JPWO2019167481A1 - Sensitive light-sensitive or radiation-sensitive resin composition, sensitive light-sensitive or radiation-sensitive film, pattern forming method, and method for manufacturing an electronic device. - Google Patents

Abstract

It has excellent LWR performance and rectangularity of the cross-sectional shape of the pattern, and has a large common DOF when forming a punched pattern (for example, an isolated hole pattern) and a remaining pattern (for example, an isolated dot pattern). Provided are a sex resin composition, and a method for producing an actinic or radiation-sensitive film, a pattern forming method, and an electronic device using the same. The active light-sensitive or radiation-sensitive resin composition is described in (A) a resin whose polarity is increased by the action of an acid and its solubility in a developing solution is changed, (B) a photoacid generator, and (C) the specification. The onion salt having an amide structure is contained in the counter cation represented by the general formula (1), and the content of the onium salt (C) is smaller than the content of the compound (B) in terms of molars.

Description

The present invention relates to a sensitive light-sensitive or radiation-sensitive resin composition, a sensitive light-sensitive or radiation-sensitive film, a pattern forming method, and a method for manufacturing an electronic device.

Since the resist for KrF excimer laser (248 nm), a pattern forming method using chemical amplification has been used to compensate for the decrease in sensitivity due to light absorption. For example, in the positive chemical amplification method, first, the photoacid generator contained in the exposed portion 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 group contained in the photosensitive composition is changed to the alkali-soluble group by the catalytic action of the generated acid. Then, for example, development is carried out using an alkaline solution. As a result, the exposed portion is removed to obtain a desired pattern.
In the above method, various alkaline developers have been proposed. For example, as this alkaline developer, a 2.38 mass% TMAH (tetramethylammonium hydroxide aqueous solution) aqueous alkaline developer is generally used.

Due to the miniaturization of semiconductor devices, the wavelength of the exposure light source has been shortened and the numerical aperture (NA) of the projection lens has been increased. Currently, an exposure machine using an ArF excimer laser having a wavelength of 193 nm as a light source has been developed. ing. As a technique for further enhancing the resolving power, a method (that is, an immersion method) of filling a liquid having a high refractive index (hereinafter, also referred to as "immersion liquid") between the projection lens and the sample has been proposed.

For example, Patent Document 1 describes a resist composition in which an acid is generated by exposure and the solubility in a developing solution is changed by the action of the acid, and the substrate component whose solubility in a developing solution is changed by the action of the acid. A resist composition containing a nitrogen-containing compound having a boiling point of 50 to 200 ° C. and a pKa of a conjugate acid of 0 to 7 and a photobase inactivating agent is described.

Patent Document 2 describes a polymer compound and an acid generator having a repeating unit in which a hydroxy group is substituted with an acid unstable group, or a repeating unit in which a hydroxy group is substituted with an acid unstable group and a repeating unit in which an acid is generated by exposure. A resist composition containing a polymer compound having a unit, a sulfonium salt or iodonium salt of fluoroalkylsulfoneamide, and an organic solvent is applied onto a substrate, and after heat treatment, the resist film is exposed to high energy rays and heat treatment is performed. A pattern forming method is described later in which an unexposed portion is dissolved using a developing solution using an organic solvent to obtain a negative pattern in which the exposed portion is not dissolved.

Japanese Unexamined Patent Publication No. 2014-2323 Japanese Unexamined Patent Publication No. 2013-145255

When exposure is performed using a resist composition, improvement of the process margin is required in order to improve the yield.
In order to improve the process margin, it is important that the depth of focus (DOF, depth of focus) is large, and a higher degree of integration is required. In particular, the focus of the isolated hole pattern and the isolated dot pattern. It is required to increase the depth (common DOC) (improve the common DOC performance). Further, in addition to the improvement of the common DOF performance, it is required that the LWR (Line Width Roughness) performance (the LWR is small) and the cross-sectional shape of the pattern are also excellent (the rectangular cross-sectional shape of the pattern is excellent).
According to the studies by the present inventors, it has been found that the conventional actinic light-sensitive or radiation-sensitive resin compositions cannot sufficiently satisfy all of the above performances.
Therefore, the problem to be solved by the present invention is excellent in LWR performance and rectangularity of the cross-sectional shape of the pattern, and at the time of forming a punched pattern (for example, an isolated hole pattern) and a remaining pattern (for example, an isolated dot pattern). To provide a sensitive light-sensitive or radiation-sensitive resin composition having a large common DOF in the above, and a method for producing a sensitive light-sensitive or radiation-sensitive film, a pattern forming method, and an electronic device using the same. is there.

The present inventors have diligently studied and found that the above-mentioned problems can be solved by using an onium salt having an amide structure (onium salt (C)) in a counter cation having a specific structure.
The onium salt (C) used in the present invention has an amide structure and has a weaker basicity than the basic compounds (typically amines) usually used in the resist composition, and thus is exposed. In the part, it is difficult to inhibit the action of the acid generated from the photoacid generator, and in the unexposed part, it sufficiently functions as an acid quencher (trap agent). It is considered that this makes it possible to improve the LWR performance.
Further, the onium salt (C) used in the present invention exhibits low volatility due to having a salt structure, and can suppress volatilization from the film surface that occurs during film formation of a sensitive light-sensitive or radiation-sensitive film. In particular, the presence of the onium salt (C) as a quencher in the upper part of the pattern makes it possible to obtain a desired pattern shape, so that the rectangularity of the cross-sectional shape of the pattern and the LWR performance can be improved. it is conceivable that.
Further, it is considered that the onium salt (C) could improve the common DOF performance probably because it has an appropriate diffusivity in addition to the above-mentioned characteristics.
The present inventors have found that the above problems can be solved by the following configuration.

[1]
(A) A resin whose polarity increases due to the action of acid and its solubility in a developing solution changes.
(B) Compounds that generate acid by irradiation with active light or radiation,
(C) Onium salt having an amide structure in the counter cation,
A sensitive light-sensitive or radiation-sensitive resin composition containing
The onium salt (C) is represented by the following general formula (1).
A sensitive light-sensitive or radiation-sensitive resin composition in which the content of the onium salt (C) in the sensitive light-sensitive or radiation-sensitive resin composition is smaller than the content of the compound (B) in terms of molars.

In the general formula (1), X ₁ represents a sulfur atom, an iodine atom, or a nitrogen atom, Q ₁ represents a group having an amide structure, and Q ₂ represents an alkyl group, a cycloalkyl group, or an aryl group. However, at least one of Q ₁ and k Q ₂ represents an alkyl group or a cycloalkyl group. When X ₁ represents a sulfur atom, k = 2, when X ₁ represents an iodine atom, k = 1, and when X ₁ represents a nitrogen atom, k = 3. Y ₁ represents an organic pair anion. At least one of Q ₁ and k Q ₂ may be coupled to each other to form a ring structure. If k is 2 or 3, it may form at least two Q ₂ is bonded to each other to form a ring structure.
[2]
The actinic or radiation-sensitive resin composition according to [1], wherein the onium salt (C) does not have a structure in which an aromatic group is directly linked to a nitrogen atom having an amide structure.
[3]
In the general formula (1), X ₁ represents a sulfur atom, and sensitive or radiation according to two Q ₂ 'represent each independently an alkyl group or a cycloalkyl group [1] or [2] Sex resin composition.
However, Q ₁ and may be bonded to form a ring structure and at least one of the two Q _2. Also, two Q ₂ is may be bonded to form a ring structure.
[4]
The actinic light-sensitive or radiation-sensitive resin composition according to any one of [1] to [3], wherein the onium salt (C) is represented by the following general formula (2).

In the general formula (2), Q ₃ and Q ₄ independently represent an alkyl group or a cycloalkyl group, L ₁ represents an alkylene group or a cycloalkylene group, and Q ₅ and Q ₆ independently represent a hydrogen atom and an alkyl, respectively. Represents a group, cycloalkyl group, alkenyl group, cycloalkenyl group, alkynyl group, cycloalkynyl group, aryl group, or heteroaryl group. Q ₃ to Q at least two of ₆ and L ₁ may be bonded to form a ring structure. Y ₂ is an organic pair anion.
[5]
The actinic cheilitis or radiation-sensitive resin composition according to any one of [1] to [4], wherein the molecular weight of the cation portion of the onium salt (C) is 100 or more and 500 or less.
[6]
The actinic cheilitis or radiation-sensitive resin composition according to any one of [1] to [5], wherein the molecular weight of the cation portion of the onium salt (C) is 120 or more and 350 or less.
[7]
Any of [1] to [6], wherein the content of the onium salt (C) in the actinic light-sensitive or radiation-sensitive resin composition is 50% or less of the content of the compound (B) in terms of molars. The sensitive light-sensitive or radiation-sensitive resin composition according to item 1.
[8]
The sensitive light beam according to any one of [1] to [7], which further contains (D) a hydrophobic resin different from the resin (A) having at least one of a fluorine atom and a silicon atom. Sexual or radiation sensitive resin composition.
[9]
The actinic light-sensitive or radiation-sensitive resin composition according to [8], wherein the hydrophobic resin (D) is a fluorine-containing (meth) acrylate-based resin.
[10]
The content of the hydrophobic resin (D) in the sensitive light-sensitive or radiation-sensitive resin composition is 1 to 10% by mass based on the total solid content of the sensitive light-sensitive or radiation-sensitive resin composition. The actinic or radiation-sensitive resin composition according to [8] or [9].
[11]
A sensitive light-sensitive or radiation-sensitive film formed by the sensitive light-sensitive or radiation-sensitive resin composition according to any one of [1] to [10].
[12]
A step of forming a sensitive light-sensitive or radiation-sensitive film by the sensitive light-sensitive or radiation-sensitive resin composition according to any one of [1] to [10].
The step of irradiating the above-mentioned sensitive light-sensitive or radiation-sensitive film with active light or radiation, and
A pattern forming method comprising a step of developing a sensitive light-sensitive or radiation-sensitive film irradiated with the active light beam or radiation using a developing solution.
[13]
A method for manufacturing an electronic device, including the pattern forming method according to [12].

According to the present invention, the LWR performance and the rectangularity of the cross-sectional shape of the pattern are excellent, and the feeling of a large common DOF when forming a punched pattern (for example, an isolated hole pattern) and a remaining pattern (for example, an isolated dot pattern). It is possible to provide an active light-sensitive or radiation-sensitive resin composition, and a method for producing an active light-sensitive or radiation-sensitive film, a pattern forming method, and an electronic device using the same.

Hereinafter, the present invention will be described in detail.
The description of the constituent elements described below may be based on a typical embodiment of the present invention, but the present invention is not limited to such an embodiment.
Regarding the notation of a group (atomic group) in the present specification, the notation that does not describe substitution or non-substitution includes those having no substituent as well as those having a substituent. For example, the "alkyl group" includes not only an alkyl group having no substituent (unsubstituted alkyl group) but also an alkyl group having a substituent (substituted alkyl group). Further, the "organic group" in the present specification means a group containing at least one carbon atom.
As used herein, the term "active light" or "radiation" refers to, for example, the emission line spectrum of a mercury lamp, far ultraviolet rays typified by an excimer laser, extreme ultraviolet rays (EUV: Extreme Ultraviolet), X-rays, and electron beams (EB:). It means Electron Beam) and the like. As used herein, "light" means active light or radiation.
Unless otherwise specified, the term "exposure" as used herein refers to not only exposure to the emission line spectrum of a mercury lamp, far ultraviolet rays represented by excimer lasers, extreme ultraviolet rays, X-rays, EUV, etc., but also electron beams and ions. It also includes drawing with particle beams such as beams.
In the present specification, "~" is used to mean that the numerical values described before and after it are included as the lower limit value and the upper limit value.

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

[Actinic cheilitis or radiation-sensitive resin composition]
The actinic or radiation-sensitive resin composition of the present invention (hereinafter, also referred to as “composition of the present invention”) will be described.
The composition of the present invention comprises (A) a resin whose polarity is increased by the action of an acid and its solubility in a developing solution is changed, (B) a compound that generates an acid by irradiation with active light or radiation, and (C) a counter cation. It contains an onium salt having an amide structure.

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

<Resin (A)>
The sensitive light-sensitive or radiation-sensitive resin composition of the present invention is also referred to as a resin (also referred to as "acid-degradable resin" or "resin (A)") whose polarity is increased by the action of an acid and its solubility in a developing solution is changed. ) Is contained.
The resin (A) preferably has a group (hereinafter, also referred to as "acid-decomposable group") that is decomposed by the action of an acid and whose polarity is increased.
The resin (A) is preferably a resin whose polarity is increased by the action of an acid and whose solubility in an alkaline developer is increased, and whose solubility in an organic developer is decreased.
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 is formed. A mold pattern is preferably formed.

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

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

The acid-degradable group preferably has a structure in which a polar group is protected by a group (leaving group) that is decomposed and eliminated by the action of an acid.
The polar groups include carboxyl 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, tris (alkylsulfonyl) methylene group, etc. (A group that dissociates in a 2.38 mass% tetramethylammonium hydroxide aqueous solution), an alcoholic hydroxyl group, and the like.

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

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

A preferred group as an acid-degradable group is a group in which the hydrogen atom of these groups is replaced with a group (leaving group) that is eliminated by the action of an acid.
Examples of the group (leaving group) desorbed by the action of acid include -C (R ₃₆ ) (R ₃₇ ) (R ₃₈ ), -C (R ₃₆ ) (R ₃₇ ) (OR ₃₉ ), and-. C (R ₀₁ ) (R ₀₂ ) (OR ₃₉ ) and the like can be mentioned.
In the formula, R _{36 to} R ₃₉ each independently represent an alkyl group, a cycloalkyl group, an aryl group, an aralkyl group or an alkenyl group. R ₃₆ and R ₃₇ may be combined 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, for example, methyl group, ethyl group, propyl group, n-butyl group, sec-butyl group and hexyl. Groups, octyl groups and the like can be mentioned.
The cycloalkyl groups of R _{36 to} R ₃₉ , R ₀₁ and R ₀₂ may be monocyclic or polycyclic. As the monocyclic type, a cycloalkyl group having 3 to 8 carbon atoms is preferable, and examples thereof include a cyclopropyl group, a cyclobutyl group, a cyclopentyl group, a cyclohexyl group, and a cyclooctyl group. The polycyclic type is preferably a cycloalkyl group having 6 to 20 carbon atoms, for example, an adamantyl group, a norbornyl group, an isobornyl group, a camphanyl group, a dicyclopentyl group, an α-pinel group, a tricyclodecanyl group, or a tetracyclododecyl. Groups, androstanyl groups and the like can be mentioned. In addition, at least one carbon atom in the cycloalkyl group may be substituted with a hetero atom such as an oxygen atom.
The aryl group of R _{36 to} R ₃₉ , R ₀₁ and R ₀₂ is preferably an aryl group having 6 to 10 carbon atoms, and examples thereof include a phenyl group, a naphthyl group and an anthryl group.
The aralkyl group of R _{36 to} R ₃₉ , R ₀₁ and R ₀₂ is preferably an aralkyl group having 7 to 12 carbon atoms, and examples thereof include a benzyl group, a phenethyl group and a naphthylmethyl group.
The alkenyl group of R _{36 to} R ₃₉ , R ₀₁ and R ₀₂ is preferably an alkenyl group having 2 to 8 carbon atoms, and examples thereof include a vinyl group, an allyl group, a butenyl group, and a cyclohexenyl group.
The ring formed by bonding R ₃₆ and R ₃₇ to each other is preferably a cycloalkyl group (monocyclic or polycyclic). As the cycloalkyl group, a monocyclic cycloalkyl group such as a cyclopentyl group and a cyclohexyl group, or a polycyclic cycloalkyl group such as a norbornyl group, a tetracyclodecanyl group, a tetracyclododecanyl group, and an adamantyl group is preferable. ..

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

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

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

Examples of the divalent linking group of 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 single bond or -COO-Rt-. As Rt, a chain alkylene group having 1 to 5 carbon atoms is preferable, and −CH ₂ −, − (CH ₂ ) ₂ −, or − (CH ₂ ) ₃ − is more preferable. More preferably, T is a single bond.

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 a methyl group, an ethyl group, a propyl group, a hydroxymethyl group and a trifluoromethyl group. The alkyl group of Xa ₁ is preferably a methyl group.

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

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

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

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

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

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

The content of the repeating unit having an acid-degradable group contained in the resin (A) (the total of a plurality of repeating units having an acid-degradable group) is determined with respect to all the repeating units of the resin (A). 10 to 90 mol% is preferable, 20 to 80 mol% is more preferable, and 30 to 70 mol% is further preferable.

The 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.

As the lactone structure or sultone structure, any one having a lactone structure or a sultone structure can be used, but a 5-7-membered ring lactone structure or a 5-7-membered ring sultone structure is preferable, and 5-7 A bicyclo structure or a spiro structure formed on a member ring lactone structure and another ring structure is condensed, or a bicyclo structure or a spiro structure is formed on a 5 to 7 member ring sultone structure. Is more preferable. It has a lactone structure represented by any of the following general formulas (LC1-1) to (LC1-21) or a sultone structure represented by any of the following general formulas (SL1-1) to (SL1-3). It is more preferred to have a repeating unit. Further, the lactone structure or the sultone structure may be directly bonded to the main chain. Preferred structures are (LC1-1), (LC1-4), (LC1-5), (LC1-8), (LC1-16), (LC1-21), (SL1-1).

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

The repeating unit having a lactone structure or a sultone structure is preferably a repeating unit represented by the following general formula (III).

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−, represents an integer of 0 to 5, is preferably 0 or 1, and more preferably 0. When n is 0, −R ₀ −Z− does not exist and a single bond is formed.
R ₀ represents an alkylene group, a cycloalkylene group, or a combination thereof. When there are a plurality of R ₀ , each independently represents an alkylene group, a cycloalkylene group, or a combination thereof.
Z represents a single bond, an ether bond, an ester bond, an amide bond, a urethane bond or a urea bond. When there are a plurality of Z, each of them independently represents a single bond, an ether bond, an ester bond, an amide bond, a urethane bond or a urea bond.
R ₈ represents a monovalent organic group having a lactone structure or a sultone structure.
R ₇ represents a hydrogen atom, a halogen atom or a monovalent organic group (preferably a methyl group).

The alkylene group or cycloalkylene group of R ₀ may have a substituent.
Z is preferably an ether bond or an ester bond, and more preferably an ester bond.

Specific examples of the monomer corresponding to the repeating unit represented by the general formula (III) and the specific example of the monomer corresponding to the repeating unit represented by the general formula (A-1) will be given below. It is not limited to these specific examples. The following specific examples, which _R ^{A 1} in the general formula (III)) in _{R 7} and formula (A-1) is equivalent to the case is a methyl group, _{R 7} and _R ^{A 1} represents a hydrogen atom, a halogen It can be optionally substituted with an atom or a monovalent organic group.

In addition to the above-mentioned monomers, the following monomers are also preferably used as raw materials for the resin (A).

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

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

The 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 paragraphs <0370> to <0414> of US Patent Application Publication No. 2016/0070167A1. It is also preferable to have the repeating unit described in 1.

The resin (A) may contain a repeating unit having at least one selected from the group consisting of a lactone structure, a sultone structure, and a carbonate structure, or may contain two or more of them in combination.

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

The resin (A) preferably has a repeating unit having a polar group.
Examples of the polar group include a hydroxyl group, a cyano group, a carboxyl group, and a fluorinated alcohol group.
The repeating unit having a polar group is preferably a repeating unit having an alicyclic hydrocarbon structure substituted with a polar group. Moreover, it is preferable that the repeating unit having a polar group does not have an acid-degradable group. The alicyclic hydrocarbon structure in the alicyclic hydrocarbon structure substituted with a polar group is preferably an adamantyl group or a norbornane group.

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

In addition to this, as a specific example of the repeating unit having a polar group, the repeating unit disclosed in paragraphs <0415> to <0433> of US Patent Application Publication No. 2016/0070167A1 can be mentioned.
The resin (A) may contain a repeating unit having a polar group alone or in combination of two or more.
The content of the repeating unit having a polar group is preferably 5 to 40 mol%, more preferably 5 to 30 mol%, still more preferably 10 to 25 mol%, based on all the repeating units in the resin (A).

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

In addition, as a specific example of the repeating unit having neither an acid-degradable group nor a polar group, the repeating unit disclosed in paragraph <0433> of US Patent Application Publication No. 2016/0070167A1 can be mentioned. Can be done.
The resin (A) may contain a repeating unit having neither an acid-decomposable group nor a polar group, or may contain two or more of them in combination.
The content of the repeating unit having neither an acid-degradable group nor a polar group is preferably 5 to 40 mol%, more preferably 5 to 30 mol%, based on all the repeating units in the resin (A). 5 to 25 mol% is more preferred.

In addition to the above-mentioned repeating structural unit, the resin (A) adjusts dry etching resistance, standard developer suitability, substrate adhesion, resist profile, and resolution, heat resistance, sensitivity, etc., which are general required properties of resist. It is possible to have various repeating structural units for the purpose of Examples of such a repeating structural unit include, but are not limited to, a repeating structural unit corresponding to a monomer.

Examples of the monomer include compounds having one addition-polymerizable unsaturated bond selected from acrylic acid esters, methacrylic acid esters, acrylamides, methacrylamides, allyl compounds, vinyl ethers, vinyl esters and the like. Can be mentioned.
In addition, any addition-polymerizable unsaturated compound that can be copolymerized with the monomers corresponding to the various repeating structural units may be copolymerized.
In the 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 for ArF exposure, it is preferable that the resin (A) has substantially no aromatic group from the viewpoint of transmitting ArF light. More specifically, among all the repeating units of the resin (A), the repeating unit having an aromatic group is preferably 5 mol% or less, more preferably 3 mol% or less, and ideally. Is more preferably 0 mol%, i.e. not having a repeating unit having an aromatic group. Further, the resin (A) preferably has a monocyclic or polycyclic alicyclic hydrocarbon structure.

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

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

The weight average molecular weight of the resin (A) is preferably 1,000 to 200,000, more preferably 2,000 to 20,000, further preferably 3,000 to 15,000, and preferably 3,000 to 11,000. Especially preferable. The dispersity (Mw / Mn) is usually 1.0 to 3.0, preferably 1.0 to 2.6, more preferably 1.0 to 2.0, and further 1.1 to 2.0. preferable.

The resin (A) may be used alone or in combination of two or more.
The content of the resin (A) in the total solid content of the composition of the present invention is generally 20% by mass or more. 40% by mass or more is preferable, 60% by mass or more is more preferable, and 80% by mass or more is further preferable. The upper limit is not particularly limited, but 99.5% by mass or less is preferable, 99% by mass or less is more preferable, and 97% by mass or less is further preferable. The total solid content in the composition represents all components other than the solvent in the composition.

<Compound (B) that generates acid by irradiation with active light or radiation>
The composition of the present invention contains a compound (also referred to as "compound (B)", "photoacid generator" or "acid generator") that generates an acid upon irradiation with active light or radiation.
As the photoacid generator, a compound that generates an organic acid by irradiation with active light or radiation is preferable. For example, a sulfonium salt compound, an iodonium salt compound, a diazonium salt compound, a phosphonium salt compound, an imide sulfonate compound, an oxime sulfonate compound, a diazodisulfone compound, a disulfone compound, and an o-nitrobenzyl sulfonate compound can be mentioned.

As the photoacid generator, a known compound that generates an acid by irradiation with active light or radiation can be appropriately selected and used alone or as a mixture thereof. For example, paragraphs <0125> to <0319> of U.S. Patent Application Publication No. 2016/0070167A1, paragraphs <0083> to <0094> of U.S. Patent Application Publication No. 2015/0004544A1, U.S. Patent Application Publication No. 2016/0237190A1. The known compounds disclosed in paragraphs <0323> to <0402> of the specification can be suitably used as the photoacid generator.

Preferable embodiments of the photoacid generator include, for example, compounds represented by the following general formulas (ZI), (ZII) or (ZIII).

In the above general formula (ZI), R ₂₀₁ , R ₂₀₂ and R ₂₀₃ each independently represent an organic group.
The carbon number of the organic group as R ₂₀₁ , R ₂₀₂ and R ₂₀₃ is generally 1 to 30, preferably 1 to 20.
Further, two of R _{201 to} R ₂₀₃ may be bonded to form a ring structure, and the ring may contain an oxygen atom, a sulfur atom, an ester bond, an amide bond, or a carbonyl group. The two of the group formed by bonding of the R ₂₀₁ to R _203, an alkylene group (e.g., butylene, pentylene) and _{-CH 2 -CH 2 -O-CH 2} -CH 2 - and the like it can.
Z ^- represents an anion.

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

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

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

The aryl group, alkyl group, and cycloalkyl group of R _{201 to} R ₂₀₃ are independently an alkyl group (for example, 1 to 15 carbon atoms), a cycloalkyl group (for example, 3 to 15 carbon atoms), and an aryl group (for example, carbon number of carbon atoms). 6 to 14), an alkoxy group (for example, 1 to 15 carbon atoms), a halogen atom, a hydroxyl group, or a phenylthio group may be used as a substituent.

Next, the compound (ZI-2) will be described.
The compound (ZI-2) is a compound in which R _{201 to} R ₂₀₃ in the formula (ZI) each independently represent an organic group having no aromatic ring. Here, the aromatic ring also includes an aromatic ring containing a hetero atom.
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.
Each of R _{201 to} R ₂₀₃ is independently preferably an alkyl group, a cycloalkyl group, an allyl group, or a vinyl group, and more preferably a linear or branched 2-oxoalkyl group or 2-oxocycloalkyl group. Alternatively, it is an alkoxycarbonylmethyl group, more preferably a linear or branched 2-oxoalkyl group.

The alkyl group and cycloalkyl group of R _{201 to} R ₂₀₃ are preferably a linear alkyl group having 1 to 10 carbon atoms or a branched alkyl group having 3 to 10 carbon atoms (for example, a methyl group, an ethyl group, a propyl group, etc.). Butyl group and pentyl group), and cycloalkyl group having 3 to 10 carbon atoms (for example, cyclopentyl group, cyclohexyl group, and norbornyl group) can be mentioned.
R _{201 to} R ₂₀₃ may be further substituted with a halogen atom, an alkoxy group (for example, 1 to 5 carbon atoms), a hydroxyl group, a cyano group, or a nitro group.

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

In the general formula (ZI-3), R _{1c to} R _5c are independently hydrogen atom, alkyl group, cycloalkyl group, aryl group, alkoxy group, aryloxy group, alkoxycarbonyl group, alkylcarbonyloxy group, cyclo. Represents an alkylcarbonyloxy group, a halogen atom, a hydroxyl group, a nitro group, an alkylthio group or an arylthio group.
R _6c and R _7c each independently represent a hydrogen atom, an alkyl group, a cycloalkyl group, a halogen atom, a cyano group or an aryl group.
R _x and R _y each independently represent an alkyl group, a cycloalkyl group, a 2-oxoalkyl group, a 2-oxocycloalkyl group, an alkoxycarbonylalkyl group, an allyl group or a vinyl group.

Even if any two or more of R _{1c to} R _5c , R _5c and R _6c , R _6c and R _7c , R _5c and R _x , and R _x and R _y are combined to form a ring structure, respectively. Often, this ring structure may independently contain an oxygen atom, a sulfur atom, a ketone group, an ester bond, or an amide bond.
Examples of the ring structure include aromatic or non-aromatic hydrocarbon rings, aromatic or non-aromatic heterocycles, and polycyclic fused rings in which two or more of these rings are combined. Examples of the ring structure include a 3- to 10-membered ring, preferably a 4- to 8-membered ring, and more preferably a 5- or 6-membered ring.

Examples of the group formed by combining any two or more of R _{1c to} R _5c , R _6c and R _7c , and R _x and R _y include a butylene group and a pentylene group.
The group formed by bonding R _5c and R _6c , and R _5c and R _x is preferably a single bond or an alkylene group. Examples of the alkylene group include a methylene group and an ethylene group.
Zc ⁻ represents an anion.

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

In the general formula (ZI-4), l represents an integer of 0 to 2.
r represents an integer from 0 to 8.
R ₁₃ represents a group having a hydrogen atom, a fluorine atom, a hydroxyl group, an alkyl group, a cycloalkyl group, an alkoxy group, an alkoxycarbonyl group, or a cycloalkyl group. These groups may have substituents.
R ₁₄ represents a hydroxyl group, an alkyl group, a cycloalkyl group, an alkoxy group, an alkoxycarbonyl group, an alkylcarbonyl group, an alkylsulfonyl group, a cycloalkylsulfonyl group, or a group having a cycloalkyl group. These groups may have substituents. When a plurality of R ₁₄ are present, each independently represents the above group such as a hydroxyl group.
Each of R ₁₅ independently represents an alkyl group, a cycloalkyl group or a naphthyl group. These groups may have substituents. Bonded to two R ₁₅ each other may form a ring. When two R ₁₅ are combined to form a ring together, in the ring skeleton may contain a hetero atom such as an oxygen atom, or a nitrogen atom. In one embodiment, two R ₁₅ is an alkylene group, it is preferable to form a ring structure.
Z ⁻ represents an anion.

In the general formula (ZI-4), the alkyl groups of R ₁₃ , R ₁₄ and R ₁₅ are linear or branched, preferably those having 1 to 10 carbon atoms, and are preferably a methyl group, an ethyl group and an n-. A butyl group, a t-butyl group, or the like is more preferable.

Next, the general formulas (ZII) and (ZIII) will be described.
In the general formulas (ZII) and (ZIII), R _{204 to} R ₂₀₇ each independently represent an aryl group, an alkyl group or a cycloalkyl group.
As the aryl group of R _{204 to} R _207, a phenyl group or a naphthyl group is preferable, and a phenyl group is more preferable. The aryl group of R _{204 to} R ₂₀₇ may be an aryl group having a heterocyclic structure having an oxygen atom, a nitrogen atom, a sulfur atom or the like. Examples of the skeleton of the aryl group having a heterocyclic structure include pyrrole, furan, thiophene, indole, benzofuran, and benzothiophene.
The alkyl group and cycloalkyl group of R _{204 to} R ₂₀₇ are preferably a linear alkyl group having 1 to 10 carbon atoms or a branched alkyl group having 3 to 10 carbon atoms (for example, a methyl group, an ethyl group, a propyl group, etc.). Butyl group and pentyl group), cycloalkyl group having 3 to 10 carbon atoms (for example, cyclopentyl group, cyclohexyl group, and norbornyl group) can be mentioned.

The aryl group, alkyl group, and cycloalkyl group of R _{204 to} R ₂₀₇ may each have an independent substituent. Examples of the substituent that the aryl group, alkyl group, and cycloalkyl group of R _{204 to} R ₂₀₇ may have include an alkyl group (for example, 1 to 15 carbon atoms) and a cycloalkyl group (for example, 3 to 15 carbon atoms). 15), aryl groups (for example, 6 to 15 carbon atoms), alkoxy groups (for example, 1 to 15 carbon atoms), halogen atoms, hydroxyl groups, phenylthio groups and the like can be mentioned.
Z ⁻ represents an anion.

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

In the general formula (3), o represents an integer of 1 to 3. p represents an integer from 0 to 10. q represents an integer from 0 to 10.
Xf each independently represents a fluorine atom or an alkyl group substituted with at least one fluorine atom.
R ₄ and R ₅ each independently represent a hydrogen atom, a fluorine atom, an alkyl group, or an alkyl group substituted with at least one fluorine atom, and when there are a plurality of them, R ₄ and R ₅ are the same, respectively. But it can be different.
L represents a divalent linking group, and when there are a plurality of L, the L may be the same or different.
W represents an organic group containing a cyclic structure.
o represents an integer of 1-3. p represents an integer from 0 to 10. q represents an integer from 0 to 10.

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

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

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

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

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

The cyclic organic group may have a substituent. The substituent may be, for example, an alkyl group (either linear or branched, preferably 1 to 12 carbon atoms) or a cycloalkyl group (single ring, polycyclic ring, or spiro ring). Often, 3 to 20 carbon atoms are preferred), aryl groups (6 to 14 carbon atoms are preferred), hydroxyl groups, alkoxy groups, ester groups, amide groups, urethane groups, ureido groups, thioether groups, sulfonamide groups, and sulfonic acids. An ester group can be mentioned. The carbon constituting the cyclic organic group (carbon that contributes to ring formation) may be carbonyl carbon.

Formula (3) As the anion represented ^{_{by, SO 3 - -CF 2 -CH 2}} -OCO- (L) q'-W, SO 3 - -CF 2 -CHF-CH 2 -OCO- (L) q'-W, SO ₃ ⁻ −CF ₂ −COO− (L) q'−W, SO ₃ ⁻ −CF ₂ −CF ₂ −CH ₂ −CH ₂ − (L) q−W, SO ₃ ⁻ −CF _2- CH (CF ₃ ) -OCO- (L) q'-W is preferred. Here, L, q and W are the same as in the general formula (3). q'represents an integer from 0 to 10.

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

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

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

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

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

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

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

n represents an integer of 0 or more. n is preferably 1 to 4, more preferably 2 to 3, and most preferably 3.

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

B represents a hydrocarbon group.

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

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

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

The above cations and anions can be arbitrarily combined and used as a photoacid generator.

The photoacid generator may be in the form of a low molecular weight compound or may be incorporated in a part of the polymer. Further, the form of the low molecular weight compound and the form incorporated in a part of the polymer may be used in combination.
The photoacid generator is preferably in the form of a low molecular weight compound.
When the 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, still more preferably 1,000 or less.
When the photoacid generator is in the form of being incorporated in a part of the polymer, it may be incorporated in a part of the resin (A) described above, or may be incorporated in a resin different from the resin (A). ..
The photoacid generator may be used alone or in combination of two or more.
The content of the photoacid generator in the composition of the present invention (the total of a plurality of types, if present) is preferably 0.1 to 35% by mass based on the total solid content of the composition of the present invention, and is 0. .5 to 25% by mass is more preferable, 3 to 20% by mass is further preferable, and 3 to 15% by mass is particularly preferable.
When the photoacid generator contains a compound represented by the above general formula (ZI-3) or (ZI-4), the content of the photoacid generator contained in the composition (if a plurality of types are present, the content thereof). The total) is preferably 5 to 35% by mass, more preferably 7 to 30% by mass, based on the total solid content of the composition.

<Onium salt (C)>
The composition of the present invention contains an onium salt (C) (also referred to as "onium salt (C)") having an amide structure in the counter cation, which is represented by the general formula (1).
The onium salt (C) can act as an acid diffusion control agent or a quencher in the actinic or radiation-sensitive film formed from the composition of the present invention.

In the general formula (1), X ₁ represents a sulfur atom, an iodine atom, or a nitrogen atom, Q ₁ represents a group having an amide structure, and Q ₂ represents an alkyl group, a cycloalkyl group, or an aryl group. However, at least one of Q ₁ and k Q ₂ represents an alkyl group or a cycloalkyl group. When X ₁ represents a sulfur atom, k = 2, when X ₁ represents an iodine atom, k = 1, and when X ₁ represents a nitrogen atom, k = 3. Y ₁ represents an organic pair anion. At least one of Q ₁ and k Q ₂ may be coupled to each other to form a ring structure. If k is 2 or 3, it may form at least two Q ₂ is bonded to each other to form a ring structure.

In the general formula _(1), Q 1 represents a group having an amide structure. The amide structure represents a group represented by the following formula (am).

In the formula (am), * 1 to * 3 represent a bond.
* 1 to * 3 each represent a bond to another atom, and examples of the other atom include, but are not limited to, a hydrogen atom and a carbon atom.
The group having an amide structure of Q _1, preferably has an amide structure, an alkyl group, a cycloalkyl group, an alkenyl group, a cycloalkenyl group, an alkynyl group, cycloalkynyl group, an aryl group, heteroaryl group, or these It is a group consisting of combinations.
When Q ₁ has an amide structure and is a group consisting of an alkyl group, a cycloalkyl group, an alkenyl group, a cycloalkenyl group, an alkynyl group, a cycloalkynyl group, an aryl group, a heteroaryl group, or a combination thereof, the above formula ( An alkyl group, a cycloalkyl group, an alkenyl group, a cycloalkenyl group, an alkynyl group, a cycloalkynyl group, an aryl group, or a heteroaryl group in which the group represented by am) is bonded by any of the bonds * 1 to * 3. , Or a group consisting of a combination thereof is preferable. In this case, among * 1 to * 3, the above-mentioned alkyl group, cycloalkyl group, alkenyl group, cycloalkenyl group, alkynyl group, cycloalkynyl group, aryl group, heteroaryl group, or a group consisting of a combination thereof is bonded. In the unbonded hands, a hydrogen atom or another alkyl group, cycloalkyl group, alkenyl group, cycloalkenyl group, alkynyl group, cycloalkynyl group, aryl group, heteroaryl group, or a combination thereof is used. It is preferable that the group consisting of is bonded.

The alkyl group may be linear or branched, preferably an alkyl group having 1 to 30 carbon atoms, more preferably an alkyl group having 1 to 12 carbon atoms, and further preferably. Is an alkyl group having 1 to 8 carbon atoms. Specifically, methyl group, ethyl group, propyl group, isopropyl group, n-butyl group, isobutyl group, sec-butyl group, pentyl group, neopentyl group, hexyl group, heptyl group, octyl group, nonyl group, decyl group. , Undecyl group, dodecyl group, tridecyl group, tetradecyl group, pentadecyl group, hexadecyl group, heptadecyl group, octadecyl group, nonadecil group, eikosyl group and the like.
The cycloalkyl group is preferably a cycloalkyl group having 3 to 30 carbon atoms, more preferably a cycloalkyl group having 3 to 12 carbon atoms, and further preferably a cycloalkyl group having 3 to 8 carbon atoms. .. Specific examples thereof include a cyclopropyl group, a cyclopentyl group, a cyclohexyl group, an adamantyl group, a norbornyl group, and a bornyl group.
The alkenyl group may be linear or branched, and is preferably an alkenyl group having 2 to 15 carbon atoms. Specifically, ethylene group, propylene gas, isopropylene group, butylene group, pentylene group, hexylene group, heptylene group, octylene group, nolen group, decylene group, undecylene group, dodecylene group, tridecylene group, tetradecylene group, pentadecylene group. Etc. can be mentioned.
The cycloalkenyl group is preferably a cycloalkenyl group having 3 to 15 carbon atoms. Specific examples thereof include a cyclopentylene group, a socrohexylene group, a cyclopentylene group, a cyclohexylene group, and a norbornene group.
The alkynyl group is preferably an alkynyl group having 1 to 15 carbon atoms, and specifically, an acetylene group, a propynyl, a butynyl group, a pentynyl group, a hexynyl group, a 3,3-dimethyl-1-bunityl group, a heptynyl group, or an octynyl group. , Nonyl group, decynyl group, undecynyl group, dodecynyl group, tridecynyl group, tetradecynyl group, pentadecynyl group and the like.
The aryl group is preferably an aryl group having 6 to 15 carbon atoms, and specific examples thereof include a phenyl group, a tolyl group, a naphthyl group, and an anthryl group.
Examples of the heteroaryl group include pyridyl group, pyrazil group, pyranyl group, pyrazolyl group, thiazolyl group, indole group, imidazolyl group, benzimidazolyl group, thiazolyl group, benzthiazolyl group, benzoxazolyl group, chromanyl group and quinolyl group. Examples thereof include an isoquinolyl group, a pyrimidyl group and a furanyl group.

Q ₁ is a group consisting of a combination of two or more selected from an alkyl group, a cycloalkyl group, an alkenyl group, a cycloalkenyl group, an alkynyl group, a cycloalkynyl group, an aryl group, and a heteroaryl group (for example, an aralkyl group). It may be a group having an amide structure. Further, Q ₁ may further have a substituent. Examples of the substituent include a hydroxyl group, an alkoxy group, a nitro group, a halogen atom (fluorine atom, chlorine atom, bromine atom, iodine atom), carboxy group, amino group, cyano group and the like.

In the general formula (1), Q ₂ represents an alkyl group, a cycloalkyl group, or an aryl group.
Alkyl group as Q _2, a cycloalkyl group or an aryl group, an alkyl group in Q _1, are similar to those described cycloalkyl group, or an aryl group.
Alkyl group as Q _2, a cycloalkyl group, or aryl group may further have a substituent. For example, the alkyl group may have an aryl group as a substituent (that is, it may be an aralkyl group).
Preferably at least one of the k Q ₂ 'is an alkyl group or a cycloalkyl group, and more preferably all of an alkyl group or a cycloalkyl group.

In the general formula (1), at least one of Q ₁ and k Q ₂ represents an alkyl group or a cycloalkyl group.
When Q ₁ represents an alkyl group or a cycloalkyl group, it represents an alkyl group having an amide structure or a cycloalkyl group having an amide structure.
In the present invention, at least one of Q ₁ and k Q ₂ in the general formula (1) represents an alkyl group or a cycloalkyl group, so that the transparency of the onium salt (C) is improved, which is even better. Pattern shape can be formed.

In the general formula (1), when X ₁ represents a sulfur atom, k = 2, when X ₁ represents an iodine atom, k = 1, and when X ₁ represents a nitrogen atom, k = 3. is there.
At least one of Q ₁ and k Q ₂ may be coupled to each other to form a ring structure. If k is 2 or 3, it may form at least two Q ₂ is bonded to each other to form a ring structure. The ring structure is not particularly limited, and examples thereof include an aliphatic ring or an aromatic ring containing X ₁ and a carbon atom as a ring member. The ring may contain a hetero atom (for example, an oxygen atom, a sulfur atom, or a nitrogen atom) as a ring member. Moreover, the said ring may have a substituent. The number of carbon atoms in the ring is preferably 3 to 20, and more preferably 4 to 15.

In the general formula (1), Y ₁ represents an organic pair anion.
Y ₁ is not particularly limited, specific examples and preferred ranges are, Z in formula (ZI) as the aforementioned photoacid generator ^-, Z in the general formula (ZII) ^-, in formula (ZI-3) Zc ⁻ and Z in the general formula (ZI-4) are similar to.

From the viewpoint of the ability to trap acids, the onium salt (C) preferably does not have a structure in which an aromatic group is directly linked to a nitrogen atom having an amide structure.

From the viewpoint of transparency and the like, in the general formula (1), X ₁ represents a sulfur atom, and preferably represent two Q ₂ 'is independently an alkyl group or a cycloalkyl group, more represents an alkyl group preferable. However, Q ₁ and may be bonded to form a ring structure and at least one of the two Q _2. Also, two Q ₂ is may be bonded to form a ring structure.

In the present invention, the onium salt (C) is preferably represented by the following general formula (2).

In the general formula (2), Q ₃ and Q ₄ independently represent an alkyl group or a cycloalkyl group, L ₁ represents an alkylene group or a cycloalkylene group, and Q ₅ and Q ₆ independently represent a hydrogen atom and an alkyl, respectively. Represents a group, cycloalkyl group, alkenyl group, cycloalkenyl group, alkynyl group, cycloalkynyl group, aryl group, or heteroaryl group. Q ₃ to Q at least two of ₆ and L ₁ may be bonded to form a ring structure. Y ₂ is an organic pair anion.

In the general formula (2), Q ₃ and Q ₄ independently represent an alkyl group or a cycloalkyl group, respectively, and are the same as those described as an alkyl group or a cycloalkyl group as Q ₂ . It is particularly preferable that Q ₃ and Q ₄ each independently represent an alkyl group.
In the general formula (2), Q ₅ and Q ₆ each independently represent a hydrogen atom, an alkyl group, a cycloalkyl group, an alkenyl group, a cycloalkenyl group, an alkynyl group, cycloalkynyl group, an aryl group, or a heteroaryl group. Alkyl group as Q ₅ and Q _6, cycloalkyl group, alkenyl group, cycloalkenyl group, an alkynyl group, cycloalkynyl group, an aryl group or a heteroaryl group, an alkyl group in Q _1,, cycloalkyl group, alkenyl group, Similar to those described as cycloalkenyl groups, alkynyl groups, cycloalkynyl groups, aryl groups, or heteroaryl groups. It is preferable that Q ₅ and Q ₆ each independently represent a hydrogen atom or an alkyl group.

In the general formula (2), L ₁ represents an alkylene group or a cycloalkylene group.
The alkylene group as L ₁ is preferably an alkylene group having 1 to 12 carbon atoms, more preferably an alkylene group having 1 to 8 carbon atoms, and specific examples thereof include a methylene group, an ethylene group and a propylene group.
The cycloalkylene group as L ₁ is preferably a cycloalkylene group having 3 to 12 carbon atoms, and more preferably a cycloalkylene group having 3 to 8 carbon atoms.
The alkylene group or cycloalkylene group may have a substituent.

In the general formula (2), Q ₃ ~Q least two of ₆ and L ₁ may be bonded to form a ring structure. As the ring structure, when Q ₁ of the general formula (1) and at least one of k Q ₂ are bonded to each other to form a ring structure, and at least two Q ₂ are bonded to each other to form a ring structure. It is the same as that described as the ring structure in the case of forming.

In the general formula (2), Y ₂ represents an organic counter anion, which is the same as Y _{1 in} the general formula (1) described above.

The molecular weight of the cation portion of the onium salt (C) is preferably 100 or more and 500 or less, and more preferably 120 or more and 350 or less. The cation portion of the onium salt (C), for example, in the general formula (1) refers to a structure other than the organic counter anion represented by Y _1. When the molecular weight of the cation portion of the onium salt (C) is in the above range, the diffusibility of the onium salt (C) becomes high, and the common DOF performance and the LWR performance become particularly excellent, which is preferable.

Specific examples of the onium salt (C) are shown below, but the present invention is not limited thereto.

The onium salt (C) can be synthesized by using a known method (for example, the method described in JP-A-2003-307839).

The onium salt (C) may be used alone or in combination of two or more.
The content of the onium salt (C) in the composition of the present invention (the total of a plurality of types, if present) is preferably 0.05 to 30% by mass based on the total solid content of the composition of the present invention. 0.1 to 20% by mass is more preferable, 0.2 to 15% by mass is further preferable, and 0.2 to 10% by mass is particularly preferable.

The content of the onium salt (C) in the composition of the present invention is smaller than the content of the photoacid generator in terms of molars. This is because the onium salt (C) has a structure that acts as a quencher, so if the content is higher than that of the photoacid generator, the acid generated by exposure will be quenched before it sufficiently acts. This is because the pattern formation becomes insufficient. The content of the onium salt (C) in the composition of the present invention is preferably 50% or less, more preferably 1 to 40%, and particularly 5 to 30% of the content of the photoacid generator in terms of molars. preferable.

<Hydrophobic resin (D)>
The composition of the present invention may further contain a hydrophobic resin (“hydrophobic resin (D)”) different from the resin (A) having at least one of (D) fluorine atoms and silicon atoms. preferable.
By containing the hydrophobic resin (D) in the composition of the present invention, it is possible to control the static / dynamic contact angle on the surface of the sensitive light-sensitive or radiation-sensitive film. This makes it possible to improve development characteristics, suppress outgas, improve immersion liquid followability in immersion exposure, reduce immersion defects, and the like.
The hydrophobic resin (D) is preferably designed to be unevenly distributed on the surface of the resist film, but unlike a surfactant, it does not necessarily have to have a hydrophilic group in the molecule, and a polar / non-polar substance is used. It does not have to contribute to uniform mixing.

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

When the hydrophobic resin (D) contains a fluorine atom, the partial structure having a fluorine atom may be a resin having an alkyl group having a fluorine atom, a cycloalkyl group having a fluorine atom, or an aryl group having a fluorine atom. preferable.
The hydrophobic resin (D) is preferably a fluorine-containing (meth) acrylate-based resin.

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

Examples of the acid group (x) include a phenolic hydroxyl group, a carboxylic acid group, a fluorinated alcohol group, a sulfonic acid group, a sulfonamide group, a sulfonylimide group, a (alkylsulfonyl) (alkylcarbonyl) methylene group, and (alkylsulfonyl) (alkyl). Carbonyl) 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 can be mentioned.
As the acid group, a fluorinated alcohol group (preferably hexafluoroisopropanol), a sulfonimide group, or a bis (alkylcarbonyl) methylene group is preferable.

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

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

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

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

On the other hand, especially if the hydrophobic resin (D) comprises a CH ₃ partial structure side chain moiety, a hydrophobic resin (D) is a form that does not contain a fluorine atom and a silicon atom substantially also preferred. Further, it is preferable that the hydrophobic resin (D) is substantially composed of only repeating units composed of only atoms selected from carbon atoms, oxygen atoms, hydrogen atoms, nitrogen atoms and sulfur atoms.

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

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

As the hydrophobic resin (D), a known resin can be appropriately selected and used alone or as a mixture thereof. For example, the known resins disclosed in paragraphs <0451> to <0704> of U.S. Patent Application Publication 2015 / 0168830A1 and paragraphs <0340> to <0356> of U.S. Patent Application Publication 2016/0274458A1 are hydrophobic. It can be suitably used as the sex resin (D). The repeating unit disclosed in paragraphs <0177> to <0258> of US Patent Application Publication No. 2016/0237190A1 is also preferable as the repeating unit constituting the hydrophobic resin (D).

A preferable example of the repeating unit constituting the hydrophobic resin (D) is shown below.

The hydrophobic resin (D) may be used alone or in combination of two or more. It is preferable to mix and use two or more kinds of hydrophobic resins (D) 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 (D) in the composition is preferably 0.01 to 10% by mass, more preferably 0.05 to 10% by mass, based on the total solid content in the composition of the present invention. It is more preferably 10% by mass. The content of the hydrophobic resin (D) in the composition is preferably 0.01% by mass or more from the viewpoint of easy control of surface characteristics, and 10% by mass or less is preferable from the viewpoint of lithography performance.

<Acid diffusion control agent>
The composition of the present invention contains an onium salt (C), but an acid diffusion control agent may be further used in combination. The acid diffusion control agent acts as a quencher that traps the acid generated from the acid generator or the like at the time of exposure and suppresses the reaction of the acid-degradable resin in the unexposed portion due to the excess generated acid. For example, a basic compound (DA), a basic compound (DB) whose basicity is reduced or eliminated by irradiation with active light or radiation, an onium salt (DC) which is a relatively weak acid with respect to an acid generator, and a nitrogen atom. A low molecular weight compound (DD) having a group having a group desorbed by the action of an acid, an onium salt compound (DE) having a nitrogen atom in the cation portion, or the like can be used as an acid diffusion control agent. In the composition of the present invention, a known acid diffusion control agent can be appropriately used. For example, paragraphs <0627> to <0664> of US Patent Application Publication No. 2016/0070167A1, paragraphs <0995> 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 the acid diffusion control agent.

As the basic compound (DA), preferably, a compound having a structure represented by the following formulas (A) to (E) can be mentioned.

In the general formulas (A) and (E), R ²⁰⁰ , R ²⁰¹ and R ²⁰² may be the same or different, and each of them independently has a hydrogen atom, an alkyl group (preferably 1 to 20 carbon atoms), and a cycloalkyl group. It represents (preferably 3 to 20 carbon atoms) or an aryl group (6 to 20 carbon atoms). R ²⁰¹ and R ²⁰² may be combined 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 the general formulas (A) and (E) may have a substituent or may be unsubstituted.
Regarding the above alkyl group, as the alkyl group having a substituent, an aminoalkyl group having 1 to 20 carbon atoms, a hydroxyalkyl group having 1 to 20 carbon atoms, or a cyanoalkyl group having 1 to 20 carbon atoms is preferable.
It is more preferable that the alkyl groups in the general formulas (A) and (E) are unsubstituted.

As the basic compound (DA), guanidine, aminopyrrolidin, pyrazole, pyrazoline, piperazin, aminomorpholine, aminoalkylmorpholin, piperidine and the like are preferable, and imidazole structure, diazabicyclo structure, onium hydroxide structure, onium carboxylate structure, etc. More preferably, 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, or an aniline derivative having a hydroxyl group and / or an ether bond.

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

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

Preferred partial structures of the proton acceptor functional group include, for example, crown ethers, azacrown ethers, 1-3-order amines, pyridines, imidazoles, and pyrazine structures.

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

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

The acid dissociation constant pKa represents the acid dissociation constant pKa in an aqueous solution, and is defined in, for example, Chemical Handbook (II) (Revised 4th Edition, 1993, edited by The Chemical Society of Japan, Maruzen Co., Ltd.). The lower the value of the acid dissociation constant pKa, the higher the acid strength. Specifically, the acid dissociation constant pKa in an aqueous solution can be measured by measuring the acid dissociation constant at 25 ° C. using an infinitely diluted aqueous solution. Alternatively, the following software package 1 can be used to calculate Hammett's substituent constants and values based on a database of publicly known literature values. All pKa values described herein indicate values calculated using this software package.

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

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

The onium salt, which is a weak acid relative to the acid generator, is preferably a compound represented by the following general formulas (d1-1) to (d1-3).

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

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

An onium salt (DC), which is a weak acid relative to an acid generator, is a compound having a cation moiety and an anion moiety in the same molecule, and the cation moiety and anion moiety are linked by a covalent bond (hereinafter referred to as “)”. , Also referred to as "compound (DCA)").
The compound (DCA) is preferably a compound represented by any of the following general formulas (C-1) to (C-3).

In the general formulas (C-1) to (C-3), R ₁ , R ₂ , and R ₃ each independently represent a substituent having one or more carbon atoms.
L ₁ represents a divalent linking group or a single bond that links the cation moiety and the anion moiety.
-X ^{- _is,} -COO ^{-, -SO} 3 - represents an anion portion selected from -R ₄ ^-, -SO ₂ -, and ^-N. R ₄ is a linking site with the adjacent N atom, a carbonyl group (-C (= O) -) , sulfonyl group _{(-S (= O) 2 -} ), and sulfinyl group (-S (= O) - ) Represents a monovalent substituent having at least one of them.
R ₁ , R ₂ , R ₃ , R ₄ , and L ₁ may be combined with each other to form a ring structure. Further, in the general formula (C-3), two of R _{1 to} R ₃ are combined to represent one divalent substituent, which may be bonded to an N atom by a double bond.

Substituents having 1 or more carbon atoms in R _{1 to} R ₃ include an alkyl group, a cycloalkyl group, an aryl group, an alkyloxycarbonyl group, a cycloalkyloxycarbonyl group, an aryloxycarbonyl group, an alkylaminocarbonyl group, and a cycloalkylamino. Examples thereof include a carbonyl group and an arylaminocarbonyl group. It is preferably an alkyl group, a cycloalkyl group, or an aryl group.

L ₁ as a divalent linking group includes 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 kinds thereof. Examples thereof include groups formed by combining the above. 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.

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

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

As R _b , a linear or branched alkyl group, a cycloalkyl group, or an aryl group is preferable, and a linear or branched alkyl group or a cycloalkyl group is more preferable.
Examples of the ring formed by connecting the two R _bs to each other include alicyclic hydrocarbons, aromatic hydrocarbons, heterocyclic hydrocarbons and derivatives thereof.
Specific structures of the group represented by the general formula (d-1) include, but are not limited to, the structure disclosed in paragraph <0466> of US Patent Publication US2012 / 0135348A1. ..

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

In the general formula (6), l represents an integer of 0 to 2, m represents an integer of 1 to 3, and satisfies l + m = 3.
_Ra represents a hydrogen atom, an alkyl group, a cycloalkyl group, an aryl group or an aralkyl group. When l is 2, the two Ras may be the same or different, and the two _Ras may be interconnected to form a heterocycle with the nitrogen atom in the equation. This heterocycle may contain a heteroatom other than the nitrogen atom in the formula.
R _b has the same meaning as _{R b} in formula (d-1), and preferred examples are also the same.
In the general formula (6), the alkyl group as R _a, a cycloalkyl group, an aryl group and aralkyl group, is each independently an alkyl group as R _b, cycloalkyl group, aryl group and aralkyl group, is substituted The group may be substituted with a group similar to the group described above.

Specific examples of the alkyl group, cycloalkyl group, aryl group, and aralkyl group of _Ra (these groups may be substituted with the above group) are the same groups as those of the above-mentioned specific example for R _b. Can be mentioned.
Specific structures of the particularly preferred compound (DD) in the present invention include, but are limited to, the compounds disclosed in paragraph <0475> of U.S. Patent Application Publication No. 2012/01335348A1. is not.

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

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

The composition of the present invention may or may not contain an acid diffusion control agent, but when it is contained, one kind may be used alone, or two or more kinds may be used in combination.
When the composition of the present invention contains an acid diffusion control agent, the content of the acid diffusion control agent in the composition (the total of a plurality of types, if present) is determined to be 0, based on the total solid content of the composition. 1 to 10% by mass is preferable, and 0.1 to 5% by mass is more preferable.

<Solvent (F)>
The compositions of the present invention usually contain a solvent.
In the composition of the present invention, a known resist solvent can be appropriately used. For example, paragraphs <0665> to <0670> of US Patent Application Publication 2016/0070167A1, paragraphs <0210> to <0235> of US Patent Application Publication 2015/0004544A1, US Patent Application Publication 2016/0237190A1. The known solvents disclosed in paragraphs <0424> to <0426> of the specification and paragraphs <0357> to <0366> of the US Patent Application Publication No. 2016/0274458A1 can be preferably used.
Examples of the solvent that can be used in preparing the composition include alkylene glycol monoalkyl ether carboxylate, alkylene glycol monoalkyl ether, lactic acid alkyl ester, alkyl alkoxypropionate, and cyclic lactone (preferably having 4 to 10 carbon atoms). Examples thereof include organic solvents such as monoketone compounds (preferably having 4 to 10 carbon atoms) which may have a ring, alkylene carbonate, alkyl alkoxyacetate, and alkyl pyruvate.

As the organic solvent, a mixed solvent in which a solvent containing a hydroxyl group in the structure and a solvent not containing a hydroxyl group may be used may be used.
As the solvent containing a hydroxyl group and the solvent not containing a hydroxyl group, the above-mentioned exemplified compounds can be appropriately selected, but as the solvent containing a hydroxyl group, alkylene glycol monoalkyl ether, alkyl lactate and the like are preferable, and propylene glycol monomethyl ether is preferable. (PGME), propylene glycol monoethyl ether (PGEE), methyl 2-hydroxyisobutyrate, or ethyl lactate is more preferred. Further, as the solvent containing no hydroxyl group, alkylene glycol monoalkyl ether acetate, alkylalkoxypropionate, monoketone compound which may contain a ring, cyclic lactone, alkyl acetate and the like are preferable, and among these, propylene glycol monomethyl Ether acetate (PGMEA), ethyl ethoxypropionate, 2-heptanone, γ-butyrolactone, cyclohexanone, cyclopentanone or butyl acetate are more preferred, propylene glycol monomethyl ether acetate, γ-butyrolactone, ethyl ethoxypropionate, cyclohexanone, Cyclopentanone or 2-heptanone is more preferred. Propylene carbonate is also preferable as the solvent containing no hydroxyl group.
The mixing ratio (mass ratio) of the solvent containing a hydroxyl group and the solvent not containing a hydroxyl group is 1/99 to 99/1, preferably 10/90 to 90/10, more preferably 20/80 to 60/40. preferable. A mixed solvent containing 50% by mass or more of a solvent containing no hydroxyl group is preferable in terms of coating uniformity.
The solvent preferably contains propylene glycol monomethyl ether acetate, and may be a propylene glycol monomethyl ether acetate single solvent or a mixed solvent of two or more kinds containing propylene glycol monomethyl ether acetate.

<Surfactant (H)>
The composition of the present invention may or may not contain a surfactant. When a surfactant is contained, a fluorine-based and / or a silicon-based surfactant (specifically, a fluorine-based surfactant, a silicon-based surfactant, or a surfactant having both a fluorine atom and a silicon atom) ) Is preferable.

By containing a surfactant in the composition of the present invention, it is possible to obtain a resist pattern having good sensitivity and resolution and few adhesions and development defects when an exposure light source of 250 nm or less, particularly 220 nm or less is used. it can.
Examples of the fluorine-based and / or silicon-based surfactant include the surfactants described in paragraph <0276> of US Patent Application Publication No. 2008/0248425.
In addition, surfactants other than the fluorine-based and / or silicon-based surfactants described in paragraph <0280> of US Patent Application Publication No. 2008/0248425 can also be used.

These surfactants may be used alone or in combination of two or more.
When the composition of the present invention contains a surfactant, the content of the surfactant is preferably 0.0001 to 2% by mass, preferably 0.0005 to 1% by mass, based on the total solid content of the composition. More preferred.
On the other hand, when the content of the surfactant is 10 ppm (parts per million) or more with respect to the total solid content of the composition, the surface uneven distribution of the hydrophobic resin is increased. As a result, the surface of the sensitive light-sensitive or radiation-sensitive film can be made more hydrophobic, and the water followability during immersion exposure is improved.

(Other additives)
The composition of the present invention may further contain an acid growth agent, a dye, a plasticizer, a photosensitizer, a light absorber, an alkali-soluble resin, a dissolution inhibitor, a dissolution accelerator and the like.

<Preparation method>
The film thickness of the sensitive light-sensitive film or the radiation-sensitive film made of the composition of the present invention is preferably 90 nm or less, more preferably 85 nm or less, from the viewpoint of improving the resolving power. Such a film thickness can be obtained by setting the solid content concentration in the composition to an appropriate range to give an appropriate viscosity and improving the coatability or film forming property.
The solid content concentration of the composition of the present invention is usually 1.0 to 10% by mass, preferably 2.0 to 5.7% by mass, and more preferably 2.0 to 5.3% by mass. The solid content concentration is the mass percentage of the mass of other resist components excluding the solvent with respect to the total mass of the composition.

The composition of the present invention is used by dissolving the above-mentioned components in a predetermined organic solvent, preferably the above-mentioned mixed solvent, filtering the mixture, and then coating the composition on a predetermined support (substrate). The pore size of the filter used for filter filtration is preferably 0.1 μm or less, more preferably 0.05 μm or less, still more preferably 0.03 μm or less. The filter is preferably made of polytetrafluoroethylene, polyethylene, or nylon. In filter filtration, for example, as disclosed in Japanese Patent Application Publication No. 2002-62667 (Japanese Unexamined Patent Publication No. 2002-62667), cyclic filtration may be performed, and a plurality of types of filters may be connected in series. Alternatively, they may be connected in parallel for filtration. Moreover, the composition may be filtered a plurality of times. Further, the composition may be degassed before and after the filter filtration.

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

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

The pattern forming method of the present invention
(I) A step of forming a sensitive light-sensitive or radiation-sensitive film on a support by the above-mentioned sensitive light-sensitive or radiation-sensitive resin composition (film formation step).
(Ii) A step of irradiating the above-mentioned sensitive light-sensitive or radiation-sensitive film with active light or radiation (exposure step), and
(Iii) A step (development step) of developing a sensitive light or radiation sensitive film irradiated with the above active light or radiation using a developing solution.
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 immersion exposure.
The pattern forming method of the present invention preferably includes (iv) preheating (PB: PreBake) step before the (ii) exposure step.
The pattern forming method of the present invention preferably includes (v) post-exposure heating (PEB: Post Exposure Bake) step after the (ii) exposure step and before the (iii) development step.
The pattern forming method of the present invention may include (ii) exposure steps a plurality of times.
The pattern forming method of the present invention may include (iv) a preheating step a plurality of times.
The pattern forming method of the present invention may include (v) a post-exposure heating step a plurality of times.

In the pattern forming method of the present invention, the above-mentioned (i) film forming step, (ii) exposure step, and (iii) developing step can be performed by a generally known method.
Further, if necessary, a resist underlayer film (for example, SOG (Spin On Glass), SOC (Spin On Carbon), antireflection film) is formed between the sensitive light-sensitive or radiation-sensitive film and the support. You may. As the resist underlayer film, a known organic or inorganic material can be appropriately used.
A protective film (top coat) may be formed on the upper layer of the sensitive light-sensitive or radiation-sensitive film. As the protective film, a known material can be appropriately used. For example, US Patent Application Publication No. 2007/0178407, US Patent Application Publication No. 2008/0085466, US Patent Application Publication No. 2007/0275326, US Patent Application Publication No. 2016/0299432, The composition for forming a protective film disclosed in US Patent Application Publication No. 2013/02444438 and International Patent Application Publication No. 2016/157988A can be preferably used. The composition for forming a protective film preferably contains the above-mentioned acid diffusion control agent.
A protective film may be formed on the upper layer of the sensitive light-sensitive or radiation-sensitive film containing the above-mentioned hydrophobic resin.

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

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

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

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

As the alkaline developer, a quaternary ammonium salt typified by tetramethylammonium hydroxide is usually used, but in addition to this, alkaline aqueous solutions such as inorganic alkali, 1st to 3rd amine, alcohol amine, and cyclic amine are also used. It can be used.
Further, the alkaline developer may contain an appropriate amount of alcohols and / or a surfactant. The alkali concentration of the alkaline developer is usually 0.1 to 20% by mass. The pH of the alkaline developer is usually 10 to 15.
The time for developing with an alkaline developer is usually 10 to 300 seconds.
The alkali concentration, pH, and development time of the alkaline developer can be appropriately adjusted according to the pattern to be formed.

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

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

Examples of the ester solvent include methyl acetate, butyl acetate, ethyl acetate, isopropyl acetate, pentyl acetate, 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, butanoic acid Butyl, methyl 2-hydroxyisobutyrate, isoamyl acetate, isobutyl isobutyrate, butyl propionate and the like can be mentioned.

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

A plurality of the above solvents may be mixed, or may be mixed with a solvent other than the above or water. The water content of the developer as a whole is preferably less than 50% by mass, more preferably less than 20% by mass, further preferably less than 10% by mass, and particularly preferably substantially free of water.
The content of the organic solvent in the organic developer is preferably 50% by mass or more and 100% by mass or less, more preferably 80% by mass or more and 100% by mass or less, and 90% by mass or more and 100% by mass or less, based on the total amount of the developing solution. The following is more preferable, and 95% by mass or more and 100% by mass or less is particularly preferable.

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

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

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

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

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

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

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

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

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

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

The rinse solution may contain an appropriate amount of a surfactant.
In the rinsing step, the substrate developed with an organic developer is washed with a rinsing solution containing an organic solvent. The cleaning treatment method is not particularly limited, but for example, a method of continuously discharging the rinse liquid onto the substrate rotating at a constant speed (rotary coating method), or immersing the substrate in a tank filled with the rinse liquid for a certain period of time. A method (dip method), a method of spraying a rinse solution on the substrate surface (spray method), or the like can be applied. Above all, it is preferable to perform the cleaning treatment by the rotary coating method, and after cleaning, rotate the substrate at a rotation speed of 2,000 to 4,000 rpm to remove the rinse liquid from the substrate. It is also preferable to include a heating step (Post Bake) after the rinsing step. This heating step removes the developer and rinse liquid remaining between 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 seconds to 90 seconds.

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

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

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

A method for improving the surface roughness of the pattern may be applied to the pattern formed by the pattern forming method of the present invention. Examples of the method for improving the surface roughness of the pattern include a method of treating the resist pattern with a plasma of a gas containing hydrogen disclosed in US Patent Application Publication No. 2015/0104957. In addition, Japanese Patent Application Publication No. 2004-235468 (Japanese Patent Laid-Open No. 2004-235468), US Patent Application Publication No. 2010/0020297, Proc. of SPIE Vol. 8328 83280N-1 "EUV Resist Curing Technology for LWR Reduction and Etch Sensitivity"
Known methods such as those described in "Enhancement" may be applied.
Further, the resist pattern formed by the above method is a spacer disclosed in, for example, Japanese Patent Application Publication No. 1991-270227 (Japanese Patent Application Laid-Open No. 3-270227) and US Patent Application Publication No. 2013/0209941. It can be used as a core material (Core) for the process.

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

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

<Synthesis of resin RA-1>
37.5 g of cyclohexanone under a nitrogen stream was placed in a three-necked flask and heated to 85 ° C. To this, 9.61 g of monomer A, 5.05 g of monomer B, 2.67 of monomer C, 14.65 g of monomer D and 1.79 g of initiator V-601 (manufactured by Wako Pure Chemical Industries, Ltd.) (monomer). A solution prepared by dissolving 69.6 g of cyclohexanone (5.0 mol%) was added dropwise over 6 hours. After completion of the dropping, the reaction was further carried out at 85 ° C. for 2 hours. After allowing the reaction solution to cool, the reaction solution was added dropwise to a mixed solution of 900 ml of methanol / 100 ml of water over 20 minutes, and the precipitated powder was collected by filtration and dried to obtain 27.2 g of resin (RA-1). The weight average molecular weight (Mw) of the obtained resin was 8500 in terms of standard polystyrene, and the dispersity (Mw / Mn) was 1.72.

Other resins (RA-2 to RA-6) were also synthesized using the same method. The weight average molecular weight was adjusted by varying the amount of initiator.
The repeating unit (the ratio of the repeating unit is the molar ratio), the weight average molecular weight (Mw), and the dispersity (Mw / Mn) of each resin are shown below.

The photoacid generators used are as follows.

The onium salt (C) used is as follows. The following (QX-1) to (QX-5) are not onium salts (C), but are listed in the column of "onium salt (C)" in Table 1 below for convenience.

[Surfactant]
W-1: Megafuck F176 (manufactured by Dainippon Ink and Chemicals Co., Ltd.) (fluorine type)
W-2: Megafuck R08 (manufactured by Dainippon Ink and Chemicals Co., Ltd.) (fluorine and silicon)

〔solvent〕
S1: Propylene glycol monomethyl ether acetate (PGMEA)
S2: 2-Heptanone
S3: Cyclohexanone
S4: γ-Butyrolactone
S5: Propylene glycol monomethyl ether (PGME)

[Hydrophobic resin]

<Preparation of resist composition>
The components shown in Table 1 below are dissolved in the solvent shown in Table 1 in the amount of addition shown in Table 1 to prepare a solution having a solid content concentration of 5% by mass, and this is filtered through a polyethylene filter having a pore size of 0.03 μm. The positive resist compositions (solutions) of each Example and Comparative Example were prepared.
Further, in Table 1 below, the ratio of the content of the onium salt (C) to the content of the photoacid generator in each resist composition in terms of mole (the content of the onium salt (C) is photoacid in terms of mole). What percentage of the content of the generator) is described.

The prepared positive resist composition was evaluated by the following method, and the results are shown in Table 2.

-Pattern formation-
An antireflection film ARC29A (manufactured by Nissan Chemical Industries, Ltd.) was applied onto a silicon wafer (diameter 12 inches) and baked at 205 ° C. for 60 seconds to form an antireflection film having a film thickness of 86 nm. The prepared resist composition was applied thereto, and the mixture was baked at 100 ° C. for 60 seconds to form a photosensitive film (resist film) having a film thickness of 100 nm. One inch is 0.0254 m. The obtained wafer was used with an ArF excimer laser immersion scanner (ASML XT1700i, NA1.20, Anallar, outer sigma 0.700, inner sigma 0.400, XY deflection), and the opening portion was 100 nm. Exposure was performed through a 6% halftone mask with a pitch between holes of 800 nm. Ultrapure water was used as the immersion liquid. Then, after heating at 100 ° C. for 60 seconds, it was developed with an aqueous solution of tetramethylammonium hydroxide (2.38% by mass) for 30 seconds, rinsed with pure water, and then spin-dried to obtain an isolated hole pattern having a diameter of 85 nm. ..
Further, the exposure treatment and the development treatment were carried out according to the same procedure as above except that the closed portion was exposed through a 6% halftone mask in which the closed portion was 115 nm and the pitch between dots was 800 nm, and the isolation with a diameter of 90 nm was performed. I got a dot pattern.

-Common tolerance evaluation of depth of focus (common DOF performance test)-
The exposure amount and depth of focus that reproduce the isolated hole pattern with a diameter of 85 nm were set to the optimum exposure amount and the optimum depth of focus, respectively, and the focus depth was changed (defocused) from the optimum focus depth while keeping the exposure amount as the optimum exposure amount. At that time, a depth of focus width (nm) was observed, which allowed a diameter of ± 10% (that is, 85 nm ± 10%) of the above diameter. Similarly, for the isolated dot pattern having a diameter of 90 nm, a depth of focus width (nm) that allows a diameter of ± 10% (that is, 90 nm ± 10%) of the diameter was observed.
The region where the depth of focus fluctuates to allow ± 10% of the diameter of both the hole pattern and the dot pattern is defined as the common depth of focus tolerance (common DOF). The larger the value of the fluctuation range, the better the performance.

-Line with sloughness (LWR)-
A line-and-space pattern was obtained under the same conditions as above, except for exposure through a 6% halftone mask of a 1: 1 line-and-space pattern with a line width of 75 nm. The optimum exposure amount is the exposure amount that resolves a line pattern with an average line size of 75 nm, and a length-measuring scanning electron is used for a 75 nm (1: 1) line-and-space resist pattern that is resolved at the optimum exposure amount. When observing from the upper part of the pattern using a microscope (SEM, S-9380II manufactured by Hitachi, Ltd.), the line width was observed at an arbitrary 32 points, and the measurement variation was evaluated in 3σ (unit: nm). The smaller the value of 3σ, the better the performance.

-Rectangle of the cross-sectional shape of the pattern-
A line-and-space pattern was obtained under the same conditions as above, except that the exposure was made through a 6% halftone mask of a 1: 1 line-and-space pattern with a line width of 100 nm.
The cross-sectional shape of a line pattern (line / space = 1/1) with a line width of 100 nm at an exposure rate that resolves a line pattern with an average line size of 100 nm is measured by a length-measuring scanning electron microscope (SEM, Hitachi, Ltd. S. It was observed using -9380II). In the cross-sectional shape of the line pattern, [the line width at the top portion (surface portion) of the line pattern / the line width at the middle portion of the line pattern (half the height of the line pattern)] was determined. The closer the value of the above ratio is to 1.0, the better the rectangularity and the better the performance.

From Table 2, it was found that the resist compositions of Examples 1 to 10 were able to form a pattern excellent in LWR performance and rectangularity of the cross-sectional shape, and were also excellent in common DOF performance.

Claims (13)

(A) A resin whose polarity increases due to the action of acid and its solubility in a developing solution changes.
(B) Compounds that generate acid by irradiation with active light or radiation,
(C) Onium salt having an amide structure in the counter cation,
A sensitive light-sensitive or radiation-sensitive resin composition containing
The onium salt (C) is represented by the following general formula (1).
A sensitive light-sensitive or radiation-sensitive resin composition in which the content of the onium salt (C) in the sensitive light-sensitive or radiation-sensitive resin composition is smaller than the content of the compound (B) in terms of molars.
In the general formula (1), X ₁ represents a sulfur atom, an iodine atom, or a nitrogen atom, Q ₁ represents a group having an amide structure, and Q ₂ represents an alkyl group, a cycloalkyl group, or an aryl group. However, at least one of Q ₁ and k Q ₂ represents an alkyl group or a cycloalkyl group. When X ₁ represents a sulfur atom, k = 2, when X ₁ represents an iodine atom, k = 1, and when X ₁ represents a nitrogen atom, k = 3. Y ₁ represents an organic pair anion. At least one of Q ₁ and k Q ₂ may be coupled to each other to form a ring structure. If k is 2 or 3, it may form at least two Q ₂ is bonded to each other to form a ring structure. The actinic or radiation-sensitive resin composition according to claim 1, wherein the onium salt (C) does not have a structure in which an aromatic group is directly linked to a nitrogen atom having an amide structure. In the general formula (1), X ₁ represents a sulfur atom, and sensitive or radiation-sensitive resin according to claim 1 or 2 representing two Q ₂ 'is independently an alkyl group or a cycloalkyl group Composition.
However, Q ₁ and may be bonded to form a ring structure and at least one of the two Q _2. Also, two Q ₂ is may be bonded to form a ring structure. The actinic or radiation-sensitive resin composition according to any one of claims 1 to 3, wherein the onium salt (C) is represented by the following general formula (2).
In the general formula (2), Q ₃ and Q ₄ independently represent an alkyl group or a cycloalkyl group, L ₁ represents an alkylene group or a cycloalkylene group, and Q ₅ and Q ₆ independently represent a hydrogen atom and an alkyl, respectively. Represents a group, cycloalkyl group, alkenyl group, cycloalkenyl group, alkynyl group, cycloalkynyl group, aryl group, or heteroaryl group. Q ₃ to Q at least two of ₆ and L ₁ may be bonded to form a ring structure. Y ₂ is an organic pair anion. The actinic light-sensitive or radiation-sensitive resin composition according to any one of claims 1 to 4, wherein the molecular weight of the cation portion of the onium salt (C) is 100 or more and 500 or less. The actinic or radiation-sensitive resin composition according to any one of claims 1 to 5, wherein the molecular weight of the cation portion of the onium salt (C) is 120 or more and 350 or less. Any one of claims 1 to 6, wherein the content of the onium salt (C) in the actinic light-sensitive or radiation-sensitive resin composition is 50% or less of the content of the compound (B) in terms of molars. The actinic or radiation-sensitive resin composition according to the item. The actinic cheilitis according to any one of claims 1 to 7, further comprising (D) a hydrophobic resin different from the resin (A) having at least one of a fluorine atom and a silicon atom. Radiation-sensitive resin composition. The actinic light-sensitive or radiation-sensitive resin composition according to claim 8, wherein the hydrophobic resin (D) is a fluorine-containing (meth) acrylate-based resin. The content of the hydrophobic resin (D) in the sensitive light-sensitive or radiation-sensitive resin composition is 1 to 10% by mass based on the total solid content of the sensitive light-sensitive or radiation-sensitive resin composition. The actinic or radiation-sensitive resin composition according to claim 8 or 9. A sensitive light-sensitive or radiation-sensitive film formed by the sensitive light-sensitive or radiation-sensitive resin composition according to any one of claims 1 to 10. A step of forming an actinic cheilitis or radiation-sensitive film by the actinic cheilitis or radiation-sensitive resin composition according to any one of claims 1 to 10.
The step of irradiating the sensitive light or radiation sensitive film with active light or radiation, and
A pattern forming method comprising a step of developing a sensitive light-sensitive or radiation-sensitive film irradiated with active light or radiation using a developing solution. A method for manufacturing an electronic device, including the pattern forming method according to claim 12.