutyl methanol. Examples of monohydric alcohols having 5 or more carbon atoms include 1-hexanol, 2-hexanol, 4-methyl-2-pentanol, 1-pentanol, 3-methyl-1-butanol and methyl iso Butyl methanol and so on.

Each component may be mixed in plural or may be used by mixing with organic solvents other than the above. The water content in the rinse liquid is preferably 10% by mass or less, more preferably 5% by mass or less, and further preferably 3% by mass or less. When the water content is 10% by mass or less, good development characteristics can be obtained.

The rinse solution may contain an appropriate amount of surfactant. In the rinsing process, a rinsing solution containing an organic solvent is used to clean the groups that have been developed using an organic developer. The method of cleaning is not particularly limited. For example, a method of continuously spraying a rinsing liquid on a substrate rotating at a certain speed (spin coating method), or a method of immersing the substrate in a tank filled with a rinsing liquid for a certain period of time ( Dipping method) or the method of spraying rinse liquid on the substrate surface (spraying method), etc. Among them, a method of performing a cleaning process by a spin coating method and rotating the substrate at a rotation speed of 2,000 to 4,000 rpm after cleaning to remove the rinse liquid from the substrate is preferred. In addition, it is also preferable to include a heating process (Post Bake) after the rinsing process. Through this heating process, the developer and rinse liquid remaining between the patterns and inside the patterns are removed. 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, preferably 30 seconds to 90 seconds.

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

As a method of removing impurities such as metals from the above-mentioned various materials, for example, filtration using a filter can be cited. As the filter pore size, the pore size is preferably 10 nm or less, more preferably 5 nm or less, and further preferably 3 nm or less. As the material of the filter, a filter made of polytetrafluoroethylene, polyethylene or nylon is preferable. The filter can be a filter previously cleaned with an organic solvent. In the filter filtration process, a plurality of filters can be connected in series or parallel to use. When a plurality of filters are used, filters with different pore sizes and/or materials can be used in combination. In addition, various materials can be filtered a plurality of times, and the process of performing the plurality of times of filtration can be a cycle filtration process. As the filter, a filter with reduced elution as disclosed in Japanese Patent Application Publication No. 2016-201426 (Japanese Patent Laid-Open No. 2016-201426) is preferred. In addition to filter filtration, impurities based on adsorbent materials can be removed, and filters and adsorbent materials can also be used in combination. As the adsorbent, a known adsorbent can be used. For example, an inorganic adsorbent such as silica gel or zeolite, or an organic adsorbent such as activated carbon can be used. As the metal adsorbent, for example, those disclosed in Japanese Patent Application Publication No. 2016-206500 (Japanese Patent Laid-Open No. 2016-206500) can be cited. In addition, as a method of reducing impurities such as metals contained in the above-mentioned various materials, a raw material with a small metal content may be selected as a raw material constituting various materials, and the raw material constituting various materials may be filtered by a filter or by Teflon (registered trademark) Methods such as lining the device and distilling as much as possible under conditions that suppress contamination. In order to reduce impurities such as metals to the ppt level, it is also preferable to perform glass lining treatment in all processes of manufacturing equipment for various materials (resins and photoacid generators) used to synthesize resist components. The preferable conditions for the filter filtration of the raw materials constituting various materials are the same as the above conditions.

In order to prevent mixing of impurities, the above-mentioned various materials are stored in US Patent Application Publication No. 2015/0227049, Japanese Patent Application Publication No. 2015-123351 (Japanese Patent Laid-Open No. 2015-123351), and Japanese Patent Application Publication No. 2017-013804 The container described in the specification (Japanese Patent Application Publication No. 2017-013804) is preferred.

A method of improving the surface roughness of the pattern can be applied to the pattern formed by the pattern forming method of the present invention. As a method for improving the surface roughness of the pattern, for example, a method for processing the pattern by plasma containing hydrogen gas disclosed in the specification of US Patent Application Publication No. 2015/0104957 can be cited. 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 Technique for LWR Reduction and Etch Selectivity Enhancement" is a well-known method. Also, the pattern formed by the above method can be used as a spacer process disclosed in, for example, Japanese Patent Application Publication No. 1991-270227 (Japanese Patent Laid-Open No. 3-270227) and US Patent Application Publication No. 2013/0209941 The core material (Core).

[Manufacturing method of electronic device] In addition, the invention also relates to a method for manufacturing an electronic device including the above-mentioned pattern forming method. The electronic device manufactured by the manufacturing method of the electronic device of the present invention is appropriately mounted on electrical and electronic equipment (for example, home appliances, OA (Office Automation) related equipment, media related equipment, optical equipment, communication equipment, etc.). [Example]

Hereinafter, the present invention will be described in further detail based on examples. The materials, usage amounts, ratios, processing contents, processing steps, etc. 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 limitedly interpreted by the embodiments shown below.

[Preparation of sensitized radiation-sensitive or radiation-sensitive resin composition] [Various components] <Resin> Resins A-1 to A-14 were synthesized using the synthesis method (Synthesis Example 1) of resin A-1 described later By. Table 1 shows the composition ratio (mole ratio; corresponding from the left in order) of each repeating unit, weight average molecular weight (Mw), and degree of dispersion (Mw/Mn). In addition, the weight average molecular weight (Mw) and dispersion degree (Mw/Mn) of resins A-1 to A-14 were measured by GPC (carrier: tetrahydrofuran (THF)) (in terms of polystyrene). In addition, the composition ratio (mol% ratio) of the resin was measured by ¹³ C-NMR (nuclear magnetic resonance: nuclear magnetic resonance).

[Table 1]

The structural formulas of the resins A-1 to A-14 shown in Table 1 are shown below.

[Chemical Formula 39]

[Chemical Formula 40]

[Chemical Formula 41]

(Synthesis Example 1: Synthesis of Resin A-1) Cyclohexanone (95 parts by mass) was heated to 85°C under a nitrogen flow. While stirring the liquid, the monomer represented by the following formula M-1 (4.5 parts by mass), the monomer represented by the following formula M-2 (15.0 parts by mass) and the following formula were added dropwise over 4 hours Monomer represented by M-3 (27.7 parts by mass), cyclohexanone (177 parts by mass), and dimethyl 2,2'-azobisisobutyrate [V-601, manufactured by Wako Pure Chemical Industries, Ltd.] (5.2 parts by mass) of a mixed solution to obtain a reaction liquid. After the dropwise addition was completed, the reaction solution was further stirred at 85°C for 2 hours. After the obtained reaction liquid was allowed to cool, it was reprecipitated using a large amount of methanol/water (mass ratio 9:1), filtered, and the solid obtained was vacuum dried to obtain 42.3 parts by mass of resin A-1.

[Chemical Formula 42]

The weight-average molecular weight (Mw: polystyrene conversion) determined from the GPC (carrier: tetrahydrofuran (THF)) of the obtained resin A-1 was 7800, and the degree of dispersion (Mw/Mn) was 1.5. The composition ratio measured by ¹³ C-NMR (nuclear magnetic resonance) is 10/30/60 in molar ratio.

<Resin for Comparison> Resins (P'-1) to (P'-4) were synthesized using the synthesis method (Synthesis Example 1) according to the above resin A-1. The structures of the resins (P'-1) to (P'-4) are shown below. In addition, the weight average molecular weight (Mw) and dispersion degree (Mw/Mn) of the resins (P'-1) to (P'-4) were measured by GPC (carrier: tetrahydrofuran (THF)) (for polystyrene) Conversion amount). In addition, the composition ratio (mol% ratio) of the resin was measured by ¹³ C-NMR (nuclear magnetic resonance).

[Chemical Formula 43]

<Photoacid generator> The structure of the photoacid generator (compounds B-1 to B-15) shown in Table 3 is shown below.

[Chemical Formula 44]

[Chemical Formula 45]

<Acid Diffusion Control Agent> The structure of the acid diffusion control agent (compounds C-1 to C-11) shown in Table 3 is shown below.

[Chemical Formula 46]

[Chemical Formula 47]

<Repellent resin and resin for top coat> The hydrophobic resin (E-1 to E-11) shown in Table 3 and the resin for top coat (PT-1 to PT-3) shown in Table 4 were used Those who get synthesized. Table 2 shows the molar ratio, weight average molecular weight (Mw), and dispersion degree (Mw/Mn) of the repeating units in the hydrophobic resin shown in Table 3 and the resin for top coat shown in Table 4. In addition, the weight average molecular weight (Mw) and the degree of dispersion (Mw/Mn) of the hydrophobic resins E-1 to E-11 and the topcoat resins PT-1 to PT-3 are determined by GPC (carrier: tetrahydrofuran (THF)) ) Was measured (converted to polystyrene). In addition, the composition ratio (mol% ratio) of the resin was measured by ¹³ C-NMR (nuclear magnetic resonance: nuclear magnetic resonance).

[Table 2]

The monomer structures used for the synthesis of the hydrophobic resins E-1 to E-11 shown in Table 3 and the resins PT-1 to PT-3 for top coat shown in Table 4 are shown below.

[Chemical Formula 48]

[Chemical Formula 49]

<surfactant> The surfactants shown in Table 3 are shown below. H-1: MEGAFACE F176 (DIC CORPORATION, fluorine-based surfactant) H-2: MEGAFACE R08 (DIC CORPORATION, fluorine and silicon surfactant) H-3: PF656 (manufactured by OMNOVA SOLUTIONS INC., fluorine-based surfactant)

<Solvent> The solvents shown in Table 3 are shown below. F-1: Propylene glycol monomethyl ether acetate (PGMEA) F-2: Propylene glycol monomethyl ether (PGME) F-3: Propylene glycol monoethyl ether (PGEE) F-4: Cyclohexanone F-5: Cyclopentanone F-6: 2-heptanone F-7: ethyl lactate F-8: γ-butyrolactone F-9: propylene carbonate

[Preparation of sensitized radiation or radiation sensitive resin composition] The components shown in Table 3 were mixed so that the solid content concentration became 4% by mass. Next, by filtering the obtained mixed liquid using a polyethylene filter with a pore diameter of 50 nm, a sensitized radiation or radiation-sensitive resin composition (hereinafter, also referred to as a resin composition) was prepared. In addition, in the resin composition, the solid content means all components except the solvent. The obtained resin composition was used in Examples and Comparative Examples. In addition, in Table 3, the content (mass %) of each component means the content with respect to the total solid content. In addition, in Table 3, "partial structure of the specific repeating unit 2" indicates that, when each resin contains the specific repeating unit 2, whether the specific repeating unit 2 has any of the partial structures of the above general formulas (3) to (8) .

[table 3]

[Preparation of top coat composition] 〔Various ingredients〕 The various components contained in the top coat composition shown in Table 4 are shown below. <Resin (PT)> As the resin (PT) shown in Table 4, the resins PT-1 to PT-3 shown in Table 2 were used. <Additive (DT)> The structure of the additive (DT) shown in Table 4 is shown below.

[Chemical Formula 50]

<Surface Active Agent (H)> As the surfactant (H) shown in Table 4, the above surfactant H-3 was used.

<Solvent (FT)> The solvents (FT) shown in Table 4 are shown below. FT-1: 4-methyl-2-pentanol (MIBC) FT-2: n-decane FT-3: Diisoamyl ether

[Preparation of top coat composition] Each component shown in Table 4 was mixed so that the solid content concentration became 3% by mass, and then, the obtained mixed solution was firstly made of a polyethylene filter with a pore diameter of 50 nm, followed by a nylon filter with a pore diameter of 10 nm, Finally, a polyethylene filter with a pore diameter of 5 nm was sequentially filtered to prepare a top coat composition. In addition, the solid content mentioned here means all components except the solvent (FT). The obtained top coat composition was used in the examples.

[Table 4]

[Pattern formation and evaluation: ArF immersion exposure, organic solvent development] 〔Pattern formation〕 An organic anti-reflection film forming composition ARC29SR (manufactured by Brewer) was coated on a silicon wafer, and baked at 205°C for 60 seconds to form an anti-reflection film with a thickness of 98 nm. A resin composition shown in Table 3 was applied thereon, and baked at 100° C. for 60 seconds to form a resist film (sensitizing radiation or radiation-sensitive film) with a thickness of 90 nm. In addition, regarding Examples 1-5, Examples 1-6, and Examples 1-7, a top coat film was formed on the upper layer of the resist film (Table 5 shows the types of top coat compositions used) . The film thickness of the top coat film is 100 nm. Using ArF excimer laser immersion scanner (manufactured by ASML; XT1700i, NA1.20, Dipole, outer sigma 0.950, inner sigma 0.850, Y bias), and via a 1:1 line with a line width of 45nm and a spatial pattern of 6 % Halftone mask to expose the resist film. Ultrapure water is used for the liquid immersion liquid. After the exposed resist film was baked at 90°C for 60 seconds, it was developed with n-butyl acetate for 30 seconds, and then rinsed with 4-methyl-2-pentanol for 30 seconds. Then, it was spin-dried to obtain a negative pattern.

[Evaluation of patterns] <Evaluation item 1: Line width roughness (LWR (nm))> Scanning electron microscope (SEM (Hitachi, Ltd.S-9380II) using length measurement for the 45nm (1:1) line and space pattern analyzed with the optimal exposure amount when the line pattern with the average line width of 45nm is analyzed )) When observing from the upper part of the pattern, observe the line width at any point and evaluate its measurement deviation with 3σ. The smaller the value, the better the performance. In addition, LWR (nm) is preferably 3.0 nm or less, more preferably 2.7 nm or less, and further preferably 2.5 nm or less.

<Evaluation Item 2: Resolution> Under the exposure and development conditions for pattern formation, the minimum space width to analyze the scum (dissolved residues/residues) and bridges without changing the exposure amount in a mask with an interval of 136 nm and a light shielding portion of 50 nm ( The minimum space size) was evaluated. From the viewpoint of developability, the smaller the minimum space size, the better. The evaluation was performed according to the following evaluation criteria. (Evaluation criteria) "A": 21nm or more and less than 23nm "B": 23nm or more and less than 25nm "C": more than 25nm and less than 28nm "D": above 28nm The results of the above evaluation tests are shown in Table 5 below.

[table 5]

It is clear from the results in Table 1 that the resist composition of the example has excellent resolution and excellent LWR of the formed pattern. Furthermore, as confirmed from the results in Table 1, when the specific repeating unit 2 includes a partial structure represented by the general formula (4), a partial structure represented by the general formula (5), or a partial structure represented by the general formula (8) (compared to Preferably, when the partial structure represented by the general formula (5) or the partial structure represented by the general formula (8) is included, it is more preferable to include the partial structure represented by the general formula (5)). Even better. In addition, Examples 1-12 include the resin (A-13) including the partial structure represented by the general formula (4) and the partial structure represented by the general formula (8) as the specific repeating unit 2 and including the general structure (3) The part of the structure shown is the resin (A-14) of the specific repeating unit 2, but the results of Examples 1-12 and Example 1-7 (using the part of the structure represented by the general formula (3) as the specific repeating unit 2 resin) When comparing, it was confirmed that the LWR of the formed pattern was poor. From this result, it is clear that in the resin, when the content of the specific repeating unit 2 is greater than the content of the specific repeating unit 1, the LWR of the formed pattern is excellent.

Comparative Example 1-1 and Comparative Example 1-2 are examples in which a resin including a repeating unit including a lactone structure was used, and the LWR of the formed pattern did not satisfy the desired requirements. Comparative Examples 1-3 are examples in which a resin that does not contain a specific repeating unit 1 is used, and the resolution does not satisfy the desired requirements. Comparative Examples 1-4 are examples in which a resin that does not contain a specific repeating unit 2 is used, and the resolution does not satisfy the desired requirements.

no

no

no.

Claims (10)

A photosensitive radioactive or radiation-sensitive resin composition comprising: a resin; and a photo-acid generator, wherein the resin comprises: a repeating unit comprising a group whose polarity is increased by the action of an acid; At least one or more repeating units in the group of repeating units represented by formula (1-1) and repeating units represented by general formula (1-2); and repeating units including a partial structure represented by general formula (2) , Wherein the resin includes a repeating unit including a group whose polarity is increased by the action of the acid, a repeating unit represented by the general formula (1-1), a repeating unit represented by the general formula (1-2) And when a repeating unit other than a repeating unit having a partial structure represented by the general formula (2) is included, the repeating unit does not substantially include a repeating unit including a lactone structure,

In the general formula (1-1), Z ¹ represents a hydrogen atom or a monovalent substituent, X ¹ represents an oxygen atom or a sulfur atom, and R ¹ represents a (n+1)-valent hydrocarbon group having one or more fluorine atoms , N represents an integer of 1 or more. In the general formula (1-2), Z ² represents a hydrogen atom or a monovalent substituent, X ² represents an oxygen atom or a sulfur atom, and R ² represents an alkylene group having 1 to 10 carbon atoms. Group, R ³ represents a monovalent substituent,

In the general formula (2), Y ¹ represents an oxygen atom or -C(R ^X1 ) ₂ -, Y ² represents a carbonyl group or a sulfonyl group, and Y ³ represents an oxygen atom, -NR ^X2 -or -C(R ^X3 ) ₂ -, R ^X1 , R ^X2 and R ^X3 each independently represent a hydrogen atom or a monovalent substituent, W ¹ represents a 5- to 7-membered ring containing at least Y ¹ , Y ² and Y ³ and which may have a substituent, wherein, W ¹ does not constitute a lactone ring. The sensitized radiation or radiation-sensitive resin composition as described in item 1 of the patent application scope, wherein the partial structure represented by the general formula (2) is selected from the general formula (3) to the general formula (8) More than one type in the group,

In the general formula (3), W ² represents a 5- to 7-membered ring containing at least one oxygen atom, one nitrogen atom, and one carbon atom, and may have a substituent, and R ⁴ represents a hydrogen atom or a monovalent substitution In the general formula (4), W ³ represents a 5- to 7-membered ring containing at least 1 nitrogen atom and 2 carbon atoms and may have a substituent, and R ⁵ , R ⁶ and R ⁷ each independently represent hydrogen An atom or a monovalent substituent, in the general formula (5), W ⁴ represents a 5- to 7-membered ring containing at least one carbon atom and two oxygen atoms, and may have a substituent, in the general formula (6) , W ⁵ represents a 5- to 7-membered ring containing at least one nitrogen atom, one sulfur atom, and one carbon atom, and may have a substituent, and R ⁸ , R ^9, and R ¹⁰ each independently represent a hydrogen atom or a monovalent In the general formula (7), W ⁶ represents a 5- to 7-membered ring containing at least one oxygen atom, one sulfur atom and one carbon atom, and may have a substituent, R ¹¹ and R ¹² are respectively It independently represents a hydrogen atom or a monovalent substituent. In the general formula (8), W ⁷ represents a 5- to 7-membered ring containing at least 1 sulfur atom and 2 carbon atoms, and may have a substituent, R ¹³ , R ¹⁴ , R ¹⁵ and R ¹⁶ each independently represent a hydrogen atom or a monovalent substituent. The sensitized radiation or radiation-sensitive resin composition as described in item 2 of the patent application scope, in which The partial structure represented by the general formula (2) is one or more types selected from the group including the general formula (5) and the general formula (8). The sensitized radioactive or radiation-sensitive resin composition as described in any one of the first to third patent applications, wherein The content of the repeating unit including the partial structure represented by the general formula (2) is 5 mol% to 40 mol% relative to all the repeating units in the resin. The sensitized radioactive or radiation-sensitive resin composition as described in any one of the first to third patent applications, wherein The content of the repeating unit including the partial structure represented by the general formula (2) is greater than that selected from the group including the repeating unit represented by the general formula (1-1) and the repeating unit represented by the general formula (1-2) The content of at least one or more repeating units in the group. The sensitized radioactive or radiation-sensitive resin composition as described in any one of the first to third patent applications, wherein The resin further includes a repeating unit including a ring structure directly bonded to the main chain. The photosensitive ray- or radiation-sensitive resin composition as described in any one of claims 1 to 3, which is a negative resist composition developed using a developer containing an organic solvent. A resist film, which is formed of the photosensitive radiation-sensitive or radiation-sensitive resin composition according to any one of claims 1 to 7. A pattern forming method, including: In the resist film forming process, a resist film is formed using the photosensitive radiation-sensitive or radiation-sensitive resin composition described in any one of claims 1 to 7; The exposure process exposes the resist film; In the development process, the exposed resist film is developed using a developing solution. A manufacturing method of an electronic device, which includes the pattern forming method described in item 9 of the patent application scope.