JP7076473B2 - Sensitive ray-sensitive or radiation-sensitive resin composition, resist film, pattern forming method, electronic device manufacturing method, compound - Google Patents

Description

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

Conventionally, in the manufacturing process of semiconductor devices such as ICs (Integrated Circuits, integrated circuits) and LSIs (Large Scale Integrated Circuits, large-scale integrated circuits), microfabrication by lithography using sensitive light-sensitive or radiation-sensitive resin compositions has been performed. Processing is being carried out.
For example, Patent Document 1 discloses a resist composition containing a compound represented by the following formula.

JP 2012-189977

When the present inventors specifically examined the compound disclosed in Patent Document 1, the sensitive light-sensitive or radiation-sensitive resin composition using the compound disclosed in Patent Document 1 has stability and stability. It was found that may not always be sufficient. It was also found that there is room for improvement in the LWR (line wizardness) performance of the obtained pattern.

An object of the present invention is to provide a sensitive ray-sensitive or radiation-sensitive resin composition capable of obtaining a pattern having excellent storage stability and excellent LWR performance.
Another object of the present invention is to provide a resist film, a pattern forming method, a method for producing an electronic device, and a compound for the above-mentioned sensitive light-sensitive or radiation-sensitive resin composition.

As a result of diligent studies to achieve the above-mentioned problems, the present inventors have found that the above-mentioned problems can be solved by using the compound Q having a specific structure, and have completed the present invention.
That is, it was found that the above problem can be solved by the following configuration.

[1]
A sensitive light-sensitive or radiation-sensitive resin composition comprising a resin having a repeating unit having a group which is decomposed by the action of an acid and whose polarity is increased, and the compound Q represented by the general formula (I).
[2]
The sensitive light-sensitive or radiation-sensitive resin composition according to [1], wherein A represents a single bond in the general formula (I).
[3]
Described in [1] or [2], wherein any one of R ¹ , R ⁵ , R ⁶ and R ¹⁰ in the general formula (I) is a group represented by the general formula (II). Sensitive ray-sensitive or radiation-sensitive resin composition.
[4]
The actinic light-sensitive or radiation-sensitive resin composition according to any one of [1] to [3], further comprising a photoacid generator other than the above compound Q.
[5]
A resist film formed by using the sensitive light-sensitive or radiation-sensitive resin composition according to any one of [1] to [4].
[6]
A step of forming a resist film on a support using the sensitive light-sensitive or radiation-sensitive resin composition according to any one of [1] to [4], a step of exposing the resist film, and the exposure. A pattern forming method comprising a step of developing a resist film formed with a developing solution.
[7]
A method for manufacturing an electronic device, which comprises the pattern forming method according to [6].
[8]
A compound represented by the general formula (I-2).
[9]
The compound according to [8], wherein A represents a single bond in the general formula (I-2).
[10]
In the general formula (I-2), any one of R ¹ , R ⁵ , R ⁶ and R ¹⁰ is a group represented by the general formula (II), [8] or [9]. The compound described in.

According to the present invention, it is possible to provide a sensitive ray-sensitive or radiation-sensitive resin composition capable of obtaining a pattern having excellent storage stability and excellent LWR performance.
Another object of the present invention is to provide a resist film, a pattern forming method, a method for producing an electronic device, and a compound for the above-mentioned sensitive light-sensitive or radiation-sensitive resin composition.

Hereinafter, the present invention will be described in detail.
The description of the constituent elements described below may be based on the representative embodiments of the present invention, but the present invention is not limited to such embodiments.
Regarding the notation of a group (atomic group) in the present specification, the notation that does not describe substitution or non-substitution includes a group having a substituent as well as a group having no substituent. For example, the "alkyl group" includes not only an alkyl group having no substituent (unsubstituted alkyl group) but also an alkyl group having a substituent (substituted alkyl group). 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 excima laser, extreme ultraviolet rays (EUV light: Extreme Ultraviolet), X-rays, and electron beams (EB). : 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 typified by excimer lasers, extreme ultraviolet rays, X-rays, and EUV light, but also electron beams and. It also includes drawing with particle beams such as ion beams.
In the present specification, "to" 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.

As used herein, (meth) acrylate represents acrylate and methacrylate.
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.). GPC measurement by 8120 GPC) (solvent: tetrahydrofuran, flow rate (sample injection amount): 10 μL, column: TSK gel Multipore HXL-M manufactured by Toso Co., Ltd., 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).

In the present specification, pKa (acid dissociation constant pKa) means an acid dissociation constant pKa in an aqueous solution, for example, Chemical Handbook (II) (Revised 4th Edition, 1993, edited by Japan Chemical Society, 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 / Labs).

In the present specification, examples of the halogen atom include a fluorine atom, a chlorine atom, a bromine atom, and an iodine atom.

[Acting light-sensitive or radiation-sensitive resin composition]
The actinic light-sensitive or radiation-sensitive resin composition of the present invention (hereinafter, also simply referred to as “composition” or “composition of the present invention”) will be described.
The composition of the present invention is a so-called resist composition, and may be a positive 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 composition of the present invention is typically a chemically amplified resist composition.

A feature of the composition of the present invention is that it contains a resin having a repeating unit having a group which is decomposed by the action of an acid and whose polarity is increased, and a compound Q represented by the general formula (I) described later. Will be.
The mechanism by which the problem of the present invention is solved by such a configuration is not always clear, but the present inventors speculate as follows.
Since the anionic group of compound Q has high acidity and low nucleophilicity, it is less likely to cause decomposition of other components (such as the above resin) in the composition as compared with the compound described in Patent Document 1, and has a composition. It is believed that the storage stability of the product has been improved.
Further, the compound Q is a betaine compound, and the charge is neutralized in the molecule, so that the ionicity is lowered. As a result, it is considered that the compatibility with the resin is improved and the LWR performance is improved by being able to disperse uniformly in the film.

Hereinafter, the components contained in the composition of the present invention will be described in detail.

<Resin having a repeating unit having a group that decomposes by the action of acid and increases its polarity>
The sensitive light-sensitive or radiation-sensitive resin composition of the present invention is a resin having a repeating unit having a group (hereinafter, also referred to as “acid-degradable group”) which is decomposed by the action of an acid and whose polarity is increased (hereinafter, also referred to as “acid-degradable group”). Also referred to as "acid-degradable resin" or "resin A").
In this case, in the pattern forming method of the present invention, typically, when an alkaline developer is used as the developer, a positive pattern is preferably formed, and when an organic developer is used as the developer. A negative pattern is preferably formed.

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

The acid-degradable group preferably has a structure in which the polar group is protected by a group (leaving group) in which the polar group is decomposed and desorbed by the action of an acid.
The polar group includes a carboxy group, a phenolic hydroxyl group, a fluorinated alcohol group, a sulfonic acid group, a sulfonamide group, a sulfonylimide group, a (alkylsulfonyl) (alkylcarbonyl) methylene group, and a (alkylsulfonyl) (alkylcarbonyl) imide group. , Bis (alkylcarbonyl) methylene group, bis (alkylcarbonyl) imide group, bis (alkylsulfonyl) methylene group, bis (alkylsulfonyl) imide group, tris (alkylcarbonyl) methylene group, and tris (alkylsulfonyl) methylene group. Such as an acidic group (a group that dissociates in a 2.38 mass% tetramethylammonium hydroxide aqueous solution), an alcoholic hydroxyl group, and the like can be mentioned.

The alcoholic hydroxyl group is a hydroxyl group bonded to a hydrocarbon group and refers to a hydroxyl group other than the hydroxyl group (phenolic hydroxyl group) directly bonded on the aromatic ring, 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, etc.). The alcoholic hydroxyl group is preferably a hydroxyl group having a pKa (acid dissociation constant) of 12 to 20.

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

A preferred group as an acid-degradable group is a group in which the hydrogen atom of these groups is replaced with a group that is eliminated by the action of an acid (leaving group).
Examples of the group (leaving group) desorbed by the action of an acid include -C (R ₃₆ ) (R ₃₇ ) (R ₃₈ ), -C (R ₃₆ ) (R ₃₇ ) (OR ₃₉ ), and -C (R ₀₁ ) (R ₀₂ ) (OR ₃₉ ) and the like can be mentioned.
In the formula, R ₃₆ to R ₃₉ 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 coupled to each other to form a ring.
R ₀₁ and R ₀₂ each independently represent a hydrogen atom, an alkyl group, a cycloalkyl group, an aryl group, an aralkyl group, or an alkenyl group.

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. The monocyclic ring is preferably a cycloalkyl group having 3 to 8 carbon atoms, and examples thereof include a cyclopropyl group, a cyclobutyl group, a cyclopentyl group, a cyclohexyl group, and a cyclooctyl group. As the polycycle, a cycloalkyl group having 6 to 20 carbon atoms is preferable, and for example, an adamantyl group, a norbornyl group, an isobornyl group, a kanfanyl group, a dicyclopentyl group, an α-pinel group, a tricyclodecanyl group and a tetracyclododecyl group. , And an androstanyl group and the like. In addition, one or more carbon atoms 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). The monocyclic cycloalkyl group is preferably a cyclopentyl group or a cyclohexyl group, and the polycyclic cycloalkyl group is a norbornyl group, a tetracyclodecanyl group, a tetracyclododecanyl group, an adamantyl group or the like. preferable.

The acid-degradable group preferably has a tertiary alkyl ester group, acetal group, cumyl ester group, enol ester group, or acetal ester group, and more preferably has an acetal group or a tertiary alkyl ester group. 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), T represents a single bond or a divalent linking group.
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.
It is more preferable that T is a single bond.

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

In the general formula (AI), Rx ₁ to Rx ₃ independently represent an alkyl group or a cycloalkyl group, respectively.
Any two of Rx ₁ to Rx ₃ may or may not be combined to form a ring structure.
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 or n-butyl. Groups, isobutyl groups, t-butyl groups and the like are preferred. The number of carbon atoms of the alkyl group is preferably 1 to 10, more preferably 1 to 5, and even more preferably 1 to 3. The alkyl groups of Rx ₁ , Rx ₂ and Rx ₃ may have a part of the carbon-carbon bond as a double bond.
The cycloalkyl groups of Rx ₁ , Rx ₂ and Rx ₃ may be monocyclic or polycyclic. Examples of the monocyclic cycloalkyl group include a cyclopentyl group and a cyclohexyl group. Examples of the polycyclic cycloalkyl group include a norbornyl group, a tetracyclodecanyl group, a tetracyclododecanyl group, and an adamantyl group.

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

Specific examples of the monomers corresponding to the repeating units represented by the general formula (AI) are given below. 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 is decomposed as a repeating unit having an acid-degradable group by the action of the acid described in paragraphs <0363> to <0364> of US Patent Application Publication No. 2016/0070167A1 to form an alcoholic hydroxyl group. It may have repeating units containing the resulting groups.

The resin A may have one type of repeating unit having an acid-decomposable group alone, or may have two or more types.

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

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

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

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

The lactone structure or sultone structure may or may not have a substituent (Rb ₂ ). Examples of the substituent (Rb ₂ ) include an alkyl group having 1 to 8 carbon atoms, a cycloalkyl group having 4 to 7 carbon atoms, an alkoxy group having 1 to 8 carbon atoms, an alkoxycarbonyl group having 2 to 8 carbon atoms, and a carboxy group. A halogen atom, a hydroxyl group, a cyano group, an acid-degradable group or the like is preferable, and an alkyl group having 1 to 4 carbon atoms, a cyano group or an acid-degradable group is more preferable. 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.

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

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

n is the number of 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-) n is a single bond.

_R0 represents an alkylene group, a cycloalkylene group, or a combination thereof. When there are a plurality of R _0s , the plurality of R _0s may be the same or different.
The alkylene group or cycloalkylene group of _R0 may have a substituent.

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's, the plurality of Z's may be the same or different.
Among them, Z is preferably an ether bond or an ester bond, and more preferably an ester bond.

R ₈ represents a monovalent organic group having a lactone structure or a sultone structure.
Among them, carbon atoms constituting a lactone structure or a sultone structure in any of the structures represented by the general formulas (LC1-1) to (LC1-22) and the general formulas (SL1-1) to (SL1-3). It is preferable that the group is formed by removing one hydrogen atom from one. It is preferable that the carbon atom from which one hydrogen atom is removed is not a carbon atom constituting a substituent (Rb ₂ ).

R ₇ represents a hydrogen atom, a halogen atom, or a monovalent organic group (preferably a methyl group).

As the repeating unit having a lactone structure or a sultone structure, a repeating unit represented by the following general formula (III-2) is also preferable.

In the general formula (III-2), RIII independently represents a hydrogen atom or a substituent. Examples of the substituent include a halogen atom and a monovalent organic group (preferably a methyl group).
RIII is preferably a hydrogen atom.
cyc represents a group having a lactone structure or a sultone structure.
Specifically, in any of the structures represented by the general formulas (LC1-1) to (LC1-22) and the general formulas (SL1-1) to (SL1-3), a lactone structure or a sultone structure. It is preferable that the group is formed by removing two hydrogen atoms from one carbon atom constituting the above. It is preferable that the carbon atom from which two hydrogen atoms are removed is not a carbon atom constituting a substituent (Rb ₂ ).

The resin A may have a repeating unit having a carbonate structure. As the carbonate structure, a cyclic carbonate ester structure is preferable.
As the repeating unit having a cyclic carbonic acid ester structure, a repeating unit represented by the following general formula (A-1) is preferable.

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 of 0 or more.
_RA ² represents a substituent. When n is 2 or more, the plurality of _RA ^2s existing may be the same or different.
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 a group represented by —O—CO—O— in the formula.

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

The resin A may have 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 have two or more kinds. good.

The following is an example of a monomer corresponding to a repeating unit having at least one selected from the group consisting of a lactone structure, a sultone structure, and a carbonate structure.
In the examples below, the methyl group attached to the vinyl group may be replaced with a hydrogen atom, a halogen atom, or a monovalent organic group.

When the resin A has a repeating unit having at least one selected from the group consisting of a lactone structure, a sultone structure, and a carbonate structure, the resin A consists of a group consisting of a lactone structure, a sultone structure, and a carbonate structure contained in the resin A. The content of the repeating unit having at least one selected (the total of multiple repeating units having at least one selected from the group consisting of a lactone structure, a sultone structure, and a carbonate structure) is a resin. It is preferably 5 to 70 mol%, more preferably 10 to 65 mol%, still more preferably 20 to 60 mol%, based on all the repeating units in A.

(Repeating unit with polar group)
The resin A may have a repeating unit having a polar group in addition to the above-mentioned group.
Examples of the polar group include a hydroxyl group, a cyano group, a carboxy group, a fluorinated alcohol group and the like.
As the repeating unit having a polar group, a repeating unit having an alicyclic hydrocarbon structure substituted with a polar group is preferable. Moreover, it is preferable that the repeating unit having a polar group does not have an acid-decomposable group. The alicyclic hydrocarbon structure in the alicyclic hydrocarbon structure substituted with the 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, specific examples of the repeating unit having a polar group include the repeating unit disclosed in paragraphs <0415> to <0433> of the US Patent Application Publication No. 2016/0070167A1.
The resin A may have one type of repeating unit having a polar group alone, or may have two or more types.
When the resin A has a repeating unit having a polar group, the content of the repeating unit having a polar group is preferably 5 to 40 mol%, more preferably 5 to 30 mol%, based on all the repeating units in the resin A. It is preferable, 10 to 25 mol% is more preferable.

(Repeating unit with neither acid-degradable group nor polar group)
In addition to the above-mentioned groups, the resin A may further have a repeating unit having 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-degradable group nor a polar group include the repeating units described in paragraphs <0236> to <0237> of US Patent Application Publication No. 2016/0026083A1. Preferred examples of monomers corresponding to repeating units having neither an acid-degradable group nor a polar group are shown below.

In addition, specific examples of the repeating unit having neither an acid-degradable group nor a polar group include the repeating unit disclosed in paragraph <0433> of US Patent Application Publication No. 2016/0070167A1. ..
The resin A may have one type of repeating unit having neither an acid-decomposable group nor a polar group, or may have two or more types.
When the resin A has a repeating unit having neither an acid-degradable group nor a polar group, the content of the repeating unit having neither an acid-degradable group nor a polar group is the total repeating unit in the resin A. On the other hand, 5 to 40 mol% is preferable, 5 to 30 mol% is more preferable, and 5 to 25 mol% is further preferable.

In addition to the above-mentioned repeating structural unit, the resin A adjusts dry etching resistance, standard developer suitability, substrate adhesion, resist profile, or further general necessary characteristics of resist such as resolution, heat resistance, and sensitivity. It may 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 predetermined monomer.

As the predetermined monomer, for example, one addition-polymerizable unsaturated bond selected from acrylic acid esters, methacrylic acid esters, acrylamides, methacrylamides, allyl compounds, vinyl ethers, vinyl esters and the like. Examples thereof include compounds having.
In addition, an addition-polymerizable unsaturated compound that can be copolymerized with the monomers corresponding to the above-mentioned various repeating structural units may be used.
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 the transparency of ArF light. More specifically, the repeating unit having an aromatic group is preferably 5 mol% or less, more preferably 3 mol% or less, and ideally, with respect to all the repeating units in the resin A. It is more preferred to have 0 mol%, i.e., no repeating units with aromatic groups. Further, the resin A preferably has a monocyclic or polycyclic alicyclic hydrocarbon structure.

In the resin A, all the repeating units may be composed of (meth) acrylate-based repeating units. In this case, all of the repeating units may be methacrylate-based repeating units, all of the repeating units may be acrylate-based repeating units, and all of the repeating units may be a combination of methacrylate-based repeating units and acrylate-based repeating units. May be. Above all, the content of the acrylate-based repeating unit is preferably 50 mol% or less with respect to all the repeating units of the resin A.

In addition, as the resin A, a known resin can be appropriately used. For example, paragraphs <0055> to <0191> of US Patent Application Publication No. 2016/0274458A1, paragraphs <0035> to <0087> of US Patent Application Publication No. 2015/0004544A1, and US Patent Application Publication 2016 /. 0147150A The known resin disclosed in paragraphs <0045> to <0090> of the first specification can be suitably used as the resin A.

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

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 particularly preferably 3,000 to 12,000. .. The degree of dispersion (Mw / Mn) is usually 1.0 to 3.0, preferably 1.0 to 2.6, more preferably 1.0 to 2.0, and further preferably 1.1 to 2.0. preferable.

As the resin A, one type may be used alone, or two or more types may be used.
The content of the resin A in the composition is generally 20% by mass or more, preferably 40% by mass or more, more preferably 60% by mass or more, and 75% by mass, based on the total solid content in the composition. % Or more is more preferable. The upper limit is not particularly limited, but is preferably 95% by mass or less, more preferably 90% by mass or less, and further preferably 85% by mass or less.
The solid content is intended to be a component of the composition excluding the solvent.

<Compound Q>
The composition of the present invention comprises compound Q.
Compound Q is a compound represented by the general formula (I).

In general formula (I),
R ¹ to R ¹⁰ independently represent a hydrogen atom or a substituent.
However, any one of R ¹ to R ¹⁰ is a group represented by the general formula (II).
In other words, among R ¹ to R ¹⁰ , one group represented by the general formula (II) exists, and the remaining nine groups are substituents other than the group represented by the general formula (II) or hydrogen. It is an atom.

* ^-AX- (II)
In general formula (II), A represents a single bond or a divalent linking group.
The divalent linking group is not particularly limited, but is, for example, -O-, -S-, -NR ^F- ( ^RF represents a hydrogen atom or an alkyl group), and a divalent hydrocarbon group (for example). , An alkylene group, an alkenylene group (eg-CH = CH-), an alkynylene group (eg-C≡C-), and an arylene group (preferably a phenylene group)), or a group in which these are combined.
As the divalent linking group, an alkylene group (preferably 1 to 3 carbon atoms) which may have a substituent, an ester group, or a group composed of a combination thereof is preferable.
As the substituent that the alkylene group may have, a halogen atom is preferable, and a fluorine atom is more preferable.
Above all, A is preferably a single bond.

X ^- is -SO ₃ ^- ,-(SO ₂ ) -N- (SO ₂ ) R ¹¹ , ^- (SO ₂ ) -N ^--- COR ¹² , -CO-N ^--- (SO ₂ ) R ¹³ , Or, it represents -CO-N ^{--COR 14} .
R ¹¹ to R ¹⁴ each independently represent an organic group.
As the organic group, an alkyl group which may have a substituent or a cycloalkyl group which may have a substituent is preferable.
The alkyl group may be linear or branched. The number of carbon atoms is preferably 1 to 6.
Of these, as the alkyl group, a methyl group, an ethyl group, a propyl group, an isopropyl group, a t-butyl group, or an n-butyl group is preferable.
The cycloalkyl group may be monocyclic or polycyclic. The number of carbon atoms is preferably 5 to 10.
As the substituent that the alkyl group and the cycloalkyl group may have, a halogen atom is preferable, and a fluorine atom is more preferable. For example, it is also preferable that a part or all of the hydrogen atom of the alkyl group and the cycloalkyl group is replaced with a halogen atom (preferably a fluorine atom). In other words, it is also preferable that the alkyl group is a fluoroalkyl group (including a perfluoroalkyl group, preferably 1 to 6 carbon atoms).
However, when R ³ or R ⁸ is a group represented by the general formula (II) and- (SO ₂ ) -N- ⁽ SO ₂ ) R ¹¹ , R ¹¹ is a group other than a trifluoromethyl group. It preferably represents an organic group.

One of ^R1 , ^R5 , ^R6 , and ^R10 out of ^R1 to ^R10 is one of R1 to R10 because a pattern having better storage stability and better LWR performance can be obtained. , It is preferable that it is a group represented by the general formula (II).

Among the substituents represented by R ¹ to R ¹⁰ , the substituents other than the group represented by the general formula (II) are hydrogen atoms or the substituents other than the group represented by the general formula (II). ..
As the substituent other than the group represented by the general formula (II), a group other than the anionic group is preferable.
Among the substituents represented by R ¹ to R ¹⁰ , the substituent other than the group represented by the general formula (II) may be, for example, an alkyl group substituted with a halogen atom (preferably a fluorine atom). Can be mentioned. The alkyl group may be linear or branched, and may have a cyclic structure. Further, the carbon atom constituting the alkyl group may be substituted with one or more groups selected from the group consisting of an ether group, a carbonyl group and an ester group (for example, the carbon atom at the root of the alkyl group). May be substituted with an ether group to form an alkyl group in the form of an alkoxy group). Of these, as the alkyl group, a methyl group, an ethyl group, a propyl group, an isopropyl group, a t-butyl group, or an n-butyl group is preferable. It is also preferable that some or all of the hydrogen atoms contained in these groups are substituted with halogen atoms (preferably fluorine atoms). In other words, it is also preferable that the alkyl group is a fluoroalkyl group (including a perfluoroalkyl group, preferably 1 to 6 carbon atoms).
Of R ¹ to R ¹⁰ other than the group represented by the general formula (II), 0 to 3 preferably represent a substituent, and more preferably 0 to 1 represent a substituent.

The compound Q is preferably a compound represented by the general formula (I-2).

In the general formula (I-2),
R ¹ to R ¹⁰ independently represent a hydrogen atom or a substituent.
However, any one of R ¹ to R ¹⁰ is a group represented by the general formula (II).
* ^-AX- (II)
In general formula (II),
A represents a single bond or a divalent linking group.
X ^- is -SO ₃ ^- ,-(SO ₂ ) -N- (SO ₂ ) R ¹¹ , ^- (SO ₂ ) -N ^--- COR ¹² , -CO-N ^--- (SO ₂ ) R ¹³ , Or, it represents -CO-N ^{--COR 14} .
R ¹¹ to R ¹⁴ each independently represent an organic group.

The group represented by each symbol in the general formula (I-2) has the same meaning as the corresponding group in the general formula (I), and the preferred range is also the same.
However, in the general formula (I-2), when R ³ or R ⁸ is a group represented by the general formula (II) and- (SO ₂ ) -N- ⁽ SO ₂ ) R ¹¹ is used. R ¹¹ represents an organic group other than the trifluoromethyl group.

Compound Q is a molecule having both positive and negative charges in the molecule, and is a so-called zwitterion.
Compound Q is preferably a compound that generates an acid by irradiation with active light or radiation.
Further, the compound Q is preferably basic in the unexposed state and acts as a so-called acid diffusion control agent. The acid diffusion control agent traps the acid generated from the photoacid generator or the like by exposure, and suppresses the reaction progress of the acid-degradable group of the resin A in the unexposed portion due to the excess generated acid.

Compound Q may be used alone or in combination of two or more.
The content of compound Q in the total solid content of the composition of the present invention is preferably 0.5% by mass or more, more preferably 1.0% by mass or more, still more preferably 2.5% by mass or more. The upper limit is not particularly limited, but is preferably 15.0% by mass or less, more preferably 7.0% by mass or less, still more preferably 5.0% by mass or less.

<Photoacid generator>
The composition of the present invention preferably contains a photoacid generator which is a compound other than compound Q.
In the present specification, the photoacid generator is a compound that generates an acid by irradiation with active light or radiation, and is a compound other than compound Q.
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-nitrobenzylsulfonate compound can be mentioned.
The photoacid generator may be zwitterion, but cannot be compound Q.

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 US Patent Application Publication No. 2016/0070167A1, paragraphs <0086> to <0094> of US Patent Application Publication No. 2015/0004544A1, and US Patent Application Publication 2016 /. The known compounds disclosed in paragraphs <0323> to <0402> of 0237190A1 can be suitably used as a photoacid generator.

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

In the above general formula (ZI)
R ₂₀₁ , R ₂₀₂ , and R ₂₀₃ each independently represent an organic group.
The number of carbon atoms 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. Examples of the group formed by bonding two of R ₂₀₁ to R ₂₀₃ include an alkylene group (for example, a butylene group and a pentylene group) and -CH ₂ -CH ₂ -O-CH ₂ -CH _2- . Be done.
Z ^- represents an anion.

Preferable embodiments of the cation in the general formula (ZI) include the compounds described below in compound (ZI-1), compound (ZI-2), compound (ZI-3), and corresponding groups in compound (ZI-4). Can be mentioned.
The photoacid generator may be a compound having a plurality of structures represented by the general formula (ZI). For example, at least one of R ₂₀₁ to R ₂₀₃ of the compound represented by the general formula (ZI) and at least one of R ₂₀₁ to R ₂₀₃ of the other compound 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 an 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 diarylalkyl sulfonium compound, an aryl dialkyl sulfonium compound, a diaryl cycloalkyl sulfonium compound, and an aryl dicycloalkyl sulfonium compound.

As the aryl group contained in 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 chain alkyl group having 3 to 15 carbon atoms, or a branched alkyl group having 3 to 15 carbon atoms. A cycloalkyl group of 15 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) independently represent an organic group having no aromatic ring. Here, the aromatic ring also includes an aromatic ring containing a heteroatom.
The organic group having no aromatic ring as R ₂₀₁ to R ₂₀₃ generally has 1 to 30 carbon atoms, and preferably 1 to 20 carbon atoms.
R ₂₀₁ to R ₂₀₃ are 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-oxo. It is a cycloalkyl group or 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 or an ethyl group, etc.). Propyl group, butyl group, and pentyl group), and cycloalkyl groups 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, cycloalkylcarbonyloxy group, halogen atom, hydroxyl group. , Nitro group, alkylthio group, or arylthio group.
R _6c and R _7c independently represent a hydrogen atom, an alkyl group, a cycloalkyl group, a halogen atom, a cyano group, or an aryl group, respectively.
R _x and R _y 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, respectively.

Any two or more of R _1c to R _5c , R _5c and R _6c , R _6c and R _7c , R _5c and R _x , and R _x and R _y , respectively, are combined to form a ring structure. Also, 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.
As the group formed by bonding R _5c and R _6c , and R _5c and R _x , a single bond or an alkylene group is preferable. 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 hydrogen atom, a fluorine atom, a hydroxyl group, an alkyl group, a cycloalkyl group, an alkoxy group, an alkoxycarbonyl group, or a group having a cycloalkyl group. These groups may have 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 of them independently represents the above group such as a hydroxyl group.
R ₁₅ independently represents an alkyl group, a cycloalkyl group, or a naphthyl group. These groups may have substituents. The two _R15s may combine with each other to form a ring. When two _R15s are bonded to each other to form a ring, the ring skeleton may contain a heteroatom such as an oxygen atom or a nitrogen atom. In one embodiment, it is preferred that the two _R15s are alkylene groups and are bonded to each other 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. The number of carbon atoms of the alkyl group is preferably 1 to 10. As the alkyl group, a methyl group, an ethyl group, an n-butyl group, a t-butyl group and the like are more preferable.

Next, the general formula (ZII) and the general formula (ZIII) will be described.
In the general formula (ZII) and the general formula (ZIII), R ₂₀₄ to R ₂₀₇ independently represent an aryl group, an alkyl group or a cycloalkyl group, respectively.
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.
Examples of the alkyl group and cycloalkyl group of R ₂₀₄ to R ₂₀₇ include a linear alkyl group having 1 to 10 carbon atoms or a branched chain alkyl group having 3 to 10 carbon atoms (for example, a methyl group, an ethyl group, a propyl group, etc.). A butyl group and a pentyl group) or a cycloalkyl group having 3 to 10 carbon atoms (for example, a cyclopentyl group, a cyclohexyl group, and a norbornyl group) are preferable.

The aryl group, alkyl group, and cycloalkyl group of R ₂₀₄ to R ₂₀₇ may each independently have a substituent. Examples of the substituents that the aryl group, the alkyl group, and the 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 carbon atoms). ~ 15), an aryl group (for example, 6 to 15 carbon atoms), an alkoxy group (for example, 1 to 15 carbon atoms), a halogen atom, a hydroxyl group, a phenylthio group and the like can be mentioned.
Z ^- represents an anion.

Z-in the general formula (ZI), Z ^- in the general formula (ZII), Zc- in the general formula (ZI ^- 3), and Z ^- in the general formula (ZI ^- 4) are as follows. The anion represented by is preferable.

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

Xf represents a fluorine atom or an alkyl group substituted with at least one fluorine atom. The number of carbon atoms of this alkyl group is preferably 1 to 10, and more preferably 1 to 4. Further, as the alkyl group substituted with at least one fluorine atom, a perfluoroalkyl group is preferable.
Xf is preferably a fluorine atom or a perfluoroalkyl group having 1 to 4 carbon atoms, and more preferably a fluorine atom or CF ₃ . Above all, it is more preferable that both Xf 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 , the plurality of R ₄ and the plurality of R ₅ may be the same or different from each other.
The alkyl group represented by R ₄ and R ₅ may have a substituent, and preferably has 1 to 4 carbon atoms. R ₄ and R ₅ are preferably hydrogen atoms.
Specific examples and preferred embodiments of the alkyl group substituted with at least one fluorine atom are the same as the specific examples and preferred embodiments of Xf in the general formula (3).

L represents a divalent linking group. When there are a plurality of L's, the plurality of L's may be the same or different.
Examples of the divalent linking group include -COO-, -OCO-, -CONH-, -NHCO-, -CO-, -O-, -S-, -SO-, -SO _2- , and an alkylene group (. Preferred are 1 to 6 carbon atoms), a cycloalkylene group (preferably 3 to 15 carbon atoms), an alkenylene group (preferably 2 to 6 carbon atoms), and a divalent linking group in which a plurality of these are combined. Be done. Among these, -COO-, -OCO-, -CONH-, -NHCO-, -CO-, -O-, -SO _2- , -COO-alkylene group-, -OCO-alkylene group-, -CONH- The alkylene group-or -NHCO-alkylene group-is preferable, and -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 monocyclic or polycyclic. 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. Among them, an alicyclic group having a bulky structure having 7 or more carbon atoms is preferable, and examples thereof include a norbornyl group, a tricyclodecanyl group, a tetracyclodecanyl group, a tetracyclododecanyl group, and an adamantyl group. Be done.

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. Polycyclics 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 heterocyclic ring having no aromaticity 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 preferable.

The cyclic organic group may have a substituent. Examples of the substituent include an alkyl group (which may be linear or branched, preferably 1 to 12 carbon atoms), a cycloalkyl group (single ring, polycyclic (spiro ring, etc.)). ), Preferably 3 to 20 carbon atoms), aryl group (preferably 6 to 14 carbon atoms), hydroxyl group, alkoxy group, ester group, amide group, urethane group, ureido group, thioether group, Examples thereof include a sulfonamide group and a sulfonic acid ester group. The carbon constituting the cyclic organic group (carbon contributing to ring formation) may be a carbonyl carbon.

Examples of the anion represented by the general formula (3) include SO ₃ ^- CF ₂ -CH ₂ -OCO- (L) q'-W and SO ₃ ^- CF ₂ -CHF-CH ₂ -OCO- (L). q'-W, SO ₃ ^- CF ₂ -COO- (L) q'-W, SO ₃ ^- CF ₂ -CF ₂ -CH ₂ -CH _2- (L) q ^- W, or SO _3- -CF ₂ -CH (CF ₃ ) -OCO- (L) q'-W is preferable. 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 the general formula (ZI), Z ⁻ in the general formula (ZII), Zc ⁻ in the general formula (ZI-3), and Z ⁻ in the general formula (ZI ^- 4) are as follows. Anions represented by the general formula (4) are also preferable.

In general formula (4),
X ^B1 and X ^B2 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 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 the general formula (ZI ^- 3), and Z ^- in the general formula (ZI ^- 4) are as follows. Anions represented by are also 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 the general formula (ZI-3), ^{and Z − in} the general formula (ZI-4) are benzenesulfonic acid anions. It is also preferable that it is a benzenesulfonic acid anion substituted with a branched chain alkyl group or a cycloalkyl group.

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

In 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. As n, 1 to 4 are preferable, 2 to 3 are more preferable, and 3 is further preferable.

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

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.

The Z- in the general formula (ZI), the ^Z- in the general formula (ZII), the Zc- in the general formula (ZI ^- 3), ^and the Z ^- in the general formula (ZI-4) are trisulfone carbanions or disulfone amides. It may be an anion.
The trisulfone carbanion is, for example, an anion represented by C- ₍ SO2 ^{- Rp} ) ₃ .
Here, R ^p represents an alkyl group which may have a substituent, a fluoroalkyl group is preferable, a perfluoroalkyl group is more preferable, and a trifluoromethyl group is further preferable.
The disulfonamide anion is, for example, an anion represented by N ⁻ (SO ₂ -R ^q ) ₂ .
Here, R ^q represents an alkyl group which may have a substituent, a fluoroalkyl group is preferable, and a perfluoroalkyl group is more preferable. The two R ^qs may be coupled to each other to form a ring. The group formed by bonding two R ^qs to each other is preferably an alkylene group which may have a substituent, preferably a fluoroalkylene group, and more preferably a perfluoroalkylene group. The alkylene group (preferably a fluoroalkylene group, more preferably a perfluoroalkylene group) preferably has 2 to 4 carbon atoms.

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 small molecule compound or may be incorporated in a part of the polymer. Further, the form of the small molecule 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 small molecule compound.
When the photoacid generator is in the form of a small molecule compound, the molecular weight is preferably 3,000 or less, more preferably 2,000 or less, still more preferably 1,000 or less. The lower limit is not particularly limited, but is usually 50 or more.
When the photoacid generator is 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 (the total of multiple types, if present) is preferably 0.1 to 35% by mass, preferably 0.5 to 25% by mass, based on the total solid content of the composition. Is more preferable, and 3 to 20% by mass is further preferable.

<Hydrophobic resin>
The composition of the present invention may contain a hydrophobic resin. The hydrophobic resin is preferably a resin different from the resin A.
By including the hydrophobic resin in the composition of the present invention, the static and / or dynamic contact angle on the surface of the sensitive light-sensitive or radiation-sensitive film can be controlled. 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 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 polar substances and non-polar substances are uniformly distributed. It does not have to contribute to mixing with.

The hydrophobic resin 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 preferably a resin having a repeating unit having seeds.
When the hydrophobic resin contains a fluorine atom and / or a silicon atom, the fluorine atom and / or the silicon atom in the hydrophobic resin may be contained in the main chain of the resin and may be contained in the side chain. You may.

When the hydrophobic resin contains a fluorine atom, it is preferable that the partial structure having a fluorine atom is a resin having an alkyl group having a fluorine atom, a cycloalkyl group having a fluorine atom, or an aryl group having a fluorine atom.

The hydrophobic resin 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 conversion group).
(Z) A group that decomposes by the action of an acid

Examples of the acid group (x) include a phenolic hydroxyl group, a carboxy group, a fluorinated alcohol group, a sulfonic acid group, a sulfonamide group, a sulfonylimide group, a (alkylsulfonyl) (alkylcarbonyl) methylene group, and (alkylsulfonyl) (alkylcarbonyl). ) Imid 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 sulfoneimide 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 carboxyester group (-COO-), and an acid anhydride group (-CO-O-CO-). ), Acidimide group (-NHCONH-), Carboxioester group (-COS-), Carbonate ester group (-O-CO _- O-), Sulfate ester group (-OSO2O-), and Sulfonate ester group. Examples thereof include (-SO ₂ O-), and a lactone group or a carboxy ester group (-COO-) is preferable.
The repeating unit containing these groups is, for example, a repeating unit in which these groups are directly bonded to the main chain of a 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 terminal of the resin by using a polymerization initiator or a 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 preferably 1 to 100 mol% with respect to all the repeating units in the hydrophobic resin. 3 to 98 mol% is more preferable, and 5 to 95 mol% is even more preferable.

Examples of the repeating unit having a group (z) that decomposes by the action of an acid in the hydrophobic resin include 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 20 to all the repeating units in the hydrophobic resin. 60 mol% is more preferred.
The hydrophobic resin 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 in the hydrophobic resin. 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 in the hydrophobic resin.

On the other hand, particularly when the hydrophobic resin contains a _CH3 partial structure in the side chain portion, a form in which the hydrophobic resin does not substantially contain fluorine atoms and silicon atoms is also preferable. Further, it is preferable that the hydrophobic resin 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 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 the oligomer component contained in the hydrophobic resin is preferably 0.01 to 5% by mass, more preferably 0.01 to 3% by mass. The dispersity (Mw / Mn) is preferably 1.0 to 5.0, more preferably 1.0 to 3.0.

As the hydrophobic resin, a known resin can be appropriately selected and used alone or as a mixture thereof. For example, known resins disclosed in paragraphs <0451> to <0704> of US Patent Application Publication 2015/016883A1 and paragraphs <0340> to <0356> of US Patent Application Publication 2016/0274458A1. Can be suitably used as a hydrophobic resin. Further, 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.

A preferred example of the monomer corresponding to the repeating unit constituting the hydrophobic resin is shown below.

The hydrophobic resin may be used alone or in combination of two or more.
It is also preferable to mix and use two or more kinds of hydrophobic resins having different surface energies from the viewpoint of achieving both immersion liquid followability and development characteristics in immersion exposure.
The content of the hydrophobic resin in the composition is preferably 0.01 to 10% by mass, more preferably 0.03 to 8% by mass, based on the total solid content in the composition of the present invention.

<Surfactant>
The composition of the present invention may contain a surfactant. When containing a surfactant, 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.

When the composition of the present invention contains a surfactant, a pattern having good sensitivity and resolution and few adhesions and development defects can be obtained when an exposure light source of 250 nm or less (particularly 220 nm or less) is used. ..
Fluorine-based and / or silicon-based surfactants include the surfactants described in paragraph <0276> of US Patent Application Publication No. 2008/0248425.
Further, other surfactants other than the fluorine-based and / or silicon-based surfactants described in paragraph <0280> of Japanese 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, more preferably 0.0005 to 1% by mass, based on the total solid content of the composition. preferable.
On the other hand, when the content of the surfactant is 10% by mass or more with respect to the total solid content of the composition, the uneven distribution of the surface of the hydrophobic resin is increased. Thereby, the surface of the sensitive light-sensitive or radiation-sensitive film can be made more hydrophobic, and the water followability at the time of immersion exposure is improved.

<Solvent>
The composition of the present invention may contain a solvent.
In the composition of the present invention, a known resist solvent can be appropriately used. For example, paragraphs <0665> to <0670> of US Patent Application Publication No. 2016/0070167A1, paragraphs <0210> to <0235> of US Patent Application Publication No. 2015/0004544A1, US Patent Application Publication No. 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. 2016/02744558A1 can be preferably used.
Examples of the solvent that can be used when 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 having a hydroxyl group in the structure and a solvent having no hydroxyl group may be used may be used.
As the solvent having a hydroxyl group and the solvent having no hydroxyl group, the above-mentioned exemplary 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 (PGME). ), Propylene glycol monoethyl ether (PGEE), methyl 2-hydroxyisobutyrate, or ethyl lactate is more preferred. Further, as the solvent having no hydroxyl group, alkylene glycol monoalkyl ether acetate, alkylalkoxypropionate, monoketone compound which may have a ring, cyclic lactone, alkyl acetate and the like are preferable, and among these, alkylene glycol monoalkyl ether acetate, alkyl acetate and the like are preferable. Propylene glycol monomethyl ether acetate (PGMEA), ethyl ethoxypropionate, 2-heptanone, γ-butyrolactone, cyclohexanone, cyclopentanone, or butyl acetate are more preferred, and propylene glycol monomethyl ether acetate, γ-butyrolactone, ethyl ethoxypro. Pionate, cyclohexanone, cyclopentanone, or 2-heptanone are more preferred. Propylene carbonate is also preferable as the solvent having no hydroxyl group.
The mixing ratio (mass ratio) of the solvent having a hydroxyl group and the solvent having no hydroxyl group is 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 having no hydroxyl group is preferable in terms of coating uniformity.
The solvent preferably contains propylene glycol monomethyl ether acetate. In this case, the solvent 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.

The solid content concentration of the composition of the present invention is preferably 1.0 to 10% by mass, more preferably 2.0 to 5.7% by mass, still more preferably 2.0 to 5.3% by mass. That is, when the composition contains a solvent, it is preferable to adjust the content of the solvent in the composition so as to satisfy the preferable range of the solid content concentration. 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.
By setting the solid content concentration in the composition to an appropriate range to give an appropriate viscosity and improving the coatability or the film-forming property, the resist film (sensitive light-sensitive or radiation-sensitive) made of the composition of the present invention. The film thickness of the sex film) can be adjusted.

<Other additives>
The composition of the present invention further comprises a resin other than those described above, a cross-linking agent, an acid growth agent, a dye, a plasticizer, a photosensitizer, a light absorber, an alkali-soluble resin, a dissolution inhibitor, a dissolution accelerator, or the like. May include.

<Preparation method>
It is preferable that 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 applying the mixture onto 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 Patent Laid-Open No. 2002-62667), cyclic filtration may be performed, and a plurality of types of filters may be connected in series or in parallel. It may be connected to and filtered. Also, the composition may be filtered multiple 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 comprises a semiconductor manufacturing process such as an IC (Integrated Circuit), a circuit board manufacturing such as a liquid crystal or a thermal head, a molding structure for imprinting, another photofabrication step, or a photofabrication step. , A flat plate printing plate, or a sensitive light-sensitive or radiation-sensitive resin composition used for producing an acid-curable composition. The 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 Electro Mechanical Systems), and the like.

[Pattern formation method, resist film]
The present invention also relates to a pattern forming method using the above-mentioned sensitive ray-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 resist film (active ray-sensitive or radiation-sensitive film) of the present invention will also be described.

The pattern forming method of the present invention is
(I) A step of forming a resist film (sensitive light-sensitive or radiation-sensitive film) on a support using the above-mentioned sensitive light-sensitive or radiation-sensitive resin composition (resist film forming step (film forming step)). ),
(Ii) A step (exposure step) of exposing the resist film (irradiating with active light rays or radiation), and
(Iii) The present invention includes a step (development step) of developing the exposed resist film with a developing solution.

The pattern forming method of the present invention is not particularly limited as long as it includes the steps (i) to (iii) above, 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 (ii) exposure step and before (iii) development step.
The pattern forming method of the present invention may include (ii) an exposure step 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) resist film forming step (forming step), (ii) exposure step, and (iii) developing step can be performed by a generally known method. ..

The film thickness of the resist film is preferably 90 nm or less, more preferably 85 nm or less, from the viewpoint of improving the resolving power.
Further, if necessary, a resist underlayer film (for example, SOG (Spin On Glass), SOC (Spin On Carbon), and antireflection film) may be formed between the resist film and the support. As a material constituting the resist underlayer film, a known organic or inorganic material can be appropriately used.
A protective film (top coat) may be formed on the upper layer of the resist film. As the protective film, a known material can be appropriately used. For example, US Patent Application Publication No. 2007/0178407, US Patent Application Publication No. 2008/0087466, 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 resist 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. The board 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 150 ° C., more preferably 80 to 120 ° C. in both the (iv) preheating step and (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) pre-heating step and (v) post-exposure heating step.
The heating can be performed by means provided in the exposure apparatus and the developing apparatus, and may be performed by using a hot plate or the like.

The light source wavelength 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, the wavelength thereof is preferably 250 nm or less, more preferably 220 nm or less, still more preferably 1 to 200 nm. Specifically, KrF excimer laser (248 nm), ArF excimer laser (193 nm), F2 excimer laser ₍ 157 nm), X-ray, EUV (13 nm), electron beam and the like are preferable, and KrF excimer laser and ArF excimer laser are preferable. , EUV, or electron beam is more 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, an alkaline aqueous solution such as an inorganic alkali, a primary to tertiary amine, an alcohol amine, and a cyclic amine is used. Can also be used.
Further, the alkaline developer may contain an appropriate amount of alcohols and / or a surfactant. The alkaline 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.

Examples of the ketone solvent include 1-octanone, 2-octanone, 1-nonanone, 2-nonanone, 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 Acetic Acid, Ethyl-3-ethoxypropionate, 3-methoxybutyl Acetic Acid, 3-Methyl-3-methoxybutyl Acetic Acid, Methyl Aliate, Ethyl Aliate, Butyl Aliate, propyl Acrate, Ethyl Lactate, Butyl Lactate, propyl Lactate, Butane Examples thereof include butyl acid, methyl 2-hydroxyisobutyrate, isoamyl acetate, isobutyl isobutyrate, and butyl propionate.

As the alcohol-based solvent, the amide-based solvent, the ether-based solvent, and the hydrocarbon-based solvent, the solvents disclosed in paragraphs <0715> to <0718> of US Patent Application Publication No. 2016/0070167A1 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 to 100% by mass, more preferably 80 to 100% by mass, further preferably 90 to 100% by mass, and 95 to 100% by mass with respect to the total amount of the developer. % Is particularly preferable.

The developer may 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 an acid diffusion control agent.

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. There are methods such as spraying the developer on the surface (spray method) and 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 be mentioned.

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.

As the rinsing solution used in the rinsing step after the developing step using the alkaline developer, for example, pure water can be used. 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 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. It is preferable to do so.
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 liquid used in the rinsing step in this case, a rinsing liquid containing a monohydric alcohol is more preferable.

Examples of the monohydric alcohol used in the rinsing step include linear, branched or 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.
The monohydric alcohol preferably has 5 or more carbon atoms, and examples thereof include 1-hexanol, 2-hexanol, 4-methyl-2-pentanol, 1-pentanol, and 3-methyl-1-butanol. , And methylisobutylcarbinol and the like.

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

In the rinsing step, the developed substrate is washed with a rinsing solution. The cleaning treatment method is not particularly limited, but for example, a method of continuously discharging the rinse liquid onto a 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. Examples thereof include a method (dip method) and a method of spraying a rinse liquid on the substrate surface (spray method). Among them, a method of performing a cleaning treatment by a rotary coating method, rotating the substrate at a rotation speed of 2,000 to 4,000 rpm after cleaning, and removing the rinsing liquid from the substrate is preferable. It is also preferable to include a heating step (Post Bake) after the rinsing step. By this heating step, the developing solution and the rinsing solution remaining between the patterns and inside the patterns are removed. In the heating step after the rinsing step, the heating temperature is usually 40 to 160 ° C., preferably 70 to 95 ° C., and the heating time is usually 10 seconds to 3 minutes, preferably 30 seconds to 90 seconds.

The 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 , Topcoat forming composition, etc.) preferably does not contain impurities such as metal components, isomers, and residual monomers. The content of these impurities contained in the above-mentioned various materials is preferably 1 mass ppm or less, more preferably 100 mass ppt or less, further preferably 10 mass ppt or less, and substantially not contained (detection by the measuring device). (Being below the limit) is particularly preferable.

Examples of the method for removing impurities such as metals from the above-mentioned various materials include filtration using a filter. The filter pore diameter 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 for use. 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 using an adsorbent, or filter filtration and an adsorbent may be used in combination. As the adsorbent, a known adsorbent can be used, and for example, an inorganic adsorbent such as silica gel or zeolite, or an organic adsorbent such as activated carbon can be used. Examples of 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. The preferred conditions for filter filtration performed on the raw materials constituting the various materials are the same as the above-mentioned conditions.

In order to prevent impurities from being mixed in, the above-mentioned various materials are described in US Patent Application Publication No. 2015/0227049, Japanese Patent Application Publication No. 2015-123351 (Japanese Patent Laid-Open No. 2015-123351) and the like. It is preferably stored in the described container.

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 pattern with plasma of a gas containing hydrogen disclosed in US Patent Application Publication No. 2015/010497. In addition, Japanese Patent Application Publication No. 2004-235468 (Japanese Patent Laid-Open No. 2004-235468), US Patent Application Publication No. 2010/0020297, and Proc. of SPIE Vol. A known method as described in 832883280N-1 “EUV Resist Curing Technology for LWR Resistion and Etch Sensitivity Enhancement” may be applied.
Further, the pattern formed by the above method is disclosed in, for example, Japanese Patent Application Publication No. 1991-270227 (Japanese Patent Laid-Open No. 3-270227) and US Patent Application Publication No. 2013/209941. It can be used as a core material (Core) for the spacer 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 suitable for electrical and electronic equipment (for example, home appliances, OA (Office Automation) related equipment, media-related equipment, optical equipment, communication equipment, etc.). It will be installed.

〔Compound〕
The present invention also includes the invention of a compound.
The compound of the present invention is the same as the compound represented by the general formula (II-2), and the preferred conditions are also the same.

Hereinafter, the present invention will be described in more detail based on examples. The materials, amounts, 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. Therefore, the scope of the present invention is not limitedly construed by the examples shown below.

[Acting light-sensitive or radiation-sensitive resin composition]
[component]
The components contained in the sensitive light-sensitive or radiation-sensitive resin composition (hereinafter, also referred to as “composition”) used in Examples or Comparative Examples are shown below.

<Acid-degradable resin>
The acid-degradable resins used in the production of the composition are shown below.
In the following formula, * represents the bond position. The numerical value attached to each repeating unit indicates the molar ratio (mol%) occupied by each repeating unit in each resin.

<Compound Q>
(Synthesis of Q-1)
Compound Q-1 was synthesized based on the following scheme.

The compound HBI (5 g) shown in the above scheme is dissolved in a 2,2,2-trifluoroethanol / dichloromethane mixture (volume ratio: 2/1) (84 ml), and then benzene (2.6 g) is further added. In addition, the resulting solution was stirred at room temperature for 12 hours. After distilling off the solvent from the above solution, compound Q-1 (2.4 g) was obtained by crystallization with methanol (yield 40%).

In the same manner, compounds Q-2 to Q-8 were synthesized.
Compound Q used to prepare the composition is shown below.
The compounds Q-9 and Q-10 were used as comparative compounds in Comparative Examples.

<Photoacid generator>
The photoacid generator used to prepare the composition is shown below.

<Hydrophobic resin>
The hydrophobic resin used to prepare the composition is shown below.
In the following formula, * represents the bond position. The numerical value attached to each repeating unit indicates the molar ratio (mol%) occupied by each repeating unit in each resin.

<Surfactant>
The surfactants used in the preparation of the composition are shown below.
・ W-1: Megafuck F176 (manufactured by Dainippon Ink and Chemicals Co., Ltd .; fluorine-based)
W-2: PolyFox PF-6320 (manufactured by OMNOVA Solutions Inc.; fluorine-based)

<Solvent>
The solvents used to prepare the composition are shown below.
SL-1: Propylene glycol monomethyl ether acetate (PGMEA)
SL-2: Propylene glycol monomethyl ether (PGME)
・ SL-3: Cyclohexanone ・ SL-4: γ-Butyrolactone

[Preparation of composition]
Each component was dissolved in a solvent according to the formulation shown in the table shown in the latter part, and a solution having a solid content concentration of 3.8% by mass was prepared for each component. Then, the obtained solution was filtered through a polyethylene filter having a pore size of 0.1 μm to prepare a sensitive light-sensitive or radiation-sensitive resin composition (composition).

〔evaluation〕
<Pattern formation>
(Formation of resist film)
ARC29SR (manufactured by Brewer) for forming an organic antireflection film was applied onto a silicon wafer and baked at 205 ° C. for 60 seconds to form an antireflection film having a film thickness of 98 nm. Each composition prepared according to the formulation shown in the table shown in the latter part was applied thereto, and baked at 100 ° C. for 60 seconds to form a resist film having a film thickness of 90 nm.

(Exposure-Development)
The obtained resist film was subjected to a line width of 44 nm using an ArF excimer laser immersion scanner (manufactured by ASML; XT1700i, NA1.20, C-Quad, outer sigma 0.730, inner sigma 0.630, XY deflection). Exposure through a 6% halftone mask with a 1: 1 line and space pattern. Ultrapure water was used as the immersion liquid. Then, it was heated at 120 ° C. for 60 seconds, developed with butyl acetate for 30 seconds, and then spin-dried to obtain a pattern.

<LWR performance>
The exposure amount (mJ / cm ² ) when forming a 1: 1 line-and-space pattern with a line width of 44 nm was taken as the optimum exposure amount. A 1: 1 line-and-space pattern with a line width of 44 nm obtained by exposure and development at the optimum exposure amount was observed. In observing the pattern, observe from the upper part of the pattern using a length-measuring scanning electron microscope (SEM (Hitachi Co., Ltd. S-8840)), observe the line width at an arbitrary point (160 points), and observe the pattern. The measurement variation was evaluated by 3σ.
The results are shown in the table below.
The smaller the value shown in the "LWR (nm)" column in the table, the better the LWR performance.
The composition used for forming the pattern in this evaluation is the composition immediately after preparation.

<Storage stability (sensitivity ratio)>
In the obtained resist film, the exposure amount (mJ / cm ² ) when forming a 1: 1 line-and-space pattern with a line width of 44 nm was taken as the optimum exposure amount. According to the sensitivity ratio (S1 / S2) between the optimum exposure amount S1 obtained when the composition immediately after preparation is used and the optimum exposure amount S2 obtained when the composition left at 4 ° C. for 1 week after preparation is used. , Sensitivity change was evaluated. When the value of S1 / S2 is close to 1, the change in sensitivity is small and the storage stability is excellent.
The results are shown in the table below.

<Storage stability (particles)>
The number of particles in the composition immediately after preparation (initial value of particles) and the number of particles in the composition after being left at 4 ° C. for 3 months (number of particles after aging) were determined by using a particle counter manufactured by Rion. And the number of particles increased calculated by "(number of particles after aging)-(initial value of particles)" was applied to the following criteria to evaluate the storage stability of the composition.
The composition with a smaller number of particles increases has better storage stability.
Here, substances having a particle size of 0.25 μm or more contained in 1.0 ml of the composition were counted as particles.
The results are shown in the table below.

A: Increase in number of particles is 0.2 / ml or less B: Increase in number of particles is more than 0.2 / ml, 1.0 or less C: Increase in number of particles is 1.0 More than / ml, 5.0 pieces / ml or less D: The number of particles increased is more than 5.0 pieces / ml

〔result〕
The table below shows the composition of the compositions and the results of evaluations performed using those compositions.
In each composition, 10 g, 0.05 g, and 0.03 g of the resin, the hydrophobic resin, and the surfactant were blended, respectively. For compound Q and the photoacid generator, the mass (g) shown in parentheses was added together with the name of each component. The solvent was adjusted so that the internal content ratio (mass ratio) of each solvent was the ratio shown in each column and the solid content concentration of the composition was 3.8% by mass.

From the results shown in the table, it was confirmed that the composition of the present invention was excellent in storage stability and a pattern excellent in LWR performance could be obtained.
Further, regarding compound Q, when any one of R ¹ , R ⁵ , R ⁶ and R ¹⁰ is a group represented by the general formula (II), the storage stability of the composition is more excellent and the LWR. It was confirmed that a pattern with better performance could be obtained (comparison of Examples 1, 2, and 5).
Regarding compound Q, it was confirmed that when A represents a single bond, a pattern having better storage stability of the composition and better LWR performance can be obtained (comparison of Examples 3, 7, and 11).
It was confirmed that when the composition further contains a photoacid generator which is a compound other than compound Q, a pattern having better LWR performance can be obtained (comparison of Examples 9 and 19).

Claims (7)

A sensitive light-sensitive or radiation-sensitive resin composition comprising a resin having a repeating unit having a group which is decomposed by the action of an acid and whose polarity is increased, and the compound Q represented by the general formula (I).

In general formula (I),
R ¹ to R ¹⁰ independently represent a hydrogen atom or a substituent.
However, any one of R ¹ , R ² , R ⁴ to R ⁷ , R ⁹ and R ¹⁰ is a group represented by the general formula (II).
* ^-AX- (II)
In general formula (II),
A represents a single bond or a divalent linking group.
X ^- is -SO ₃ ^- ,-(SO ₂ ) -N- (SO ₂ ) R ¹¹ , ^- (SO ₂ ) -N ^--- COR ¹² , -CO-N ^--- (SO ₂ ) R ¹³ , Or, it represents -CO-N ^{--COR 14} .
R ¹¹ to R ¹⁴ each independently represent an organic group. The actinic light-sensitive or radiation-sensitive resin composition according to claim 1, wherein A represents a single bond. The active ray-sensitive or radiation-sensitive radiation according to claim 1 or 2, wherein any one of R ¹ , R ⁵ , R ⁶ and R ¹⁰ is a group represented by the general formula (II). Sex resin composition. The actinic light-sensitive or radiation-sensitive resin composition according to any one of claims 1 to 3, further comprising a photoacid generator other than the compound Q. A resist film formed by using the sensitive light-sensitive or radiation-sensitive resin composition according to any one of claims 1 to 4. A step of forming a resist film on a support using the sensitive light-sensitive or radiation-sensitive resin composition according to any one of claims 1 to 4.
The step of exposing the resist film and
A pattern forming method comprising a step of developing the exposed resist film with a developing solution. A method for manufacturing an electronic device, including the pattern forming method according to claim 6.