JP7124094B2 - Actinic ray-sensitive or radiation-sensitive resin composition, resist film, pattern forming method, electronic device manufacturing method - Google Patents

Description

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

Since the resist for KrF excimer laser (248 nm), a pattern forming method using chemical amplification has been used in order to compensate for the decrease in sensitivity due to light absorption. For example, in a positive chemical amplification method, first, a photoacid generator contained in an exposed area is decomposed by light irradiation to generate an acid. Then, in the post-exposure baking (PEB: Post Exposure Bake) process or the like, the alkali-insoluble groups of the resin contained in the actinic ray-sensitive or radiation-sensitive resin composition are converted into alkali-soluble groups by the catalytic action of the generated acid. The solubility in the developer is changed by, for example, changing the base. Thereafter, development is performed using, for example, a basic aqueous solution. Thereby, the exposed portion is removed to obtain a desired pattern.
For the miniaturization of semiconductor devices, the wavelength of the exposure light source is shortened and the numerical aperture (NA) of the projection lens is increased. Currently, an exposure machine using an ArF excimer laser with a wavelength of 193 nm as a light source has been developed. ing.
Under such circumstances, various structures have been proposed as actinic ray-sensitive or radiation-sensitive resin compositions.

For example, Patent Document 1 discloses "a radiation-sensitive resin composition (claim 1) containing an acid generator that generates a compound represented by the following formula (1) upon exposure to radiation".

JP 2013-083944 A

The present inventors specifically examined the technique disclosed in Patent Document 1 and found that the composition of Patent Document 1 has room for improvement in the LWR (line width roughness) performance of the resulting pattern. did.

Accordingly, an object of the present invention is to provide an actinic ray-sensitive or radiation-sensitive resin composition capable of obtaining a pattern having excellent LWR performance.
Another object of the present invention is to provide a resist film, a pattern forming method, and an electronic device manufacturing method relating to the actinic ray-sensitive or radiation-sensitive resin composition.

As a result of intensive studies aimed at solving the above problems, the inventors of the present invention have found that the above problems can be solved by the following configuration.

[1]
An actinic ray-sensitive or radiation-sensitive resin composition comprising a compound that generates an acid represented by the general formula (I) described below upon exposure to actinic rays or radiation, and a resin.
[2]
The actinic ray-sensitive or radiation-sensitive resin composition according to [1], wherein in general formula (I) described later, Rf represents a trifluoromethyl group.
[3]
The actinic ray-sensitive or radiation-sensitive resin composition according to [1] or [2], wherein X in general formula (I) described later represents -COO-.
[4]
The actinic ray-sensitive or radiation-sensitive resin composition according to any one of [1] to [3], wherein R ¹ in general formula (I) described later has a cyclic organic group.
[5]
The actinic ray-sensitive or radiation-sensitive resin composition according to any one of [1] to [4], wherein in general formula (I) described later, R ¹ has an alicyclic group.
[6]
The actinic ray-sensitive or radiation-sensitive resin composition according to any one of [1] to [5], wherein the pKa of the acid represented by the general formula (I) described later is -2.0 or more.
[7]
The actinic ray-sensitive or radiation-sensitive resin composition according to any one of [1] to [6], wherein R ¹ does not have a fluorine atom in general formula (I) described later.
[8]
The actinic ray-sensitive or radiation-sensitive resin composition according to any one of [1] to [7], wherein R ² in general formula (I) described later does not have a fluorine atom.
[9]
[1] A resist film formed using the actinic ray-sensitive or radiation-sensitive resin composition according to any one of [1] to [8].
[10]
forming a resist film on a support using the actinic ray-sensitive or radiation-sensitive resin composition according to any one of [1] to [8];
exposing the resist film;
and developing the exposed resist film using a developer.
[11]
A method for manufacturing an electronic device, comprising the pattern forming method according to [10].

ADVANTAGE OF THE INVENTION According to this invention, the actinic-ray-sensitive or radiation-sensitive resin composition which can obtain the pattern which is excellent in LWR performance can be provided.
In addition, the present invention can provide a resist film, a pattern forming method, and an electronic device manufacturing method related to the actinic ray-sensitive or radiation-sensitive resin composition.

The present invention will be described in detail below.
The description of the constituent elements described below may be made based on representative embodiments of the present invention, but the present invention is not limited to such embodiments.
Regarding the notation of groups (atomic groups) in the present specification, as long as it does not contradict the spirit of the present invention, the notation that does not indicate substituted or unsubstituted includes groups having substituents as well as groups not having substituents. do. For example, an "alkyl group" includes not only an alkyl group having no substituent (unsubstituted alkyl group) but also an alkyl group having a substituent (substituted alkyl group). Also, the term "organic group" as used herein refers to a group containing at least one carbon atom.
The term "actinic rays" or "radiation" as used herein means, for example, the emission line spectrum of a mercury lamp, far ultraviolet rays represented by excimer lasers, extreme ultraviolet rays (EUV light: Extreme Ultraviolet), X-rays, and electron beams (EB : Electron Beam) and the like. As used herein, "light" means actinic rays or radiation.
The term "exposure" as used herein means, unless otherwise specified, not only exposure by the emission line spectrum of a mercury lamp, far ultraviolet rays represented by excimer lasers, extreme ultraviolet rays, X-rays, and EUV light, but also electron beams, and It also includes drawing with particle beams such as ion beams.
In the present specification, the term "~" is used to include the numerical values before and after it as lower and upper limits.
The bonding direction of the divalent groups described herein is not limited unless otherwise specified. For example, in the compound represented by the general formula "X-Y-Z", when Y is -COO-, the compound may be "X-O-CO-Z" and "X-CO —OZ”.

As used herein, (meth)acrylate refers to acrylate and methacrylate, and (meth)acryl refers to acrylic and methacrylic.
In this specification, the weight average molecular weight (Mw), number average molecular weight (Mn), and dispersity (also referred to as molecular weight distribution) (Mw/Mn) of the resin are measured using a GPC (Gel Permeation Chromatography) device (HLC-8120GPC manufactured by Tosoh Corporation). ) by GPC measurement (solvent: tetrahydrofuran, flow rate (sample injection volume): 10 μL, column: TSK gel Multipore HXL-M manufactured by Tosoh Corporation, column temperature: 40 ° C., flow rate: 1.0 mL / min, detector: differential refractive index It is defined as a polystyrene conversion value by a detector (Refractive Index Detector).

As used herein, pKa (acid dissociation constant pKa) represents the acid dissociation constant pKa in an aqueous solution. Defined. The lower the value of the acid dissociation constant pKa, the higher the acid strength. The value of pKa is obtained by calculation using the following software package 1 and based on Hammett's substituent constant and a database of known literature values. All pKa values described herein are calculated using this software package.

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

As used herein, halogen atoms include, for example, fluorine, chlorine, bromine, and iodine atoms.

[Actinic ray-sensitive or radiation-sensitive resin composition]
The actinic ray-sensitive or radiation-sensitive resin composition of the present invention (hereinafter also simply referred to as "composition" or "composition of the present invention") will be described.
The composition of the present invention is a so-called resist composition, and may be a positive resist composition or a negative resist composition. Moreover, it may be a resist composition for alkali development or a resist composition for organic solvent development.
The composition of the present invention is typically a chemically amplified resist composition.

The composition of the present invention contains a compound that generates an acid represented by the general formula (I) described below upon exposure to actinic rays or radiation, and a resin.
Although the mechanism by which the problems of the present invention are solved by such a configuration is not necessarily clear, the inventors presume as follows.
In the acid, the α-carbon atom of the sulfonic acid group is substituted with a fluoroalkyl group and an organic group having a predetermined linking group, so that the acidity can be made relatively low. Moreover, since the acid has a bulky structure, it is easy to control diffusion in the resist film. It is surmised that these properties combine to improve the LWR performance of patterns obtained using the composition of the present invention.

<Resin>
The composition of the invention contains a resin.
The resin is preferably an acid-decomposable resin (hereinafter also referred to as "resin A").
The acid-decomposable resin usually has a repeating unit having a group that is decomposed by the action of acid to increase its polarity (hereinafter also referred to as "acid-decomposable group").
In the pattern forming method of the present invention, typically, when an alkaline developer is used as the developer, a positive pattern is preferably formed, and when an organic developer is used as the developer, a negative pattern is typically formed. A mold pattern is preferably formed.

(Repeating unit having an acid-decomposable group)
Resin A preferably has a repeating unit having an acid-decomposable group.
The acid-decomposable group preferably has a structure in which a polar group is protected by a group (leaving group) that decomposes and leaves under the action of an acid.
Polar groups include carboxy groups, phenolic hydroxyl groups, fluorinated alcohol groups, sulfonic acid groups, sulfonamide groups, sulfonylimide groups, (alkylsulfonyl)(alkylcarbonyl)methylene groups, and (alkylsulfonyl)(alkylcarbonyl)imide groups. , bis(alkylcarbonyl)methylene group, bis(alkylcarbonyl)imide group, bis(alkylsulfonyl)methylene group, bis(alkylsulfonyl)imide group, tris(alkylcarbonyl)methylene group, and tris(alkylsulfonyl)methylene group and other acidic groups (groups that dissociate in a 2.38% by mass tetramethylammonium hydroxide aqueous solution), alcoholic hydroxyl groups, and the like.

The alcoholic hydroxyl group is a hydroxyl group bonded to a hydrocarbon group, and refers to a hydroxyl group other than a hydroxyl group directly bonded to an aromatic ring (phenolic hydroxyl group). It excludes aliphatic alcohols substituted with functional groups (eg, hexafluoroisopropanol groups, etc.). As the alcoholic hydroxyl group, a hydroxyl group having a pKa (acid dissociation constant) of 12 to 20 is preferable.

The polar group is preferably a carboxy group, a phenolic hydroxyl group, a fluorinated alcohol group (preferably a hexafluoroisopropanol group), or a sulfonic acid group.

Preferred groups as acid-decomposable groups are groups in which the hydrogen atoms of these groups are substituted with groups (leaving groups) that leave under the action of acid.
Examples of groups that leave by the action of an acid (leaving groups) include -C(R ₃₆ )(R ₃₇ )(R ₃₈ ), -C(R ₃₆ )(R ₃₇ )(OR ₃₉ ), and —C(R ₀₁ )(R ₀₂ )(OR ₃₉ ) and the like.
In the formula, R ₃₆ to R ₃₉ each independently represent an alkyl group, cycloalkyl group, aryl group, aralkyl group or alkenyl group. R ₃₆ and R ₃₇ may combine with 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.

The alkyl groups of R ₃₆ to R ₃₉ , R ₀₁ and R ₀₂ are preferably alkyl groups having 1 to 8 carbon atoms, such as methyl, ethyl, propyl, n-butyl, sec-butyl, hexyl. and an octyl group.
Cycloalkyl groups of R ₃₆ to R ₃₉ , R ₀₁ and R ₀₂ may be monocyclic or polycyclic. The monocyclic ring is preferably a cycloalkyl group having 3 to 8 carbon atoms, such as cyclopropyl, cyclobutyl, cyclopentyl, cyclohexyl, and cyclooctyl groups. The polycyclic ring is preferably a cycloalkyl group having 6 to 20 carbon atoms, such as adamantyl group, norbornyl group, isobornyl group, camphanyl group, dicyclopentyl group, α-pinel group, tricyclodecanyl group, tetracyclododecyl group. , and androstanyl group. One or more carbon atoms in the cycloalkyl group may be substituted with a heteroatom such as an oxygen atom.
The aryl groups represented by R ₃₆ to R ₃₉ , R ₀₁ and R ₀₂ are preferably aryl groups having 6 to 10 carbon atoms, such as phenyl, naphthyl and anthryl groups.
The aralkyl groups represented by R ₃₆ to R ₃₉ , R ₀₁ and R ₀₂ are preferably aralkyl groups having 7 to 12 carbon atoms, such as benzyl, phenethyl and naphthylmethyl groups.
The alkenyl groups represented by R ₃₆ to R ₃₉ , R ₀₁ and R ₀₂ are preferably alkenyl groups having 2 to 8 carbon atoms, such as vinyl, allyl, butenyl and cyclohexenyl groups. .
The ring formed by combining R ₃₆ and R ₃₇ is preferably a cycloalkyl group (monocyclic or polycyclic). The monocyclic cycloalkyl group is preferably a cyclopentyl group, a cyclohexyl group, or the like, and the polycyclic cycloalkyl group is a norbornyl group, a tetracyclodecanyl group, a tetracyclododecanyl group, an adamantyl group, or the like. preferable.

The acid-decomposable group preferably has a tertiary alkyl ester group, acetal group, cumyl ester group, enol ester group, or acetal ester group, more preferably an acetal group or a tertiary alkyl ester group. preferable.

Resin A preferably has a repeating unit represented by the following general formula (AI) as a repeating unit having an acid-decomposable group.

In general formula (AI), T represents a single bond or a divalent linking group.
Examples of the divalent linking group for T include an alkylene group, an arylene group, -COO-Rt-, and -O-Rt-. In the formula, Rt represents an alkylene group, a cycloalkylene group or an arylene group.
T is preferably a single bond or -COO-Rt-. Rt is preferably a chain alkylene group having 1 to 5 carbon atoms, more preferably -CH ₂ -, -(CH ₂ ) ₂ -, or -(CH ₂ ) ₃ -.
More preferably T is a single bond.

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

In general formula (AI), Rx ₁ to Rx ₃ each independently represent an alkyl group or a cycloalkyl group.
Any two of Rx ₁ to Rx ₃ may or may not combine to form a ring structure.
The alkyl groups of Rx ₁ , Rx ₂ and Rx ₃ may be linear or branched, and may be methyl, ethyl, n-propyl, isopropyl, n-butyl. group, isobutyl group, t-butyl group and the like are preferred. The number of carbon atoms in the alkyl group is preferably 1-10, more preferably 1-5, and even more preferably 1-3. Some of the carbon-carbon bonds in the alkyl groups of Rx ₁ , Rx ₂ and Rx ₃ may be double bonds.
The cycloalkyl groups of Rx ₁ , Rx ₂ and Rx ₃ may be monocyclic or polycyclic. A cyclopentyl group, a cyclohexyl group, etc. are mentioned as a monocyclic cycloalkyl group. Polycyclic cycloalkyl groups include norbornyl, tetracyclodecanyl, tetracyclododecanyl, and adamantyl groups.

The ring formed by combining two of Rx ₁ , Rx ₂ and Rx ₃ may be monocyclic or polycyclic. Examples of monocyclic rings include monocyclic cycloalkane rings such as cyclopentyl ring, cyclohexyl ring, cycloheptyl ring, and cyclooctane ring. Examples of polycyclic rings include polycyclic cycloalkyl rings such as norbornane, tetracyclodecane, tetracyclododecane, and adamantane rings. Among them, a cyclopentyl ring, a cyclohexyl ring, or an adamantane ring is preferable.
As the ring formed by combining two of Rx ₁ , Rx ₂ and Rx ₃ , the ring shown below is also preferable.

Specific examples of the monomer corresponding to the repeating unit represented by formula (AI) are given below. The following specific examples correspond to the case where Xa ₁ in general formula (AI) is a methyl group, and Xa ₁ can optionally be substituted with a hydrogen atom, a halogen atom, or a monovalent organic group.

Resin A preferably has repeating units described in paragraphs [0336] to [0369] of US Patent Application Publication No. 2016/0070167A1 as repeating units having an acid-decomposable group.

In addition, Resin A, as a repeating unit having an acid-decomposable group, is decomposed by the action of an acid described in paragraphs [0363] to [0364] of US Patent Application Publication No. 2016/0070167A1 to form an alcoholic hydroxyl group. You may have a repeat unit containing the resulting group.

The content of repeating units having an acid-decomposable group contained in Resin A is preferably 10 to 90 mol%, more preferably 20 to 80 mol%, and 30 to 70 mol%, based on the total repeating units of Resin A. is more preferred.
Resin A may have one repeating unit having an acid-decomposable group, or may have two or more repeating units. When two or more types are present, the total content is preferably within the range of the above preferred content.

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

The lactone structure or sultone structure may have a lactone ring or a sultone ring, and a lactone structure having a 5- to 7-membered lactone ring or a sultone structure having a 5- to 7-membered sultone ring is preferred.
A lactone structure in which a 5- to 7-membered lactone ring is condensed with another ring to form a bicyclo structure or a spiro structure is also preferred. A sultone structure in which a 5- to 7-membered sultone ring is condensed with another ring to form a bicyclo structure or a spiro structure is also preferred.

Among them, Resin A has a lactone structure represented by any of the following general formulas (LC1-1) to (LC1-22), or any of the following general formulas (SL1-1) to (SL1-3). It is preferred to have repeating units having the represented sultone structure. Also, the lactone structure or sultone structure may be directly bonded to the main chain.
Among them, general formula (LC1-1), general formula (LC1-4), general formula (LC1-5), general formula (LC1-8), general formula (LC1-16), general formula (LC1-21), Alternatively, a lactone structure represented by general formula (LC1-22) or a sultone structure represented by general formula (SL1-1) is preferable.

The lactone structure or sultone structure may or may not have a substituent (Rb ₂ ). The substituent (Rb ₂ ) includes an alkyl group having 1 to 8 carbon atoms, a cycloalkyl group having 4 to 7 carbon atoms, an alkoxy group having 1 to 8 carbon atoms, an alkoxycarbonyl group having 2 to 8 carbon atoms, a carboxy group, A halogen atom, a hydroxyl group, a cyano group, or an acid-decomposable group is preferable, and an alkyl group having 1 to 4 carbon atoms, a cyano group, or an acid-decomposable group is more preferable. n2 represents an integer from ₀ to 4; When n ₂ is 2 or more, the multiple substituents (Rb ₂ ) may be the same or different. Also, a plurality of substituents (Rb ₂ ) may be bonded to each other to form a ring.

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

In the above general formula (III),
A represents an ester bond (group represented by -COO-) or an amide bond (group represented by -CONH-).

n is the number of repetitions of the structure represented by -R ₀ -Z- and represents an integer of 0 to 5, preferably 0 or 1, more preferably 0; When n is 0, (-R ₀ -Z-)n becomes a single bond.

R ₀ represents an alkylene group, a cycloalkylene group, or a combination thereof. When multiple R ₀ are present, the multiple R ₀ may be the same or different.
The alkylene group or cycloalkylene group of R ₀ may have a substituent.

Z represents a single bond, ether bond, ester bond, amide bond, urethane bond or urea bond. When there are multiple Z's, the multiple Z's may be the same or different.
Among them, Z is preferably an ether bond or an ester bond, more preferably an ester bond.

_R8 represents a monovalent organic group having a lactone structure or a sultone structure.
Among them, in any of the structures represented by general formulas (LC1-1) to (LC1-22) and the structures represented by general formulas (SL1-1) to (SL1-3), a lactone structure or a sultone structure is preferably a group obtained by removing one hydrogen atom from one carbon atom constituting The carbon atoms from which one hydrogen atom is removed are preferably not carbon atoms constituting the substituent (Rb ₂ ).

_R7 represents a hydrogen atom, a halogen atom, or a monovalent organic group (preferably a methyl group).

Examples of monomers corresponding to repeating units having at least one selected from the group consisting of lactone structures and sultone structures are shown below.
In the examples below, the methyl group attached to the vinyl group may be replaced with a hydrogen atom, a halogen atom, or a monovalent organic group.

Resin A may have a repeating unit having a carbonate structure. As the carbonate structure, a cyclic carbonate structure is preferred.
As the repeating unit having a cyclic carbonate structure, a repeating unit represented by the following general formula (A-1) is preferable.

In general formula (A-1), R _A ¹ represents a hydrogen atom, a halogen atom, or a monovalent organic group (preferably a methyl group).
n represents an integer of 0 or more.
R _A ² represents a substituent. When n is 2 or more, a plurality of R _A ² may be the same or different.
A represents a single bond or a divalent linking group.
Z represents an atomic group forming a monocyclic or polycyclic ring together with the group represented by -O-CO-O- in the formula.

Resin A is a repeating unit having at least one selected from the group consisting of a lactone structure, a sultone structure, and a carbonate structure, as described in paragraphs [0370] to [0414] of US Patent Application Publication No. 2016/0070167A1. It is also preferred to have the stated repeating units.

When the resin A has a repeating unit having at least one selected from the group consisting of a lactone structure, a sultone structure, and a carbonate structure, the lactone structure contained in the resin A, the sultone structure, and the group consisting of a carbonate structure The content of repeating units having at least one selected type is preferably 5 to 70 mol%, more preferably 10 to 65 mol%, more preferably 20 to 60 mol%, based on the total repeating units in resin A. preferable.
Resin A may have one type of repeating unit having at least one type selected from the group consisting of a lactone structure, a sultone structure, and a carbonate structure, or may have two or more types. . When two or more types are present, the total content is preferably within the range of the above preferred content.

(Repeating unit having a polar group)
Resin A may have a repeating unit having a polar group, in addition to the repeating units described above.
Polar groups include hydroxyl groups, cyano groups, carboxy groups, and fluorinated alcohol groups.
As the repeating unit having a polar group, a repeating unit having an alicyclic hydrocarbon structure substituted with a polar group is preferred. Moreover, the repeating unit having a polar group preferably does not have an acid-decomposable group. Among the alicyclic hydrocarbon structures substituted with a polar group, the alicyclic hydrocarbon structure is preferably an adamantyl group or a norbornane group.

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

In addition, specific examples of repeating units having a polar group include repeating units disclosed in paragraphs [0415] to [0433] of US Patent Application Publication No. 2016/0070167A1.
When the resin A has a repeating unit having a polar group, the content of the repeating unit having a polar group is preferably 5 to 40 mol%, more preferably 5 to 30 mol%, based on the total repeating units in the resin A. Preferably, 10 to 25 mol % is more preferable.
The resin A may have one repeating unit having a polar group, or may have two or more repeating units. When two or more types are present, the total content is preferably within the range of the above preferred content.

(Repeating unit having neither acid-decomposable group nor polar group)
Resin A may further have a repeating unit having neither an acid-decomposable group nor a polar group, in addition to the repeating units described above. A repeating unit having neither an acid-decomposable group nor a polar group preferably has an alicyclic hydrocarbon structure such as an alicyclic group. Examples of repeating units having neither an acid-decomposable group nor a polar group include repeating units described in paragraphs [0236] to [0237] of US Patent Application Publication No. 2016/0026083A1. Preferred examples of monomers corresponding to repeating units having neither acid-decomposable groups nor polar groups are shown below.

In addition, specific examples of the repeating unit having neither an acid-decomposable group nor a polar group include repeating units disclosed in paragraph [0433] of US Patent Application Publication No. 2016/0070167A1. .
When Resin A has repeating units having neither an acid-decomposable group nor a polar group, the content of repeating units having neither an acid-decomposable group nor a polar group is On the other hand, 5 to 40 mol % is preferable, 5 to 30 mol % is more preferable, and 5 to 25 mol % is even more preferable.
The resin A may have one repeating unit having neither an acid-decomposable group nor a polar group, or may have two or more repeating units. When two or more types are present, the total content is preferably within the range of the above preferred content.

In addition to the repeating structural unit described above, resin A can be used to adjust dry etching resistance, standard developer suitability, substrate adhesion, resist profile, or generally necessary properties of resist such as resolution, heat resistance, and sensitivity. It may have various repeating structural units for the purpose of
Examples of such repeating structural units include, but are not limited to, repeating structural units corresponding to predetermined monomers.

Examples of the predetermined monomer include compounds having one addition-polymerizable unsaturated bond selected from (meth)acrylic acid esters, (meth)acrylamides, allyl compounds, vinyl ethers, and vinyl esters. is mentioned.
In addition, addition-polymerizable unsaturated compounds that are copolymerizable with the monomers corresponding to the above-mentioned various repeating structural units may also be used.
In Resin A, the molar ratio of each repeating structural unit is appropriately set in order to adjust various performances.

When the composition of the present invention is used for ArF exposure, the resin A preferably has substantially no aromatic groups from the viewpoint of ArF light transmission. More specifically, the repeating unit having an aromatic group is preferably 5 mol% or less, more preferably 3 mol% or less, and ideally, based on the total repeating units in Resin A. It is even more preferred to have 0 mol %, ie no repeating units with aromatic groups. Moreover, the resin A preferably has a monocyclic or polycyclic alicyclic hydrocarbon structure.

The resin A is preferably a (meth)acrylic acid ester-based resin, more preferably a methacrylic acid ester-based resin.
The (meth)acrylic acid ester resin (or methacrylic acid ester resin) has a content of (meth)acrylate repeating units (or methacrylate repeating units) of 80 mol% or more with respect to the total repeating units of the resin A. is preferably 90 mol % or more, more preferably 95 mol % or more, and still more preferably 99 mol % or more.
In the resin A, all repeating units may be composed of (meth)acrylate repeating units. In this case, all of the repeating units may be methacrylate-based repeating units, all of the repeating units may be acrylate-based repeating units, and all of the repeating units are a combination of methacrylate-based repeating units and acrylate-based repeating units. may be Above all, the content of the acrylate-based repeating units is preferably 50 mol % or less with respect to the total repeating units of the resin A.

In addition, as the resin A, a known resin can be used as appropriate. For example, paragraphs [0055]-[0191] of US Patent Application Publication No. 2016/0274458A1, paragraphs [0035]-[0085] of US Patent Application Publication No. 2015/0004544A1, and US Patent Application Publication No. 2016/ Known resins disclosed in paragraphs [0045] to [0090] of 0147150A1 can be suitably used as resin A.

When the composition of the present invention is for KrF exposure, EB exposure, or EUV exposure, the resin A preferably has a repeating unit having an aromatic hydrocarbon group, and the resin A preferably contains a repeating unit containing a phenolic hydroxyl group. It is more preferable to have units. Repeating units containing a phenolic hydroxyl group include hydroxystyrene repeating units and hydroxystyrene (meth)acrylate repeating units.
When the composition of the present invention is for KrF exposure, EB exposure, or EUV exposure, the resin A is a group (leaving group) in which hydrogen atoms of phenolic hydroxyl groups are decomposed and eliminated by the action of an acid. It is preferred to have a protected structure.
In this case, the content of the repeating unit having an aromatic hydrocarbon group contained in the resin A is preferably 30 to 100 mol%, more preferably 40 to 100 mol%, based on the total repeating units in the resin A. 50 to 100 mol % is more preferred.

The weight average molecular weight of Resin A is preferably 1,000 to 200,000, more preferably 2,000 to 20,000, and still more preferably 3,000 to 19,000. The dispersity (Mw/Mn) is usually 1.00 to 3.00, preferably 1.00 to 2.60, more preferably 1.00 to 2.00, and further 1.10 to 2.00. preferable.

Resin A may be used individually by 1 type, and may use 2 or more types.
The content of resin A in the composition is usually 20% by mass or more, preferably 40% by mass or more, more preferably 60% by mass or more, and even more preferably 75% by mass or more, relative to the total solid content in the composition. . Although the upper limit is not particularly limited, it is preferably 95% by mass or less, more preferably 90% by mass or less.
When two or more resins A are used in the composition, the total content is preferably within the range of the preferred content described above.
In addition, solid content intends the component except the solvent in a composition, and if it is a component other than a solvent, even if it is a liquid component, it will be considered as solid content.

<Specific photoacid generator>
The composition of the present invention is a compound (photoacid generator) that generates an acid upon exposure to actinic rays or radiation, and the generated acid is a photoacid generator represented by the general formula (I) described below. containing agents.
A photoacid generator that generates an acid represented by formula (I) is hereinafter also referred to as a specific photoacid generator.

The pKa of the acid generated from the specific photoacid generator is preferably -3.00 or higher, more preferably -2.50 or higher, and still more preferably -2.00 or higher.
Although there is no particular upper limit for the pKa of the acid generated from the specific photoacid generator, it is preferably 2.00 or less.
The acid generated from the specific photoacid generator is a compound represented by the following general formula (I).

In general formula (I), Rf represents a fluoroalkyl group.
A fluoroalkyl group is an alkyl group having at least one fluorine atom as a substituent, and as long as it has at least one fluorine atom, the alkyl group may have a substituent other than a fluorine atom.
In the fluoroalkyl group of Rf, 30 mol% or more of the hydrogen atoms in the alkyl group are preferably substituted with fluorine atoms, more preferably 60 mol% or more are substituted with fluorine atoms, and 90 mol% More preferably, the above are substituted with fluorine atoms. Among them, the fluoroalkyl group of Rf is particularly preferably a perfluoroalkyl group in which all hydrogen atoms of the alkyl group are substituted with fluorine atoms.
The fluoroalkyl group of Rf may be linear or branched, and may have a cyclic structure.
The number of carbon atoms in the fluoroalkyl group of Rf is preferably 1-10, more preferably 1-3, and still more preferably 1.
The number of fluorine atoms in the fluoroalkyl group of Rf is preferably 1-10.
Among them, Rf is preferably a trifluoromethyl group.

In general formula (I), t represents 0 or 1;
In general formula (I), X represents -COO-, -O-, -CO-, -S(O) _n -, -CS-, -NR ³ -, or a group consisting of a combination thereof.
R ³ in —NR ³ — represents a hydrogen atom or an organic group (preferably an alkyl group, preferably having 1 to 3 carbon atoms).
n in -S(O) _n - represents an integer of 0 to 3; For example, when n=0, -S(O) _n - represents -S-, when n=1, -S(O) _n - represents -SO-, and when n=2, -S (O) _n - represents -SO ₂ -, and when n=3, -S(O) _n - represents -SO ₃ -.
Examples of the group consisting of the above combination include -NR ³ -CO-.
Moreover, the group consisting of the above combination is preferably a group other than -COO- and -S(O) _n -.
Among them, X is preferably -COO-. ^The bonding direction of -COO- may be any direction, for example, the carbonyl group portion in -COO- may be bonded to ^R2 , or the ether group portion in may be
Also, when t is 1, X is preferably -S(O) _n - or -NR ³ -.

In general formula (I), R ¹ represents an organic group.
The organic group of R ¹ preferably has a cyclic group. When the organic group of R ¹ has a cyclic group, R ¹ may partially contain the cyclic group, or R ¹ may be the cyclic group itself.
The cyclic group may be monocyclic or polycyclic. The cyclic group preferably has 3 to 20 carbon atoms, more preferably 5 to 15 carbon atoms, and even more preferably 6 to 10 carbon atoms. The number of carbon atoms possessed by the substituent which the cyclic group may have is not included in the number of carbon atoms of the cyclic group. The cyclic group may or may not have aromaticity, and preferably does not.
The cyclic group is preferably a cyclic organic group, more preferably an alicyclic group or the like.
As the cyclic group, a cyclohexyl group and an adamantyl group are preferable.
Also, R ¹ preferably does not have a fluorine atom.

R ¹ is preferably, for example, a group represented by general formula (II) below.

In general formula (II), p represents an integer of 0-10, and q represents an integer of 0-10. * represents a binding position. p is preferably 0 to 2, more preferably 0 or 1. q is preferably 0 to 2, more preferably 0 or 1.

R ⁴ and R ⁵ each independently represent a hydrogen atom, a fluorine atom, or an alkyl group, preferably a hydrogen atom or an alkyl group, more preferably a hydrogen atom.
When multiple R ⁴ and R ⁵ are present, each of R ⁴ and R ⁵ may be the same or different.
The alkyl group represented by R ⁴ and R ⁵ may have a substituent (preferably a substituent other than a fluorine atom) and preferably has 1 to 4 carbon atoms.

L represents a divalent linking group. When there are multiple L's, each L may be the same or different.
Examples of divalent linking groups include -COO-, -CONH-, -CO-, -O-, -S-, -SO-, -SO ₂ -, and alkylene groups (preferably having 1 to 6 carbon atoms). , a cycloalkylene group (preferably having 3 to 15 carbon atoms), an alkenylene group (preferably having 2 to 6 carbon atoms), and a divalent linking group combining a plurality of these.

W represents an organic group having a cyclic structure. W is preferably a cyclic organic group itself.
Cyclic organic groups include, for example, alicyclic groups, aryl groups, and heterocyclic groups.
The alicyclic group may be monocyclic or polycyclic. Monocyclic alicyclic groups include, for example, monocyclic cycloalkyl groups such as a cyclopentyl group, a cyclohexyl group, and a cyclooctyl group. The polycyclic alicyclic group includes, for example, a norbornyl group, a tricyclodecanyl group, a tetracyclodecanyl group, a tetracyclododecanyl group, and a polycyclic cycloalkyl group such as an adamantyl group.

Aryl groups may be monocyclic or polycyclic. This aryl group includes, for example, a phenyl group, a naphthyl group, a phenanthryl group, and an anthryl group.
A heterocyclic group may be monocyclic or polycyclic. Moreover, the heterocyclic group may or may not have aromaticity. Heterocyclic groups having aromaticity include, for example, a pyrrole ring group, a furan ring group, a thiophene ring group, a benzofuran ring group, a benzothiophene ring group, a dibenzofuran ring group, a dibenzothiophene ring group, and a pyridine ring. groups. Non-aromatic heterocyclic groups include, for example, a tetrahydropyran ring group, a lactone ring group, a sultone ring group, and a decahydroisoquinoline ring group.

The cyclic organic group may have a substituent. Examples of such substituents include alkyl groups (either linear or branched, preferably having 1 to 12 carbon atoms), cycloalkyl groups (monocyclic, polycyclic (including spirocyclic) preferably having 3 to 20 carbon atoms), an aryl group (preferably having 6 to 14 carbon atoms), a hydroxyl group, and an alkoxy group. Substituents may also include ester groups, amide groups, urethane groups, ureido groups, thioether groups, sulfonamide groups, and/or sulfonate groups.
One or more carbon atoms (carbon atoms that contribute to ring formation) constituting the cyclic organic group may or may not be substituted with carbonyl carbon atoms.

In general formula (I), R ² represents an organic group.
Organic groups for R ² include alkyl groups, alkenyl groups, alicyclic groups, aryl groups, and heterocyclic groups.
The alkyl group as the organic group may be linear or branched, and preferably has 1 to 10 carbon atoms, more preferably 1 to 5 carbon atoms. Preferred alkyl groups are, for example, methyl group, ethyl group, n-propyl group, isopropyl group, n-butyl group, isobutyl group and t-butyl group.
The alkenyl group as the organic group may be linear or branched, and preferably has 2 to 10 carbon atoms, more preferably 2 to 5 carbon atoms. The alkenyl group is preferably, for example, a group in which one or more ethylene groups (or ethyl groups) are substituted with a vinylene group (or vinyl group) in the groups given as examples of the above alkyl groups.
The alicyclic group, aryl group and heterocyclic group as the organic group are preferably, for example, the alicyclic group, aryl group and heterocyclic group in W described above.
Also preferably, R ² does not have a fluorine atom.

The specific photoacid generator is not particularly limited as long as the generated acid satisfies the above requirements, and may be an onium salt compound or a zwitterion.
Among them, the specific photoacid generator is preferably an onium salt compound having an anion and a cation.
The specific photoacid generator is preferably a compound represented by general formula (ZaI) (compound (ZaI)) or a compound represented by general formula (ZaII) (compound (ZaII)).

Rf, R ¹ , R ² , t and X in general formula (ZaI) are synonymous with Rf, R ¹ , R ² , t and X in general formula (I) above.

In the above general formula (ZaI),
R ²⁰¹ , R ²⁰² and R ²⁰³ each independently represent an organic group.
The number of carbon atoms in the organic group as R ²⁰¹ , R ²⁰² and R ²⁰³ is generally 1-30, preferably 1-20. Also, two of R ²⁰¹ to R ²⁰³ may combine to form a ring structure, and the ring may contain an oxygen atom, a sulfur atom, an ester group, an amide group, or a carbonyl group. Groups formed by bonding two of R ²⁰¹ to R ²⁰³ include, for example, an alkylene group (eg, a butylene group and a pentylene group), and —CH ₂ —CH ₂ —O—CH ₂ —CH ₂ — is mentioned.

Preferred embodiments of the cation in general formula (ZaI) include compound (ZaI-1), compound (ZaI-2), and compounds represented by general formula (ZaI-3b) (compound (ZaI-3b) ), and corresponding groups in the compound represented by general formula (ZaI-4b) (compound (ZaI-4b)).
The specific photoacid generator may be a compound having a plurality of structures represented by general formula (ZaI). For example, at least one of R ²⁰¹ to R ²⁰³ of the compound represented by general formula (ZaI) and at least one of R ²⁰¹ to R ²⁰³ of another compound represented by general formula (ZaI) are single bonds. Alternatively, it may be a compound having a structure bonded via a linking group.

First, the compound (ZaI-1) will be explained.
Compound (ZaI-1) is an arylsulfonium compound in which at least one of R ²⁰¹ to R ²⁰³ in general formula (ZaI) is an aryl group, that is, a compound having arylsulfonium as a cation.
In the arylsulfonium compound, all of R ²⁰¹ to R ²⁰³ may be aryl groups, or part of R ²⁰¹ to R ²⁰³ may be aryl groups and the rest may be alkyl groups or cycloalkyl groups.
In addition, one of R ²⁰¹ to R ²⁰³ may be an aryl group, and the remaining two of R ²⁰¹ to R ²⁰³ may combine to form a ring structure, in which an oxygen atom, a sulfur atom, It may contain an ester group, an amide group, or a carbonyl group. The group formed by bonding two of R ²⁰¹ to R ²⁰³ includes, for example, one or more methylene groups substituted with an oxygen atom, a sulfur atom, an ester group, an amide group and/or a carbonyl group. alkylene group (eg, butylene group, pentylene group, or —CH ₂ —CH ₂ —O—CH ₂ —CH ₂ —).
Arylsulfonium compounds include, for example, triarylsulfonium compounds, diarylalkylsulfonium compounds, aryldialkylsulfonium compounds, diarylcycloalkylsulfonium compounds, and aryldicycloalkylsulfonium compounds.

The aryl group contained in the arylsulfonium compound is preferably a phenyl group or a naphthyl group, more preferably a phenyl group. The aryl group may be an aryl group having a heterocyclic structure having an oxygen atom, a nitrogen atom, a sulfur atom, or the like. Heterocyclic structures include pyrrole residues, furan residues, thiophene residues, indole residues, benzofuran residues, and benzothiophene residues. When the arylsulfonium compound has two or more aryl groups, the two or more aryl groups may be the same or different.
The alkyl group or cycloalkyl group optionally possessed by the arylsulfonium compound is a linear alkyl group having 1 to 15 carbon atoms, a branched alkyl group having 3 to 15 carbon atoms, or 3 to 3 carbon atoms. 15 cycloalkyl groups are preferred, such as methyl, ethyl, propyl, n-butyl, sec-butyl, t-butyl, cyclopropyl, cyclobutyl, and cyclohexyl groups.

The substituents that the aryl group, alkyl group and cycloalkyl group of R ²⁰¹ to R ²⁰³ may have each independently include an alkyl group (eg, 1 to 15 carbon atoms) and a cycloalkyl group (eg, carbon 3 to 15), aryl groups (eg, 6 to 14 carbon atoms), alkoxy groups (eg, 1 to 15 carbon atoms), cycloalkylalkoxy groups (eg, 1 to 15 carbon atoms), halogen atoms, hydroxyl groups, and phenylthio groups. is mentioned.
The above substituent may further have a substituent if possible. For example, the above alkyl group may have a halogen atom as a substituent to form a halogenated alkyl group such as a trifluoromethyl group. .

Next, the compound (ZaI-2) will be explained.
Compound (ZaI-2) is a compound in which R ²⁰¹ to R ²⁰³ in formula (ZaI) each independently represents an organic group having no aromatic ring. Here, the aromatic ring also includes an aromatic ring containing a heteroatom.
The organic group having no aromatic ring as R ²⁰¹ to R ²⁰³ generally has 1 to 30 carbon atoms, preferably 1 to 20 carbon atoms.
R ²⁰¹ to R ²⁰³ are each independently preferably an alkyl group, a cycloalkyl group, an allyl group, or a vinyl group, and a linear or branched 2-oxoalkyl group, 2-oxocycloalkyl group, or , an alkoxycarbonylmethyl group is more preferred, and a linear or branched 2-oxoalkyl group is even more preferred.

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

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

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

Any two or more of R _1c to R _5c , R _5c and R _6c , R _6c and R _7c , R _5c and R _x , and R _x and R _y may combine to form a ring. This ring may each independently contain an oxygen atom, a sulfur atom, a ketone group, an ester bond, or an amide bond.
Examples of the ring include aromatic or non-aromatic hydrocarbon rings, aromatic or non-aromatic hetero rings, and polycyclic condensed rings in which two or more of these rings are combined. The ring includes a 3- to 10-membered ring, preferably a 4- to 8-membered ring, more preferably a 5- or 6-membered ring.

Examples of groups formed by bonding two or more of R _1c to R _5c , R _6c and R _7c , and R _x and R _y include alkylene groups such as a butylene group and a pentylene group. A methylene group in this alkylene group may be substituted with a heteroatom such as an oxygen atom.
The group formed by combining R _5c and R _6c and R _5c and R _x is preferably a single bond or an alkylene group. The alkylene group includes a methylene group, an ethylene group, and the like.
Zac- has the same meaning as "R ² -X-(CH ₂ ) _t -C(Rf)(R ¹ )-SO ₃ ^- " in general formula ( ^ZaI ).

Next, the compound (ZaI-4b) will be described.
Compound (ZaI-4b) is a compound represented by the following general formula (ZaI-4b).

In the general formula (ZaI-4b),
l represents an integer of 0 to 2;
r represents an integer of 0 to 8;
R ₁₃ is a hydrogen atom, a fluorine atom, a hydroxyl group, an alkyl group, an alkoxy group, an alkoxycarbonyl group, or a group having a cycloalkyl group (it may be a cycloalkyl group itself, or a group partially containing a cycloalkyl group may be). These groups may have a substituent.
R ₁₄ is a hydroxyl group, an alkyl group, an alkoxy group, an alkoxycarbonyl group, an alkylcarbonyl group, an alkylsulfonyl group, a cycloalkylsulfonyl group, or a group having a cycloalkyl group (it may be a cycloalkyl group itself, or a cycloalkyl It may be a group containing a group as a part). These groups may have a substituent. Each of R 14 independently represents the above group such as a hydroxyl group when a plurality of R ₁₄ are present.
Each R ₁₅ independently represents an alkyl group, a cycloalkyl group, or a naphthyl group. These groups may have a substituent. Two R ₁₅ may be joined together to form a ring. When two R ₁₅ are combined to form a ring, the ring skeleton may contain a heteroatom such as an oxygen atom or a nitrogen atom. In one aspect, two R ₁₅ are alkylene groups, preferably joined together to form a ring structure.
Za ^— has the same meaning as “R ² —X—(CH ₂ ) _t —C(Rf)(R ¹ )—SO ₃ ^— ” in general formula (ZaI).

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

Next, general formula (ZaII) will be described.
In general formula (ZaII), R ²⁰⁴ and R ²⁰⁵ each independently represent an aryl group, an alkyl group or a cycloalkyl group.
The aryl group for R ²⁰⁴ and R ²⁰⁵ is preferably a phenyl group or a naphthyl group, more preferably a phenyl group. The aryl group for R ²⁰⁴ and R ²⁰⁵ may be an aryl group having a heterocyclic ring having an oxygen atom, a nitrogen atom, a sulfur atom, or the like. Skeletons of heterocyclic aryl groups include, for example, pyrrole, furan, thiophene, indole, benzofuran, and benzothiophene.
The alkyl group and cycloalkyl group for R ²⁰⁴ and R ²⁰⁵ include a linear alkyl group having 1 to 10 carbon atoms or a branched alkyl group having 3 to 10 carbon atoms (e.g., methyl group, ethyl group, propyl group, A butyl group or a pentyl group) or a cycloalkyl group having 3 to 10 carbon atoms (eg, a cyclopentyl group, a cyclohexyl group, or a norbornyl group) is preferred.

The aryl group, alkyl group and cycloalkyl group of R ²⁰⁴ and R ²⁰⁵ may each independently have a substituent. Examples of substituents that the aryl group, alkyl group and cycloalkyl group of R ²⁰⁴ and R ²⁰⁵ may have include an alkyl group (eg, having 1 to 15 carbon atoms) and a cycloalkyl group (eg, having 3 carbon atoms). 15), aryl groups (eg, 6 to 15 carbon atoms), alkoxy groups (eg, 1 to 15 carbon atoms), halogen atoms, hydroxyl groups, and phenylthio groups.
"R ² -X-(CH ₂ ) _t -C(Rf)(R ¹ )-SO ₃ ^- " in general formula (ZaII) is an anion, and "R ² -X- (CH ₂ ) _t —C(Rf)(R ¹ )—SO ₃ ⁻ ”.

Preferred examples of the specific photoacid generator are shown below. In the examples below, the combination of anions and cations may be used interchangeably.

The specific photoacid generator may be in the form of a low-molecular-weight compound, or may be in the form of being incorporated into a part of the polymer. Moreover, the form of a low-molecular-weight compound and the form incorporated into a part of a polymer may be used in combination.
The specific photoacid generator is preferably in the form of a low molecular weight compound.
When the specific photoacid generator is in the form of a low-molecular-weight compound, the molecular weight is preferably 3,000 or less, more preferably 2,000 or less, even more preferably 1,000 or less.

The content of the specific photoacid generator is preferably 0.1 to 35% by mass, more preferably 0.5 to 30% by mass, still more preferably 10 to 25% by mass, relative to the total solid content of the composition.
The content of the specific photoacid generator is preferably 0.01 to 1.00 mmol, more preferably 0.05 to 0.70 mmol, and further preferably 0.10 to 0.40 mmol, relative to 1 g of the solid content of the composition. preferable.
The specific photoacid generator may be used singly or in combination of two or more. When two or more are used, the total content is preferably within the range of the preferred content.

<Acid diffusion control agent>
The compositions of the present invention preferably contain an acid diffusion control agent. The acid diffusion control agent traps the acid generated from the photoacid generator (including the specific photoacid generator) during exposure, and suppresses the reaction of the acid-decomposable resin in the unexposed area due to excess generated acid. Acts as a char.
Examples of acid diffusion control agents include basic compounds (DA), basic compounds (DB) whose basicity decreases or disappears when exposed to actinic rays or radiation, and nitrogen atoms that desorb by the action of an acid. Low molecular weight compounds (DD) having a leaving group can be mentioned. Known acid diffusion control agents can be used as appropriate in the composition of the present invention. For example, paragraphs [0627] to [0664] of US Patent Application Publication No. 2016/0070167A1, paragraphs [0095] to [0187] of US Patent Application Publication No. 2015/0004544A1, US Patent Application Publication No. 2016/0237190A1. Known compounds disclosed in paragraphs [0403] to [0423] of the specification and paragraphs [0259] to [0328] of US Patent Application Publication No. 2016/0274458A1 can be suitably used as acid diffusion control agents.

(Basic compound (DA))
Preferred examples of the basic compound (DA) include compounds having structures represented by the following formulas (A) to (E).

In 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), or a cycloalkyl group (preferably having 3 to 20 carbon atoms) , or represents an aryl group (having 6 to 20 carbon atoms). R ²⁰¹ and R ²⁰² may combine with 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 groups in general formulas (A) and (E) may be substituted or unsubstituted.
Regarding the above alkyl group, the substituted alkyl group is preferably 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.
The alkyl groups in general formulas (A) and (E) are more preferably unsubstituted.

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

(Compound (DB))
A basic compound (DB) whose basicity is reduced or lost by irradiation with actinic rays or radiation (hereinafter also referred to as "compound (DB)") has a proton acceptor functional group, and actinic rays or It is a compound whose proton acceptor property is reduced or lost, or whose proton acceptor property is changed to acidic by being decomposed by irradiation with radiation.

The proton-accepting functional group is a functional group having electrons or a group capable of electrostatically interacting with protons, for example, a functional group having a macrocyclic structure such as cyclic polyether, It means a functional group having a nitrogen atom with a non-contributing lone pair of electrons. A nitrogen atom having a lone pair of electrons that does not contribute to π-conjugation is, for example, a nitrogen atom having a partial structure represented by the following formula.

Preferred partial structures of proton acceptor functional groups include, for example, crown ether, azacrown ether, primary to tertiary amine, pyridine, imidazole, and pyrazine structures.

The compound (DB) is decomposed by exposure to actinic rays or radiation to reduce or eliminate its proton acceptor property, or to generate a compound whose proton acceptor property is changed to an acidic one. Here, the reduction or disappearance of proton acceptor property, or the change from proton acceptor property to acidity is a change in proton acceptor property due to the addition of protons to the proton acceptor functional group. means that when a proton adduct is produced from a compound (DB) having a proton-accepting functional group and a proton, the equilibrium constant in the chemical equilibrium decreases.
Proton acceptor properties can be confirmed by measuring pH.

The acid dissociation constant pKa of the compound generated by decomposition of the compound (DB) by irradiation with actinic rays or radiation is preferably pKa<-1, more preferably -13<pKa<-1, and -13<pKa<-3. is more preferred.

Compound (DB) is preferably a compound represented by general formula (c-1).
R-B-X-A-W ₁ -N ^- -W ₂ -R _f [C ⁺ ] (c-1)

In general formula (c-1),
W ₁ and W ₂ each independently represent -SO ₂ - or -CO-.
R _f represents an optionally substituted alkyl group, an optionally substituted cycloalkyl group, or an optionally substituted aryl group.
A represents a single bond or a divalent linking group.
X represents a single bond, —SO ₂ —, or —CO—.
B represents a single bond, an oxygen atom, or -N(R _x )R _y -.
R _x represents a hydrogen atom or an organic group.
R _y represents a single bond or a divalent organic group.
R represents a monovalent organic group having a proton acceptor functional group.
R _x may combine with R _y to form a ring, or may combine with R to form a ring.
[C ⁺ ] represents a counter cation.

At least one of W ₁ and W ₂ is preferably —SO ₂ —, more preferably both are —SO ₂ —.

Rf is preferably an alkyl group having 1 to 6 carbon atoms which may have a fluorine atom, more preferably a perfluoroalkyl group having 1 to 6 carbon atoms, and a perfluoroalkyl group having 1 to 3 carbon atoms. Alkyl groups are more preferred.

The divalent linking group for A is preferably a divalent linking group having 2 to 12 carbon atoms, such as an alkylene group and a phenylene group. Among them, an alkylene group having at least one fluorine atom is preferred, and the number of carbon atoms is preferably 2-6, more preferably 2-4. A linking group such as an oxygen atom or a sulfur atom may be present in the alkylene chain. The alkylene group is preferably an alkylene group in which 30 to 100% of the hydrogen atoms are substituted with fluorine atoms, and more preferably the carbon atoms bonded to the Q site have fluorine atoms. Among them, the divalent linking group for A is preferably a perfluoroalkylene group, more preferably a perfluoroethylene group, a perfluoropropylene group, or a perfluorobutylene group.

The monovalent organic group for Rx preferably has 2 to 30 carbon atoms, such as an alkyl group, a cycloalkyl group optionally having an oxygen atom in the ring, an aryl group, an aralkyl group, and an alkenyl group. is mentioned.
The alkyl group for Rx may have a substituent, preferably a linear or branched alkyl group having 1 to 20 carbon atoms, and an oxygen atom, a sulfur atom and/or a nitrogen atom in the alkyl chain. may have
As the alkyl group having a substituent, a group in which a linear or branched alkyl group is substituted with a cycloalkyl group (e.g., adamantylmethyl group, adamantylethyl group, cyclohexylethyl group, camphor residue, etc.) is mentioned.
The cycloalkyl group for Rx may have a substituent, and is preferably a cycloalkyl group having 3 to 20 carbon atoms. Moreover, the cycloalkyl group may have an oxygen atom in the ring.
The aryl group for Rx may have a substituent, and is preferably an aryl group having 6 to 14 carbon atoms.
The aralkyl group for Rx may have a substituent, preferably an aralkyl group having 7 to 20 carbon atoms.
The alkenyl group for Rx may have a substituent, and examples thereof include groups having a double bond at any position of the alkyl group exemplified for Rx.

When B represents -N(Rx)Ry-, the divalent organic group for Ry is preferably an alkylene group. In this case, the ring that can be formed by combining Rx and Ry includes, for example, a 5- to 8-membered ring containing a nitrogen atom, particularly preferably a 6-membered ring. The nitrogen atom contained in the ring may be a nitrogen atom other than the nitrogen atom directly bonded to X in -N(Rx)Ry-.

When B represents -N(Rx)Ry-, it is preferred that R and Rx are bonded together to form a ring. The formation of a ring improves the stability and the storage stability of the composition using it. The ring preferably has 4 to 20 carbon atoms, may be monocyclic or polycyclic, and may contain an oxygen atom, a sulfur atom and/or a nitrogen atom in the ring. The nitrogen atom contained in the ring may be a nitrogen atom other than the nitrogen atom directly bonded to X in -N(Rx)Ry-.

Monocyclic rings include 4-, 5-, 6-, 7-, and 8-membered rings containing a nitrogen atom. Such ring structures include, for example, a piperazine ring and a piperidine ring. Polycyclic rings include structures consisting of combinations of two or more monocyclic structures. Each of the monocyclic and polycyclic rings may have a substituent, such as a halogen atom, a hydroxyl group, a cyano group, a carboxy group, a carbonyl group, a cycloalkyl group (preferably having 3 to 10 carbon atoms), and an aryl group. (preferably with 6 to 14 carbon atoms), alkoxy groups (preferably with 1 to 10 carbon atoms), acyl groups (preferably with 2 to 15 carbon atoms), acyloxy groups (preferably with 2 to 15 carbon atoms), alkoxycarbonyl groups ( preferably 2 to 15 carbon atoms), or an aminoacyl group (preferably 2 to 20 carbon atoms). These substituents may have further substituents if possible. Examples of aryl groups and cycloalkyl groups further having substituents include alkyl groups (preferably having 1 to 15 carbon atoms). Examples of substituents further possessed by the aminoacyl group include alkyl groups (preferably having 1 to 15 carbon atoms).

The proton-accepting functional group for R is as described above, and partial structures include, for example, structures of crown ethers, primary to tertiary amines, and nitrogen-containing heterocycles (pyridine, imidazole, pyrazine, etc.). It is preferred to have
As the proton acceptor functional group, a functional group having a nitrogen atom is preferable, and a group having a primary to tertiary amino group or a nitrogen-containing heterocyclic group is more preferable. In these structures, all atoms adjacent to the nitrogen atoms contained in the structure are preferably carbon atoms or hydrogen atoms. Further, it is preferable that an electron-withdrawing functional group (carbonyl group, sulfonyl group, cyano group, halogen atom, etc.) is not directly connected to the nitrogen atom.
The monovalent organic group in such a monovalent organic group (group R) containing a proton-accepting functional group preferably has 2 to 30 carbon atoms, and is an alkyl group, a cycloalkyl group, an aryl group, an aralkyl group. and alkenyl groups, and each group may have a substituent.

The alkyl group, cycloalkyl group, aryl group, aralkyl group, and alkenyl group in the alkyl group, cycloalkyl group, aryl group, aralkyl group, and alkenyl group containing a proton-accepting functional group in R are , the same groups as the alkyl group, cycloalkyl group, aryl group, aralkyl group, and alkenyl group mentioned as Rx.

Examples of substituents that each of the above groups may have include, for example, a halogen atom, a hydroxyl group, a nitro group, a cyano group, a carboxy group, a cycloalkyl group (preferably having 3 to 10 carbon atoms. may be substituted with a group having (such as an ester group)), an aryl group (preferably having 6 to 14 carbon atoms), an alkoxy group (preferably having 1 to 10 carbon atoms), an acyl group (preferably having 2 to 20), acyloxy groups (preferably having 2 to 10 carbon atoms), alkoxycarbonyl groups (preferably having 2 to 20 carbon atoms), and aminoacyl groups (preferably having 2 to 20 carbon atoms). Examples of substituents possessed by cyclic groups such as aryl groups and cycloalkyl groups include alkyl groups (preferably having 1 to 20 carbon atoms). Substituents possessed by the aminoacyl group include, for example, 1 or 2 alkyl groups (preferably having 1 to 20 carbon atoms).

[C ⁺ ] is preferably a sulfonium cation or an iodonium cation as a counter cation. As the sulfonium cation and iodonium cation, for example, a sulfonium cation and an iodonium cation in the cation that the specific photoacid generator may have (more specifically, a cation in the compound represented by the general formula (ZaI), and cations in compounds represented by general formula (ZaII)) can be used in the same manner.

(Compound (DC))
In the composition of the present invention, an onium salt (DC) (hereinafter also referred to as "compound (DC)"), which is a relatively weak acid relative to the photoacid generator, can be used as an acid diffusion controller.
When a photoacid generator and an onium salt that generates an acid that is relatively weak to the acid generated from the acid generator are mixed and used, the photoacid generator is activated by actinic rays or by irradiation with radiation. When the acid generated from collides with an onium salt with an unreacted weak acid anion, salt exchange releases the weak acid to yield an onium salt with a strong acid anion. In this process, the strong acid is exchanged for a weak acid with a lower catalytic activity, so that the acid is apparently deactivated, so that the acid diffusion can be controlled.

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

In the formulas, general formulas (d1-1) to (d1-3) R ⁵¹ are hydrocarbon groups which may have a substituent (preferably aryl groups. Hydroxyl groups are preferred as substituents). Z ^2c is an optionally substituted hydrocarbon group having 1 to 30 carbon atoms (provided that the carbon adjacent to S does not have a fluorine atom and/or a fluoroalkyl group as a substituent) . R ⁵² is an organic group (such as an alkyl group), Y ³ is —SO ₂ —, a linear, branched or cyclic alkylene group, or an arylene group, and Y ⁴ is —CO— or —SO ₂ —, and Rf is a hydrocarbon group having a fluorine atom (such as a fluoroalkyl group). Each M ⁺ is independently an ammonium cation, a sulfonium cation, or an iodonium cation.

Preferred examples of the sulfonium cation or iodonium cation represented by M ⁺ include the sulfonium cations exemplified by general formula (ZaI) and the iodonium cations exemplified by general formula (ZaII).

The compound (DC) is a compound (hereinafter also referred to as "compound (DCA)") having a cation site and an anion site in the same molecule and in which the cation site and the anion site are linked by a covalent bond. may
The compound (DCA) is preferably a compound represented by any one of the following general formulas (C-1) to (C-3).

In general formulas (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 a single bond that links the cation site and the anion site.
—X ^— represents an anionic moiety selected from the group consisting of —COO ⁻ , —SO ₃ ⁻ , —SO ₂ ⁻ , and —N ⁻ —R ₄ . R ₄ is a monovalent substitution having at least one of a carbonyl group (—CO—), a sulfonyl group (—SO ₂ —), and a sulfinyl group (—SO—) at the site connecting to the adjacent N atom represents a group.
R ₁ , R ₂ , R ₃ , R ₄ and L ₁ may combine with each other to form a ring structure. In general formula (C-3), two of R ₁ to R ₃ together represent one divalent substituent, which may be bonded to the N atom via a double bond.

Examples of substituents having 1 or more carbon atoms in R ₁ to R ₃ include alkyl groups, cycloalkyl groups, aryl groups, alkyloxycarbonyl groups, cycloalkyloxycarbonyl groups, aryloxycarbonyl groups, alkylaminocarbonyl groups, cyclo Alkylaminocarbonyl groups and arylaminocarbonyl groups are included. Among them, an alkyl group, a cycloalkyl group, or an aryl group is preferable.

L ₁ as a divalent linking group is a linear or branched alkylene group, a cycloalkylene group, an arylene group, a carbonyl group, an ether bond, an ester bond, an amide bond, a urethane bond, a urea bond, and two of these A group formed by combining more than one species and the like can be mentioned. Among them, L ₁ is preferably an alkylene group, an arylene group, an ether bond, an ester bond, or a group formed by combining two or more of these.

(Compound (DD))
A low-molecular-weight compound (DD) having a nitrogen atom and a group that leaves under the action of an acid (hereinafter also referred to as "compound (DD)") has a group that leaves under the action of an acid on the nitrogen atom. It is preferably an amine derivative having
The group that is eliminated by the action of an acid is preferably an acetal group, a carbonate group, a carbamate group, a tertiary ester group, a tertiary hydroxyl group, or a hemiaminal ether group, more preferably a carbamate group or a hemiaminal ether group. preferable.
The molecular weight of the compound (DD) is preferably 100-1000, more preferably 100-700, even more preferably 100-500.
Compound (DD) may have a carbamate group with a protecting group on the nitrogen atom. A protective group constituting a carbamate group can be represented by the following general formula (d-1).

In general formula (d-1),
Rb each independently represents a hydrogen atom, an alkyl group (preferably having 1 to 10 carbon atoms), a cycloalkyl group (preferably having 3 to 30 carbon atoms), an aryl group (preferably having 3 to 30 carbon atoms), an aralkyl group ( preferably 1 to 10 carbon atoms) or an alkoxyalkyl group (preferably 1 to 10 carbon atoms). Rb's may be linked together to form a ring.
The alkyl group, cycloalkyl group, aryl group, and aralkyl group represented by Rb are each independently a hydroxyl group, a cyano group, an amino group, a pyrrolidino group, a piperidino group, a morpholino group, a functional group such as an oxo group, an alkoxy group, or , may be substituted with a halogen atom. The same applies to the alkoxyalkyl group represented by Rb.

Rb is preferably a linear or branched alkyl group, cycloalkyl group or aryl group, more preferably a linear or branched alkyl group or cycloalkyl group.
Examples of the ring formed by connecting two Rb's together include an alicyclic hydrocarbon ring, an aromatic hydrocarbon ring, a heterocyclic hydrocarbon ring, derivatives thereof, and the like.
Specific structures of the group represented by general formula (d-1) include, but are not limited to, structures disclosed in paragraph [0466] of US Patent Publication No. US2012/0135348A1. .

Compound (DD) is preferably a compound represented by the following general formula (6).

In general formula (6),
l represents an integer of 0 to 2, m represents an integer of 1 to 3, and satisfies l+m=3.
Ra represents a hydrogen atom, an alkyl group, a cycloalkyl group, an aryl group, or an aralkyl group. When l is 2, the two Ra's may be the same or different, and the two Ra's may be linked together to form a heterocyclic ring together with the nitrogen atom in the formula. This heterocyclic ring may contain a heteroatom other than the nitrogen atom in the formula.
Rb has the same definition as Rb in formula (d-1) above, and preferred examples are also the same.
In general formula (6), the alkyl group, cycloalkyl group, aryl group and aralkyl group as Ra are each independently substituted with an alkyl group, cycloalkyl group, aryl group and aralkyl group as Rb. may be substituted with the same groups as the groups described above as groups which may be substituted.

Specific examples of the alkyl group, cycloalkyl group, aryl group, and aralkyl group (these groups may be substituted with the above groups) for Ra include the same groups as the specific examples described above for Rb. mentioned.
Specific structures of particularly preferred compounds (DD) in the present invention include, for example, compounds disclosed in paragraph [0475] of US Patent Application Publication No. 2012/0135348A1.

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

Preferred examples of acid diffusion control agents are shown below.

When the composition contains an acid diffusion control agent, the content of the acid diffusion control agent is preferably 0.1 to 12% by mass, more preferably 0.2 to 10% by mass, based on the total solid content of the composition. , 0.3 to 8% by mass is more preferable.
When the composition contains an acid diffusion controller, the content of the acid diffusion controller is preferably 0.01 to 1.00 mmol, more preferably 0.02 to 0.30 mmol, per 1 g of the solid content of the composition. , 0.03 to 0.20 mmol are more preferred.

<Hydrophobic resin>
The composition of the invention may contain a hydrophobic resin. It should be noted that the hydrophobic resin is preferably a resin different from the resin A.
When the composition of the present invention contains a hydrophobic resin, it is easy to control the static and/or dynamic contact angle on the surface of the resist film (actinic ray-sensitive or radiation-sensitive film). This makes it possible to improve development characteristics, suppress outgassing, improve immersion liquid followability in immersion exposure, reduce immersion defects, and the like.
Hydrophobic resins are preferably designed to be unevenly distributed on the surface of the resist film. It does not have to contribute to mixing.

Hydrophobic resin, from the viewpoint of uneven distribution to the film surface layer, at least one selected from the group consisting of "fluorine atom", "silicon atom", and " _CH3 partial structure contained in the side chain portion of the resin" It is preferably a resin having repeating units with seeds.
When the hydrophobic resin contains fluorine atoms and/or silicon atoms, the fluorine atoms and/or silicon atoms in the hydrophobic resin may be contained in the main chain of the resin, or may be contained in side chains. may

When the hydrophobic resin contains a fluorine atom, the partial structure containing a fluorine atom is preferably a resin containing an alkyl group containing a fluorine atom, a cycloalkyl group containing a fluorine atom, or an aryl group containing a fluorine atom.

The hydrophobic resin preferably has at least one group selected from the group (x) to (z) below.
(x) an acid group (y) a group that decomposes under the action of an alkaline developer to increase its solubility in the alkaline developer (hereinafter also referred to as a polarity conversion group)
(z) a group that decomposes under the action of an acid

The acid group (x) includes a phenolic hydroxyl group, a carboxyl group, a fluorinated alcohol group, a sulfonic acid group, a sulfonamide group, a sulfonylimide group, an (alkylsulfonyl)(alkylcarbonyl)methylene group, an (alkylsulfonyl)(alkylcarbonyl ) imide group, bis(alkylcarbonyl)methylene group, bis(alkylcarbonyl)imide group, bis(alkylsulfonyl)methylene group, bis(alkylsulfonyl)imide group, tris(alkylcarbonyl)methylene group, and tris(alkylsulfonyl ) methylene group and the like.
The acid group is preferably a fluorinated alcohol group (preferably hexafluoroisopropanol), a sulfonimide group, or a bis(alkylcarbonyl)methylene group.

Examples of the group (y) that is decomposed by the action of an alkaline developer to increase the solubility in the alkaline developer include a lactone group, a carboxyester group (--COO--), an acid anhydride group (--CO--O--CO-- ), acid imide group (-NHCONH-), carboxythioester group (-COS-), carbonate group (-O-CO-O-), sulfate group (-OSO ₂ O-), and sulfonate group (--SO ₂ O--) and the like, preferably a lactone group or a carboxyester group (--COO--).
Repeating units containing these groups are, for example, repeating units in which these groups are directly bonded to the main chain of the resin, and examples thereof include repeating units of acrylic acid esters and methacrylic acid esters. These repeating units may be bonded to the main chain of the resin via a linking group. Alternatively, this repeating unit may be introduced at the end of the resin using a polymerization initiator or chain transfer agent having these groups during polymerization.
Examples of repeating units having a lactone group include repeating units similar to the repeating units having a lactone structure described above in the section of resin A.

When the hydrophobic resin has a repeating unit having a group (y) that decomposes under the action of an alkaline developer to increase the solubility in the alkaline developer, the content thereof is 1 to 100 mol % is preferred, 3 to 98 mol % is more preferred, and 5 to 95 mol % is even more preferred.

The repeating unit having a group (z) decomposable by the action of acid in the hydrophobic resin includes repeating units similar to the repeating unit having an acid-decomposable group exemplified for Resin A. A repeating unit having a group (z) decomposable under the action of an acid may have at least one of a fluorine atom and a silicon atom. When the hydrophobic resin has a repeating unit having a group (z) that decomposes under the action of an acid, the content thereof is preferably 1 to 80 mol%, preferably 10 to 80 mol%, based on the total repeating units in the hydrophobic resin. mol % is more preferred, and 15 to 60 mol % is even more preferred.
The hydrophobic resin may further have repeating units other than the repeating units described above.

When the hydrophobic resin has repeating units containing fluorine atoms, the content thereof is preferably 10 to 100 mol %, more preferably 30 to 100 mol %, based on the total repeating units in the hydrophobic resin. Further, when the hydrophobic resin has repeating units containing silicon atoms, the content thereof is preferably 10 to 100 mol %, more preferably 20 to 100 mol %, based on the total repeating units in the hydrophobic resin.

On the other hand, especially when the hydrophobic resin contains a CH ₃ partial structure in the side chain portion, it is also preferable that the hydrophobic resin does not substantially contain fluorine atoms and silicon atoms. Moreover, it is preferable that the hydrophobic resin is substantially composed only of repeating units composed only of atoms selected from carbon atoms, oxygen atoms, hydrogen atoms, nitrogen atoms, and sulfur atoms.

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

The total content of residual monomers and/or oligomer components contained in the hydrophobic resin is preferably 0.01 to 5% by mass, more preferably 0.01 to 3% by mass. Further, the dispersity (Mw/Mn) is preferably 1.0 to 5.00, more preferably 1.0 to 3.00.

As the hydrophobic resin, known resins can be appropriately selected and used either singly or as a mixture thereof. For example, 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 suitably used as the hydrophobic resin. Further, the repeating units disclosed in paragraphs [0177] to [0258] of US Patent Application Publication No. 2016/0237190A1 are also preferable as repeating units constituting the hydrophobic resin.

Preferred examples of monomers corresponding to repeating units constituting the hydrophobic resin are shown below.

Hydrophobic resin may be used individually by 1 type, and may use 2 or more types.
It is also preferable to use a mixture of two or more hydrophobic resins having different surface energies from the viewpoint of achieving both immersion liquid followability and development characteristics in immersion exposure.
The content of the hydrophobic resin in the composition is preferably 0.01 to 10% by mass, more preferably 0.03 to 8.0% by mass, more preferably 0.03 to 8.0% by mass, based on the total solid content in the composition of the present invention. 10 to 1.0% by mass is more preferable. When two or more types of hydrophobic resins are used, the total content is preferably within the range of the above preferred content.

<Solvent>
The composition of the invention may contain a solvent.
A known resist solvent can be appropriately used in the composition of the present invention. For example, paragraphs [0665]-[0670] of US Patent Application Publication No. 2016/0070167A1, paragraphs [0210]-[0235] of US Patent Application Publication No. 2015/0004544A1, US Patent Application Publication No. 2016/0237190A1 Known solvents disclosed in paragraphs [0424] to [0426] of the specification and paragraphs [0357] to [0366] of US Patent Application Publication No. 2016/0274458A1 can be suitably used.
Solvents that can be used in preparing the composition include, for example, alkylene glycol monoalkyl ether carboxylates, alkylene glycol monoalkyl ethers, alkyl lactate esters, alkyl alkoxypropionates, cyclic lactones (preferably having 4 to 10 carbon atoms), Organic solvents such as monoketone compounds which may have a ring (preferably having 4 to 10 carbon atoms), alkylene carbonates, alkyl alkoxyacetates, and alkyl pyruvates can be mentioned.

As the organic solvent, a mixed solvent in which a solvent having a hydroxyl group in its structure and a solvent having no hydroxyl group are mixed may be used.
As the solvent having a hydroxyl group and the solvent not having a hydroxyl group, the above-described exemplary compounds can be appropriately selected. ), propylene glycol monoethyl ether (PGEE), methyl 2-hydroxyisobutyrate, or ethyl lactate are more preferred. As the solvent having no hydroxyl group, alkylene glycol monoalkyl ether acetate, alkylalkoxypropionate, monoketone compound which may have a ring, cyclic lactone, or alkyl acetate are preferable. Propylene glycol monomethyl ether acetate (PGMEA), ethyl ethoxypropionate, 2-heptanone, γ-butyrolactone, cyclohexanone, cyclopentanone, or butyl acetate are more preferable, and propylene glycol monomethyl ether acetate, γ-butyrolactone, ethyl ethoxypropionate Pionate, cyclohexanone, cyclopentanone or 2-heptanone are more preferred. Propylene carbonate is also preferred as the solvent having no hydroxyl group.
The mixing ratio (mass ratio) of the solvent having a hydroxyl group and the solvent having no hydroxyl group is preferably 1/99 to 99/1, more preferably 10/90 to 90/10, and 20/80 to 60/40. More preferred. A mixed solvent containing 50% by mass or more of a solvent having no hydroxyl group is preferable from the viewpoint of coating uniformity.
Preferably, the solvent comprises propylene glycol monomethyl ether acetate. In this case, the solvent may be a single solvent of propylene glycol monomethyl ether acetate, or a mixed solvent of two or more kinds including propylene glycol monomethyl ether acetate.

The solid content concentration of the composition of the present invention is preferably 1.0 to 10% by mass, more preferably 2.0 to 5.7% by mass, even more preferably 2.0 to 5.3% by mass. That is, when the composition contains a solvent, the content of the solvent in the composition is preferably adjusted so as to satisfy the preferred range of solid content concentration. The solid content concentration is the mass percentage of the mass of other resist components excluding the solvent relative to the total mass of the composition.
By setting the solid content concentration in the composition to an appropriate range to give an appropriate viscosity, coating property or film forming property is improved, resist film (actinic ray sensitive or radiation sensitive) made of the composition of the present invention film) can be adjusted.

<Surfactant>
The composition of the invention may also contain a surfactant.
The surfactant is preferably 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). .

When the composition of the present invention contains a surfactant, when an exposure light source of 250 nm or less, particularly 220 nm or less is used, it is easy to obtain a pattern with good sensitivity and resolution, good adhesion, and few development defects.
Fluorinated and/or silicon-based surfactants include surfactants described in paragraph [0276] of US Patent Application Publication No. 2008/0248425.
Also, other surfactants than the fluorine-based and/or silicon-based surfactants described in paragraph [0280] of US Patent Application Publication No. 2008/0248425 may be used.

One type of surfactant may be used alone, or two or more types may be used.
When the composition of the present invention contains a surfactant, the content of the surfactant is preferably 0.0001 to 2% by mass, and 0.0005 to 1% by mass, based on the total solid content of the composition. more preferred.
One type of surfactant may be used alone, or two or more types may be used. When two or more surfactants are used, the total content is preferably within the range of the above preferred content.
On the other hand, if the content of the surfactant is 10 ppm by mass or more relative to the total solid content of the composition, the uneven surface distribution of the hydrophobic resin increases. As a result, the surface of the resist film can be made more hydrophobic, and the followability to water during immersion exposure is improved.

<Other additives>
The composition of the present invention further contains resins other than those described above, cross-linking agents, acid multipliers, dyes, plasticizers, photosensitizers, light absorbers, alkali-soluble resins, dissolution inhibitors, dissolution accelerators, and the like. may contain

<Preparation method>
The composition of the present invention is preferably used by dissolving the above components in a predetermined organic solvent (preferably the above mixed solvent), filtering the solution, and coating it on a predetermined support (substrate).
The pore size of the filter used for filtration is preferably 0.1 µm or less, more preferably 0.05 µm or less, and even more preferably 0.03 µm or less. When the composition has a high solid content concentration (for example, 25% by mass or more), the pore size of the filter used for filtration is preferably 3 μm or less, more preferably 0.5 μm or less, and even more preferably 0.3 μm or less. This filter is preferably a polytetrafluoroethylene, polyethylene or nylon filter. In filter filtration, for example, as disclosed in Japanese Patent Application Publication No. 2002-62667 (JP 2002-62667), cyclic filtration may be performed, and multiple types of filters are connected in series or in parallel. Filtration may be performed by connecting to Also, the composition may be filtered multiple times. Furthermore, before and after filtering, the composition may be subjected to a degassing treatment or the like.

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

[Pattern Forming Method, Resist Film]
The present invention also relates to a pattern forming method using the actinic ray-sensitive or radiation-sensitive resin composition. The pattern forming method of the present invention will be described below. The resist film (actinic ray-sensitive or radiation-sensitive film) of the present invention will also be explained together with the explanation of the pattern forming method.

The pattern forming method of the present invention comprises
(i) A step of forming a resist film (actinic ray-sensitive or radiation-sensitive film) on a support using the actinic ray-sensitive or radiation-sensitive resin composition described above (resist film forming step (film-forming step) ),
(ii) a step of exposing the resist film (irradiating actinic rays or radiation) (exposure step), and
(iii) a step of developing the exposed resist film using a developer (development step);
have

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

In the pattern forming method of the present invention, the above-described (i) resist film forming step (film forming step), (ii) exposing step, and (iii) developing step can be performed by generally known methods.

From the viewpoint of improving resolution, the thickness of the resist film is preferably 110 nm or less, more preferably 95 nm or less.
If necessary, a resist underlayer film (for example, SOG (Spin On Glass), SOC (Spin On Carbon), and antireflection film) may be formed between the resist film and the support. As a material constituting the resist underlayer film, a known organic or inorganic material can be appropriately used.
A protective film (top coat) may be formed on the resist film. A known material can be appropriately used as the protective film. For example, US2007/0178407, US2008/0085466, US2007/0275326, US2016/0299432, The composition for forming a protective film disclosed in US Patent Application Publication No. 2013/0244438 and International Patent Application Publication No. 2016/157988A can be preferably used. The protective film-forming composition preferably contains the acid diffusion control agent described above.
A protective film may be formed on the resist film containing the hydrophobic resin described above.

The support is not particularly limited, and a substrate generally used in the manufacturing process of semiconductors such as ICs, the manufacturing process of circuit boards such as liquid crystals or thermal heads, and the lithography process of other photofabrication is used. can. Specific examples of the support include inorganic substrates such as silicon, SiO ₂ , and SiN.

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

The wavelength of the light source used in the exposure process is not limited, but 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 preferred, and its wavelength is preferably 250 nm or less, more preferably 220 nm or less, and still more preferably 1 to 200 nm. Specifically, KrF excimer laser (248 nm), ArF excimer laser (193 nm), F2 excimer laser ₍ 157 nm), X-ray, EUV (13 nm), electron beam, etc. are preferable, and KrF excimer laser, ArF excimer laser , EUV, or electron beam are more preferred.

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

As the alkali developer, quaternary ammonium salts such as tetramethylammonium hydroxide are usually used, but in addition to this, inorganic alkalis, primary to tertiary amines, alcohol amines, and alkaline aqueous solutions such as cyclic amines are also used. is also available.
Furthermore, the alkaline developer may contain an appropriate amount of alcohols and/or surfactants. The alkali concentration of the alkali developer is usually 0.1 to 20 mass %. The pH of the alkaline developer is usually 10-15.
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 appropriately adjusted according to the pattern to be formed.

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

Ketone solvents include, for example, 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, methylethylketone, methylisobutylketone, acetylacetone, acetonylacetone, ionone, diacetonyl alcohol, acetylcarbinol, acetophenone, methylnaphthylketone, isophorone, and propylene carbonate.

Examples of ester solvents include methyl acetate, butyl acetate, ethyl acetate, isopropyl acetate, pentyl acetate, isopentyl acetate, amyl acetate, propylene glycol monomethyl ether acetate, ethylene glycol monoethyl ether acetate, diethylene glycol monobutyl ether acetate, and diethylene glycol monoethyl. ether acetate, ethyl-3-ethoxypropionate, 3-methoxybutyl acetate, 3-methyl-3-methoxybutyl acetate, methyl formate, ethyl formate, butyl formate, propyl formate, ethyl lactate, butyl lactate, propyl lactate, butane Butyl acid, methyl 2-hydroxyisobutyrate, isoamyl acetate, isobutyl isobutyrate, and butyl propionate.

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

A plurality of the above solvents may be mixed, or may be mixed with a solvent other than the above or water. The water content of the developer as a whole is preferably less than 50% by mass, more preferably less than 20% by mass, even more preferably less than 10% by mass, and particularly preferably substantially free of water.
The content of the organic solvent in the organic developer is preferably 50 to 100% by mass, more preferably 80 to 100% by mass, still more preferably 90 to 100% by mass, and 95 to 100% by mass, relative to the total amount of the developer. % is particularly preferred.

The developer may contain an appropriate amount of a known surfactant as required.

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

The organic developer may contain an acid diffusion control agent.

Examples of the developing method include a method of immersing the substrate in a tank filled with a developer for a certain period of time (dip method), a method of raising the developer on the surface of the substrate by surface tension and resting the substrate for a certain period of time (paddle method), and a substrate. A method of spraying the developer onto the surface (spray method), and a method of continuously ejecting the developer while scanning the developer ejection nozzle at a constant speed on the substrate rotating at a constant speed (dynamic dispensing method). mentioned.

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

(iii) A step of washing with a rinse solution (rinsing step) is preferably included after the developing step.

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

The rinsing solution used in the rinsing step after the developing step using the developing solution containing an organic solvent is not particularly limited as long as it does not dissolve the pattern, and a common solution containing an organic solvent can be used. As the rinse liquid, a rinse liquid containing at least one organic solvent selected from the group consisting of hydrocarbon solvents, ketone solvents, ester solvents, alcohol solvents, amide solvents, and ether solvents is used. preferably.
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 for the developer containing an organic solvent.
As the rinse solution used in the rinse step in this case, a rinse solution containing a monohydric alcohol is more preferable.

Linear, branched, or cyclic monohydric alcohols may be used as monohydric alcohols used in the rinsing step. Specifically, 1-butanol, 2-butanol, 3-methyl-1-butanol, tert-butyl alcohol, 1-pentanol, 2-pentanol, 1-hexanol, 4-methyl-2-pentanol, 1 -heptanol, 1-octanol, 2-hexanol, cyclopentanol, 2-heptanol, 2-octanol, 3-hexanol, 3-heptanol, 3-octanol, 4-octanol, and methylisobutylcarbinol.
It is also preferred that the monohydric alcohol has 5 or more carbon atoms, examples of which are 1-hexanol, 2-hexanol, 4-methyl-2-pentanol, 1-pentanol, 3-methyl-1-butanol. , and methyl isobutyl carbinol.

A plurality of each component may be mixed, or may be used by mixing with an organic solvent other than the above.
The water content in the rinse solution used in the rinse step after the development step using the developer containing an organic solvent is preferably 10% by mass or less, more preferably 5% by mass or less, and even more preferably 3% by mass or less. If the water content is 10% by mass or less, good developing properties can be obtained.
A rinse solution after a development step using a developer containing an organic solvent may contain an appropriate amount of a surfactant.

In the rinsing step, the developed substrate is washed with a rinsing liquid. The method of the cleaning treatment is not particularly limited, but for example, a method of continuously discharging the rinse solution onto the substrate rotating at a constant speed (rotation coating method), or a method of immersing the substrate in a bath filled with the rinse solution for a certain period of time. method (dip method), a method in which the substrate surface is heaped up with the rinse liquid by surface tension and remains stationary for a certain period of time (paddle method), or a method in which the rinse liquid is sprayed onto the substrate surface (spray method). It is also preferable to rotate the substrate at a rotation speed of 2,000 to 4,000 rpm after washing to remove the rinsing liquid from the substrate. It is also preferable to include a heating step (Post Bake) after the rinsing step. This heating process removes the developer and rinse remaining between the patterns and inside the patterns. In the heating step after the rinsing step, the heating temperature is usually 40 to 160°C, preferably 70 to 95°C, and the heating time is usually 10 seconds to 3 minutes, preferably 30 to 90 seconds.

The actinic ray-sensitive or radiation-sensitive resin composition of the present invention, and various materials used in the pattern forming method of the present invention (e.g., resist solvent, developer, rinse, antireflection film-forming composition, or , topcoat-forming composition, etc.) preferably does not contain impurities such as metal components, isomers, and residual monomers. The content of these impurities contained in the above various materials is preferably 1 mass ppm or less, more preferably 100 mass ppt or less, still more preferably 10 mass ppt or less, and substantially free (measurement device detection below the limit) is particularly preferred.

As a method for removing impurities such as metals from the above various materials, for example, filtration using a filter can be mentioned. The pore size of the filter is preferably 10 nm or less, more preferably 5 nm or less, and even more preferably 3 nm or less. As the material of the filter, a filter made of polytetrafluoroethylene, polyethylene, or nylon is preferable. A filter pre-washed with an organic solvent may be used. In the filter filtration step, multiple types of filters may be connected in series or in parallel for use. When multiple types of filters are used, filters with different pore sizes and/or materials may be used in combination. Further, various materials may be filtered multiple times, and the process of filtering multiple times may be a circulation filtration process. As the filter, a filter with reduced extractables as disclosed in Japanese Patent Application Publication No. 2016-201426 (JP 2016-201426) is preferable.
In addition to filter filtration, an adsorbent may be used to remove impurities, or filter filtration and an adsorbent may be used in combination. As the adsorbent, a known adsorbent can be used, and for example, an inorganic adsorbent such as silica gel or zeolite, or an organic adsorbent such as activated carbon can be used. Examples of metal adsorbents include materials disclosed in Japanese Patent Application Publication No. 2016-206500 (JP 2016-206500).
In addition, as a method for reducing impurities such as metals contained in the various materials, selecting raw materials with a low metal content as raw materials constituting various materials, performing filter filtration on raw materials constituting various materials, Alternatively, distillation may be performed under conditions in which contamination is suppressed as much as possible by, for example, lining the inside of the apparatus with Teflon (registered trademark). It is also preferable to apply glass lining to all processes of manufacturing equipment for synthesizing various materials (binders, PAG, etc.) of resist components in order to reduce metals to the ppt order. Preferable conditions for filter filtration for raw materials constituting various materials are the same as those described above.

In order to prevent contamination of impurities, the above various materials are described in US Patent Application Publication No. 2015/0227049, Japanese Patent Application Publication No. 2015-123351 (JP 2015-123351), and Japan It is preferably stored in a container described in Japanese Patent Application Publication No. 2017-13804 (Japanese Patent Application Laid-Open No. 2017-13804).

A method for improving surface roughness of the pattern may 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, there is a method of treating the pattern with hydrogen-containing gas plasma disclosed in US Patent Application Publication No. 2015/0104957. In addition, Japanese Patent Application Publication No. 2004-235468 (Japanese Patent Application Publication No. 2004-235468), US Patent Application Publication No. 2010/0020297, and Proc. of SPIE Vol. 8328 83280N-1 “EUV Resist Curing Technique for LWR Reduction and Etch Selectivity Enhancement” may be applied.
In addition, the pattern formed by the above method is disclosed in, for example, Japanese Patent Application Publication No. 1991-270227 (JP-A-3-270227) and US Patent Application Publication No. 2013/0209941. It can be used as a core for the spacer process.

[Method for producing electronic device]
The present invention also relates to a method of manufacturing an electronic device, including the pattern forming method described above. The electronic device manufactured by the method for manufacturing an electronic device of the present invention is suitable for electrical and electronic equipment (e.g., home appliances, OA (Office Automation)-related equipment, media-related equipment, optical equipment, communication equipment, etc.). to be installed.

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

[Components of the composition]
Components contained in the actinic ray-sensitive or radiation-sensitive resin composition (hereinafter also referred to as "composition") used in Examples or Comparative Examples are shown below.

<Acid-decomposable resin (resin A)>
The acid-decomposable resin (resin A) used for producing the composition is shown below.
The number attached to the repeating unit of each resin indicates the mole fraction of each repeating unit. The weight average molecular weight (Mw) and the degree of dispersion (Mw/Mn) of each resin are also shown.

<Photoacid generator>
(PAG-1)
PAG-1 was synthesized according to the scheme below.

A reaction solution was prepared by mixing compound (1) (5.0 g), sodium hydrogen sulfite (2.2 g), methanol (60 mL) and water (6 mL), and stirred at room temperature for 12 hours. The solvent was distilled off from the reaction solution to obtain compound (2).
The entire amount of compound (2) thus obtained was suspended in a mixture of water (60 mL) and chloroform (60 mL) to prepare a reaction solution. Further, triphenylsulfonium bromide (4.9 g) was added to the reaction solution, and the mixture was stirred at room temperature for 1 hour. The reaction solution was transferred to a separatory funnel and the organic phase was washed with water (20 mL) three times. The organic phase was concentrated with an evaporator to obtain compound (3) (6.0 g).
After dissolving the obtained compound (3) whole quantity in chloroform (60 mL), triethylamine (1.1 g) was added to prepare a reaction solution. Cyclohexanecarbonyl chloride (2.2 g) was further added to the reaction solution, and the mixture was stirred at room temperature for 12 hours. After adding water (60 mL) to the reaction solution, it was transferred to a separating funnel and the organic phase was washed with water (20 mL) three times. The organic phase was concentrated by an evaporator to obtain PAG-1 (4.7 g).

(PAG-2 to PAG-20)
PAG-2 to PAG-20 were synthesized with reference to the synthesis method of PAG-1.

The photoacid generators used in the preparation of the composition are shown below.
Among the photoacid generators below, PAG-1 to PAG-20 correspond to specific photoacid generators.

The pka of acids generated from PAG-1 to PAG-20 are as follows.

<Acid diffusion control agent>
The acid diffusion controllers used in preparing the composition are shown below.

<Hydrophobic resin>
The hydrophobic resins used to prepare the composition are shown below.
The number attached to the repeating unit of each hydrophobic resin indicates the molar fraction of each repeating unit. The weight average molecular weight (Mw) and the degree of dispersion (Mw/Mn) of each resin are also shown.

<Solvent>
The solvents used in preparing the compositions are shown below.
SL-1: Propylene glycol monomethyl ether acetate (PGMEA: 1-methoxy-2-acetoxypropane)
SL-2: Propylene glycol monomethyl ether (PGME: 1-methoxy-2-propanol)
SL-3: γ-butyrolactone

[Preparation of composition]
A solution was prepared by dissolving each component shown in the latter table in a solvent so that the formulation shown in the latter table 2 was satisfied and the solid content concentration was 3.8% by mass.
Then, the obtained solution was filtered through a polyethylene filter having a pore size of 0.1 μm to prepare a composition (actinic ray-sensitive or radiation-sensitive resin composition).

〔evaluation〕
<Formation of pattern>
An organic antireflection film-forming composition ARC29SR (manufactured by Nissan Chemical Industries, Ltd.) was applied onto a silicon wafer and baked at 205° C. for 60 seconds to form an antireflection film with a thickness of 95 nm. The composition was applied onto the obtained antireflection film and baked (PB: Prebake) at 100° C. for 60 seconds to form a resist film with a thickness of 85 nm. Using an ArF excimer laser immersion scanner (manufactured by ASML; XT1700i, NA 1.20, C-Quad, outer sigma 0.900, inner sigma 0.812, XY deflection), the resulting wafer was scanned with a 1:1 line width of 44 nm. It was exposed through a 6% halftone mask with a 1 line and space pattern. Ultrapure water was used as the immersion liquid. Then, it was heated at 105° C. for 60 seconds (PEB: Post Exposure Bake). Then, it was developed by puddling with an organic developer (butyl acetate) for 30 seconds, and rinsed with a rinsing liquid (methyl isobutyl carbinol (MIBC)) for 30 seconds. Subsequently, the wafer was rotated at a rotational speed of 4000 rpm for 30 seconds to form a 1:1 line-and-space pattern with a line width of 44 nm.

<LWR performance>
The resulting 1:1 line-and-space pattern with a line width of 44 nm was observed from above the pattern with a length-measuring scanning electron microscope (SEM (Hitachi Ltd. S-8840)).
The line width was measured at 50 points in a range of 2 μm along the longitudinal edge of the line pattern, the standard deviation of the measurement variation was obtained, 3σ (nm) was calculated, and this value was defined as LWR (nm). The obtained LWR (nm) was classified according to the following criteria, and the LWR performance was evaluated.
A smaller LWR (nm) value indicates better LWR performance.

"4": LWR<3.3 nm
“3”: 3.3 nm≦LWR<3.5 nm
“2”: 3.5 nm≦LWR<3.7 nm
“1”: 3.7 nm≦LWR

〔result〕
The formulations of the compositions and the results of evaluations performed using those compositions are shown in the table below.
The number written under each component name in the column of "solid content" indicates the amount ("g" or "mmol") of each component added. To each composition, 10 g of the resin, 3 mmol of the photoacid generator, 1 mmol of the acid diffusion controller, and 0.05 g of the hydrophobic resin were added. Solvents were added at the mass ratio shown in the table.
The column "Rf" in the table shows the structure of the group corresponding to Rf when the acid generated by the specific photoacid generator in each composition is applied to general formula (I).
The column of "X" in the table indicates whether the group corresponding to X is "-COO-" when the acid generated by the specific photoacid generator in each composition is applied to the general formula (I). or When the above requirements are met, it is described as A, and when it is not satisfied, it is described as B.

From the results shown in the table, it was confirmed that the composition of the present invention can provide patterns with excellent LWR performance.
Further, when the group corresponding to Rf of the acid generated by the specific photoacid generator was a trifluoromethyl group, it was confirmed that the LWR of the obtained pattern was superior (comparison with Examples 15 and 16, etc.). ).
Further, when the group corresponding to X of the acid generated by the specific photoacid generator is -COO-, it was confirmed that the LWR of the resulting pattern is superior (comparison with Examples 2 and 7, etc.). .

Claims (9)

An actinic ray- or radiation-sensitive resin composition comprising a compound that generates an acid represented by formula (I) upon exposure to actinic rays or radiation, and a resin.

In general formula (I), Rf represents a fluoroalkyl group.
t represents 0 or 1 ;
R ¹ and R ² each independently represent an organic group, and R ¹ represents an organic group having a cyclic group . 2. The actinic ray-sensitive or radiation-sensitive resin composition according to claim 1, wherein Rf represents a trifluoromethyl group. The actinic ray-sensitive or radiation-sensitive resin composition according to claim 1 or 2 , wherein ^R1 has an alicyclic group. 4. The actinic ray-sensitive or radiation-sensitive resin composition according to any one of claims 1 to 3 , wherein the pKa of the acid represented by formula (I) is -2.00 or more. The actinic ray-sensitive or radiation-sensitive resin composition according to any one of claims 1 to 4 , wherein R ¹ does not have a fluorine atom. 6. The actinic ray-sensitive or radiation-sensitive resin composition according to any one of claims 1 to 5 , wherein ^R2 does not have a fluorine atom. A resist film formed using the actinic ray-sensitive or radiation-sensitive resin composition according to any one of claims 1 to 6 . forming a resist film on a support using the actinic ray-sensitive or radiation-sensitive resin composition according to any one of claims 1 to 7 ;
exposing the resist film;
and developing the exposed resist film using a developer. A method for manufacturing an electronic device, comprising the pattern forming method according to claim 8 .