WO2020105523A1

WO2020105523A1 - Active ray-sensitive or radiation-sensitive resin composition, resist film, pattern forming method, method for manufacturing electronic device

Info

Publication number: WO2020105523A1
Application number: PCT/JP2019/044494
Authority: WO
Inventors: 直紘丹呉; 惠瑜王; 秀知高橋; 研由後藤
Original assignee: 富士フイルム株式会社
Priority date: 2018-11-22
Filing date: 2019-11-13
Publication date: 2020-05-28
Also published as: JPWO2020105523A1; JP7239611B2

Abstract

The purpose of the present invention is to provide an active ray-sensitive or radiation-sensitive resin composition capable of forming a resist film having excellent post-exposure delay stability. Another purpose of the present invention is to provide: a resist film using the active ray-sensitive or radiation-sensitive resin composition; a pattern forming method; and a method for manufacturing an electronic device. This active ray-sensitive or radiation-sensitive resin composition is an active ray-sensitive or radiation-sensitive resin composition comprising: a resin X having a specific structure; a resin Y having a specific structure; a compound producing an acid by being irradiated with active rays or radiation; and a solvent. The receding contact angle, to water, of a film formed by using the active ray-sensitive or radiation-sensitive resin composition is 73° or greater.

Description

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

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

Conventionally, in the manufacturing process of semiconductor devices such as IC (Integrated Circuit, integrated circuit) and LSI (Large Scale Integrated circuit, large scale integrated circuit), fine processing by lithography using a chemically amplified resist composition has been performed. There is.

Especially recently, immersion exposure is used as a pattern forming method that enables finer processing. For example, in Patent Document 1, as an actinic ray-sensitive or radiation-sensitive resin composition suitable for immersion exposure, a first polymer having a fluorine atom and a structural unit containing a group of a specific structure, and an acid Disclosed is a resist composition containing a second polymer having a structural unit containing a dissociative group and a radiation-sensitive acid generator.

JP, 2016-126309, A

The present inventors examined the resist composition described in Patent Document 1, and found that a resist film (a film of an actinic ray-sensitive or radiation-sensitive resin composition) formed by the resist composition was exposed before and after exposure. It has been clarified that the line width dimension of the pattern obtained after exposure and development varies when the film is left behind after the exposure. That is, it has been found that there is room for further improving the stability of the resist film over time.

Therefore, an object of the present invention is to provide an actinic ray-sensitive or radiation-sensitive resin composition capable of forming a resist film having excellent stability over time.
Another object of the present invention is to provide a resist film using the above actinic ray-sensitive or radiation-sensitive resin composition, a pattern forming method, and an electronic device manufacturing method.

As a result of earnest studies to solve the above problems, the present inventors have found that an actinic ray-sensitive or radiation-sensitive resin composition having a predetermined composition can solve the above problems, and completed the present invention.

[1] An actinic ray-sensitive or radiation-sensitive resin composition comprising a resin X, a resin Y, a compound that generates an acid upon irradiation with actinic rays or radiation, and a solvent,
The resin X is a resin whose solubility in an alkaline developer is increased by the action of an acid, and is selected from a repeating unit A derived from one or more kinds of monomers selected from the monomer group A described later and a monomer group B described later. A repeating unit B derived from one or more monomers,
The resin Y contains at least one repeating unit of a repeating unit D1 containing a group represented by the formula (I) described below and a repeating unit D2 derived from a monomer represented by the formula (II) described below,
An actinic ray-sensitive or radiation-sensitive resin composition, wherein a film formed by using the actinic ray-sensitive or radiation-sensitive resin composition has a receding contact angle with water of 73 ° or more.
[2] The actinic ray-sensitive or radiation-sensitive resin composition according to [1], wherein the monomer group A is a monomer group A1 described later.
[3] The actinic ray-sensitive or radiation-sensitive resin composition according to [1] or [2], wherein the monomer group B is a monomer group B1 described later.
[4] The actinic ray-sensitive material according to any one of [1] to [3], wherein the resin X further contains a repeating unit C derived from one or more kinds of monomers selected from the monomer group C described later. Radiation-sensitive resin composition.
[5] The actinic ray-sensitive or radiation-sensitive resin composition according to [4], wherein the repeating unit C is a repeating unit derived from a monomer represented by the formula (c-2) described later.
[6] The actinic ray-sensitive or radiation-sensitive material according to any one of [1] to [5], wherein the resin X is a resin represented by formulas (X-1) to (X-10) described below. Resin composition.
[7] The compound that generates an acid upon irradiation with actinic rays or radiation is one or more selected from the group consisting of formulas (P-1) to (P-8) described below, [1] to [6] ] The actinic ray-sensitive or radiation-sensitive resin composition as described in any one of the above.
[8] The repeating unit D1 contains a repeating unit represented by the formula (Y-1) described below, and the repeating unit D2 contains a repeating unit represented by the formula (Y-2) described below [1] The actinic ray-sensitive or radiation-sensitive resin composition according to any one of to [7].
[9] The actinic ray-sensitive or radiation-sensitive resin composition according to any one of [1] to [8], wherein the receding contact angle is 81 ° or more.
[10] The actinic ray-sensitive or radiation-sensitive resin composition according to any one of [1] to [9], which further contains an acid diffusion controller.
[11] A resist film obtained by using the actinic ray-sensitive or radiation-sensitive resin composition according to any one of [1] to [10].
[12] A resist film forming step of forming a resist film using the actinic ray-sensitive or radiation-sensitive resin composition according to any one of [1] to [10],
An exposure step of exposing the resist film,
And a developing step of developing the exposed resist film with a developing solution.
[13] The pattern forming method according to [12], wherein the exposure step is a liquid immersion exposure step at a scan speed of 700 mm / s or more.
[14] A method for manufacturing an electronic device, including the pattern forming method according to [12] or [13].

According to the present invention, it is possible to provide an actinic ray-sensitive or radiation-sensitive resin composition capable of forming a resist film having excellent stability over time with storage.
Further, according to the present invention, there can be provided a resist film using the actinic ray-sensitive or radiation-sensitive resin composition, a pattern forming method, and an electronic device manufacturing method.

Hereinafter, the present invention will be described in detail.
The description of the constituent elements described below may be made based on the representative embodiment of the present invention, but the present invention is not limited to such an embodiment.
The term “actinic ray” or “radiation” used herein refers to, for example, a bright line spectrum of a mercury lamp, deep ultraviolet rays typified by an excimer laser, extreme ultraviolet rays (EUV light: Extreme Ultraviolet), X-rays, and electron beams (EB). : Electron Beam) and the like. The term "light" as used herein means actinic rays or radiation.
Unless otherwise specified, the term "exposure" in the present specification means not only exposure using a bright line spectrum of a mercury lamp, deep ultraviolet rays represented by excimer laser, extreme ultraviolet rays, X-rays, EUV light, etc., 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.

In the present specification, (meth) acrylate represents acrylate and methacrylate.
In the present specification, the “organic group” refers to a group containing at least one carbon atom.
In the present specification, the weight average molecular weight (Mw), number average molecular weight (Mn), and dispersity (also referred to as molecular weight distribution) (Mw / Mn) of the resin are GPC (Gel Permeation Chromatography) device (HLC-manufactured by Tosoh Corporation). 8120 GPC) GPC measurement (solvent: tetrahydrofuran, flow rate (sample injection amount): 10 μL, column: TSK gel Multipore HXL-M manufactured by Tosoh Corporation, column temperature: 40 ° C., flow rate: 1.0 mL / min, detector: differential refraction It is defined as a polystyrene conversion value obtained by a rate detector (Refractive Index Detector).

In the present specification, the pKa (acid dissociation constant pKa) represents the acid dissociation constant pKa in an aqueous solution, and is described in, for example, Chemical Handbook (II) (Revised 4th Edition, 1993, edited by The Chemical Society of Japan, Maruzen Co., Ltd.). Is defined. The lower the acid dissociation constant pKa, the higher the acid strength. The value of pKa is calculated by using the software package 1 below, based on a database of Hammett's substituent constants and known literature values. All the pKa values described herein are the values calculated by using this software package.

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

Regarding the notation of the group (atomic group) in the present specification, notation that does not indicate substituted or unsubstituted 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, in the present specification, the kind of the substituent, the position of the substituent, and the number of the substituents when the phrase “may have a substituent” are not particularly limited. The number of substituents may be, for example, 1, 2, 3, or more. Examples of the substituent include a monovalent non-metallic atomic group excluding a hydrogen atom, which can be selected from the following substituent group T, for example.
(Substituent T)
As the substituent T, a halogen atom such as a fluorine atom, a chlorine atom, a bromine atom and an iodine atom; an alkoxy group such as a methoxy group, an ethoxy group and a tert-butoxy group; an aryloxy group such as a phenoxy group and a p-tolyloxy group; Alkoxycarbonyl group such as methoxycarbonyl group, butoxycarbonyl group and phenoxycarbonyl group; Acyloxy group such as acetoxy group, propionyloxy group and benzoyloxy group; Acetyl group, benzoyl group, isobutyryl group, acryloyl group, methacryloyl group and methoxalyl group An acyl group; an alkylsulfanyl group such as a methylsulfanyl group and a tert-butylsulfanyl group; an arylsulfanyl group such as a phenylsulfanyl group and a p-tolylsulfanyl group; an alkyl group; a cycloalkyl group; an aryl group; a heteroaryl group; a hydroxyl group; Carboxy group; formyl group; sulfo group; cyano group; alkylaminocarbonyl group; arylaminocarbonyl group; sulfonamide group; silyl group; amino group; monoalkylamino group; dialkylamino group; arylamino group; and combinations thereof. Can be mentioned.

[Actinic ray-sensitive or radiation-sensitive resin composition]
A feature of the actinic ray-sensitive or radiation-sensitive resin composition of the present invention (hereinafter, also referred to as “composition of the present invention”) is that the resin X described later (the solubility of which in an alkali developing solution increases due to the action of an acid). Resin) and a resin Y described below, and a film formed by using the above composition under the conditions described below has a receding contact angle of 73 ° or more with respect to water.
Although the mechanism of action has not been clarified, the present inventors have made clear that the resist film obtained from the above composition has remarkably excellent stability over time. In particular, when the receding contact angle is 81 ° or more, the stability with storage over time is further improved.
In the following, first, each component of the composition of the present invention will be described in detail.

[Resin X (acid decomposable resin)]
The composition of the present invention comprises resin X.
The resin X is a resin whose solubility in an alkaline developer is increased by the action of an acid (hereinafter, also referred to as “acid-decomposable resin”), and a group which is decomposed by the action of an acid to increase its polarity (hereinafter, referred to as “acid Also referred to as a "degradable group").
In the pattern forming method of the present invention, typically, when an alkali developing solution is used as a developing solution, a positive pattern is preferably formed, and when an organic developing solution is used as a developing solution, a negative pattern is typically used. Are preferably formed.

The resin X contains a repeating unit A derived from one or more kinds of monomers selected from the monomer group A described below and a repeating unit B derived from one or more kinds of monomers selected from the monomer group B described below. The repeating unit B derived from the monomer in the monomer group B corresponds to the repeating unit having an acid-decomposable group.
Further, the resin X preferably further contains a repeating unit C derived from one or more kinds of monomers selected from the monomer group C described later.

Hereinafter, the repeating unit A, the repeating unit B, and the repeating unit C will be described in detail.

<Repeating unit A>
The repeating unit A is a repeating unit derived from one or more kinds of monomers selected from the monomer group A shown below.
Monomer group A:

As the monomer group A, the following monomer group A1 is preferable because the receding contact angle of the resist film to be formed is more easily adjusted.
Monomer group A1:

The resin X may include the repeating unit A alone or in combination of two or more.

The content of the repeating unit A contained in the resin X (when there are a plurality of repeating units A, the total thereof) is preferably 10 to 90 mol%, and preferably 20 to 70 mol% based on all the repeating units of the resin X. Is more preferable, and 20 to 60 mol% is even more preferable.

<Repeating unit B>
The repeating unit B is a repeating unit derived from one or more kinds of monomers selected from the monomer group B shown below.
Monomer group B:

As the monomer group B, the following monomer group B1 is preferable because the receding contact angle of the resist film to be formed is more easily adjusted.
Monomer group B1:

The resin X may contain the repeating unit B alone or in combination of two or more.

The content of the repeating unit B contained in the resin X (when there are a plurality of repeating units B, the total thereof) is preferably 10 to 90 mol%, and preferably 25 to 80 mol% based on all the repeating units of the resin X. Is more preferable, and 30 to 60 mol% is even more preferable.

<Repeating unit C>
The repeating unit C is a repeating unit derived from one or more kinds of monomers selected from the monomer group C shown below.
Monomer group C:

The repeating unit C is preferably a repeating unit derived from a monomer represented by the following formula (c-2), because the receding contact angle of the resist film to be formed is more easily adjusted.

The resin X may include the repeating unit C alone or in combination of two or more.

When the resin X contains the repeating unit C, the content of the repeating unit C contained in the resin X (when there are plural repeating units C, the total thereof) is 5 to 5 with respect to all the repeating units of the resin X. 30 mol% is preferable, 5 to 20 mol% is more preferable, and 5 to 15 mol% is further preferable.

As the resin X, resins represented by the following formulas (X-1) to (X-10) are preferable. The resins represented by the following formulas (X-1) to (X-10) mean a resin containing a repeating unit in each formula, and the content of each repeating unit is not particularly limited. For example, the resin represented by the formula (X-1) only needs to contain four repeating units, and the content of each repeating unit is not limited. * In the formula represents a bonding position.

Another example of the resin X that can be used in the present invention is shown below.

In addition to the repeating structural units described above, the resin X includes, as other repeating units, dry etching resistance, standard developer suitability, substrate adhesion, resist profile, and resolution and heat resistance which are general necessary properties of resist. It may have various repeating structural units for the purpose of adjusting properties, sensitivity and the like.
Examples of such a repeating structural unit include, but are not limited to, repeating structural units derived from a predetermined monomer.
The resin X can be synthesized by a known method.

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

The resin X may be used alone or in combination of two or more.
In the composition of the present invention, the content of the resin X is typically 20.0% by mass or more, preferably 40.0% by mass or more, and 60.0% by mass based on the total solid content. The above is more preferable, and 80.0 mass% or more is still more preferable. The upper limit is not particularly limited, but is preferably 99.5% by mass or less, more preferably 99.0% by mass or less, and further preferably 97.0% by mass or less.
The solid content is intended to mean a component excluding the solvent in the composition, and a liquid component is regarded as a solid content as long as it is a component other than the solvent.

[Resin Y]
The composition of the present invention comprises resin Y.
The resin Y is a resin different from the resin X, and contains at least a repeating unit D1 containing a group represented by the formula (I) described below and a repeating unit D2 derived from a monomer represented by the formula (II) described below. Contains one repeating unit.
It is presumed that the repeating unit D1 and the repeating unit D2 have high water repellency due to their structural characteristics and are unevenly distributed on the surface of the resist film, which is one of the factors that increase the receding contact angle of the formed resist film. it is conceivable that.

In the following, the repeating unit D1 and the repeating unit D2 will be described in detail.

<Repeating unit D1>
The repeating unit D1 includes a group represented by the following formula (I).
Formula (I):

In formula (I), R ¹ represents a monovalent alkali-dissociable group having 1 to 20 carbon atoms. M represents a divalent hydrocarbon group having 1 to 20 carbon atoms. L represents a divalent organic group having 1 to 20 carbon atoms and having a carbon atom bonded to an adjacent carbonyl group. The L and the M may be bonded to each other to form an alicyclic structure or an aliphatic heterocyclic structure having 3 to 20 ring members. * Represents a bond.

The "alkali dissociative group" is a group that substitutes a hydrogen atom in a polar functional group such as a carboxy group, and in the presence of an alkali (in a tetramethylammonium hydroxide 2.38 mass% aqueous solution at 23 ° C). Refers to a group that dissociates with.
The monovalent alkali dissociative group having 1 to 20 carbon atoms represented by R ¹ is not particularly limited as long as it dissociates in the presence of alkali to generate a polar group.
Examples of the alkali dissociative group include a monovalent fluorinated hydrocarbon group. In addition, the alkali dissociative group, when a fluorine atom is bonded to at least one of the carbon atom bonded to the carbonyl group of the ester bond adjacent to R ¹ and the carbon atom bonded to the carbon atom, for example, 1 Examples thereof include a valent hydrocarbon group.

Examples of the monovalent hydrocarbon group include an alkyl group such as a methyl group, an ethyl group, a propyl group, and a butyl group, an alkenyl group such as an ethenyl group, a propenyl group, a butenyl group, and a pentenyl group, and an ethynyl group. A chain hydrocarbon group such as an alkynyl group such as a propynyl group, a butynyl group and a pentynyl group; a monocyclic cycloalkyl group such as a cyclobutyl group, a cyclopentyl group and a cyclohexyl group, a cyclobutenyl group, a cyclopentenyl group, and a cyclohexynyl group Such as monocyclic cycloalkenyl group, norbornyl group, adamantyl group, and tricyclodecyl group, and other polycyclic cycloalkyl groups, and norbornenyl group, tricyclodecenyl group, and other polycyclic cycloalkenyl groups, etc. Alicyclic hydrocarbon group; aryl group such as phenyl group, tolyl group, xylyl group, and naphthyl group; and aromatic hydrocarbon group such as aralkyl group such as benzyl group, phenethyl group, and phenylpropyl group; Can be mentioned.

The monovalent fluorinated hydrocarbon group includes, for example, a group obtained by substituting a part or all of the hydrogen atoms of the monovalent hydrocarbon group with fluorine atoms.

The alkali dissociable group is preferably a fluorinated hydrocarbon group, and a fluorine atom is bonded to at least one of the carbon atom bonded to the carbonyl group of the ester bond adjacent to R ¹ and the carbon atom bonded to this carbon atom. More preferred is a fluorinated hydrocarbon group. Further, the alkali dissociative group preferably has a primary or secondary carbon atom bonded to an adjacent oxygen atom from the viewpoint of enhancing alkali dissociability. Furthermore, 2 is preferable as the lower limit of the number of carbon atoms of the alkali-dissociable group. On the other hand, the upper limit of the number of carbon atoms of the alkali-dissociable group is preferably 10, more preferably 8, and even more preferably 6.

Examples of the divalent hydrocarbon group having 1 to 20 carbon atoms represented by M include alkanediyl group such as methanediyl group, ethanediyl group, propanediyl group, and butanediyl group, ethenediyl group, propenediyl group, and butenediyl group. Chain hydrocarbon groups such as alkynediyl groups such as groups, and ethynediyl groups, propynediyl groups, and butynediyl groups; monocyclic cycloalkanediyl groups such as cyclobutanediyl groups, cyclopentanediyl groups, and cyclohexanediyl groups Group, cyclobutenediyl group, cyclopentenediyl group, and monocyclic cycloalkenediyl group such as cyclohexenediyl group, norbornanediyl group, tricyclodecanediyl group, and polycyclic cycloalkanediyl group such as adamantanediyl group, and , Norbornenediyl group, and alicyclic hydrocarbon group such as polycyclic cycloalkenediyl group such as tricyclodecenediyl group; arenediyl group such as benzenediyl group, toluenediyl group, and xylenediyl group, and benzenediyl group And aromatic hydrocarbon groups such as arenediylalkanediyl group and arenediylcycloalkanediyl group such as methanediyl group and naphthalenediylcyclohexanediyl group; and the like.
Of these, a methanediyl group, an ethanediyl group, or a benzenediyl group is preferable, and a methanediyl group is more preferable.

The divalent hydrocarbon group having 1 to 20 carbon atoms represented by M may further have a substituent. Examples of the substituent include a halogen atom, a hydroxy group, a carbonyl group, a carboxy group, a nitro group, a cyano group, an ether group, an ester group, a hydrocarbon group, and a fluorinated hydrocarbon group. Of these, a halogen atom or a fluorinated hydrocarbon group is preferable, and a fluorine atom or a trifluoromethyl group is more preferable.

When the above-mentioned substituents are plural, the above-mentioned substituents may be bonded to each other to form an alicyclic structure or an aliphatic heterocyclic structure having 3 to 20 ring members. Examples of the alicyclic structure or aliphatic heterocyclic structure having 3 to 20 ring members include oxacyclopentane structure, oxacycloalkane structure such as oxacyclohexane structure; dioxacyclopentane structure, and dioxacyclohexane structure. And other lactone structures such as butyrolactone structure and valerolactone structure. Of these, an oxacycloalkane structure or a lactone structure is preferable, and an oxacyclohexane structure or a valerolactone structure is more preferable.

Examples of the divalent organic group having 1 to 20 carbon atoms represented by L include hydrocarbon groups similar to those exemplified as M above, and a hetero atom between carbon and carbon of the hydrocarbon group. Examples thereof include a group having a group.
The group containing a hetero atom which may be contained between carbon and carbon is, for example, one selected from the group consisting of —O—, —S—, —NR ^A —, —CO—, and —CS—. Alternatively, a group in which two or more kinds are combined is included. R ^A is a hydrocarbon group having 1 to 10 carbon atoms. Examples of the hydrocarbon group represented by R ^A include the same hydrocarbon groups as those exemplified as R ¹ above.

The upper limit of the carbon number of the divalent organic group represented by L is preferably 10, more preferably 8, and even more preferably 6. The divalent organic group represented by L is preferably a chain hydrocarbon group and an alicyclic hydrocarbon group, more preferably an alkanediyl group or a cycloalkanediyl group, a methanediyl group or a cyclohexanediyl group. More preferred are groups.

Examples of the alicyclic structure or aliphatic heterocyclic structure having 3 to 20 ring members formed by the above L and M bonded to each other include cyclopentane structure, cycloalkane structure such as cyclohexane structure; butyrolactone structure. And a lactone structure such as a valerolactone structure. Of these, an alicyclic structure is preferable, and a cyclohexane structure is more preferable.

The following are specific examples of the group represented by formula (I).

In the formulas (I-1) to (I-30), * represents a bond.
The repeating unit D1 is preferably a repeating unit represented by the following formula (IA), and more preferably a repeating unit represented by the following formula (Y-1).
In the formula (IA) below, R ² represents a hydrogen atom, a fluorine atom, a methyl group, or a trifluoromethyl group. Z represents a group represented by the above formula (I).

The resin Y may contain the repeating unit D1 alone or in combination of two or more.

When the resin Y contains the repeating unit D1, the content of the repeating unit D1 contained in the resin Y (when a plurality of repeating units D1 is present, the total thereof) is 20 mol based on all repeating units of the resin Y. % Or more, more preferably 40 mol% or more, further preferably 50 mol% or more, particularly preferably 60 mol% or more. The upper limit is not particularly limited, but is, for example, 100 mol% or less, preferably 95 mol% or less, more preferably 80 mol% or less, still more preferably 75 mol% or less.

<Repeating unit D2>
The repeating unit D2 is a repeating unit derived from a monomer represented by the following formula (II).
Formula (II):

In the formula (II), R ¹¹ represents a hydrogen atom, an alkyl group having 1 to 6 carbon atoms which may have a halogen atom, or a halogen atom. R ¹² represents a fluorinated hydrocarbon group having 1 to 10 carbon atoms or a group represented by the formula (IIA). R ¹³ and R ¹⁴ each independently represent an alkyl group having 1 to 4 carbon atoms. A ¹¹ and ^{A 12} are each independently alkanediyl group having 1 to 6 carbon atoms, or ^{^{^{* -A 13 -X 11 - (A}}} 14 -X 12) a-A 15 - represents a. * Represents a bond with an oxygen atom. However, in A ¹¹ and A ¹² , the carbon atom bonded to the oxygen atom is not a tertiary carbon atom. A ¹³ , A ¹⁴ and A ¹⁵ each independently represent an alkanediyl group having 1 to 6 carbon atoms. X ¹¹ and X ¹² each independently represent an oxygen atom, —CO—O—, or —O—CO—. a represents 0 or 1.

Formula (IIA):

Wherein (IIA), A ^T1 represents a divalent aliphatic hydrocarbon group which has ~ 1 carbon atoms which may 18 have a fluorine atom. X ^T1 represents —CO—O— or —O—CO—. A ^T2 represents an aliphatic hydrocarbon group having 1 to 17 carbon atoms, which may have a fluorine atom. However, at least one of A ^T1 and A ^T2 contains one or more fluorine atoms. * Represents a bond with the carbonyl group.

Examples of the halogen atom in the alkyl group having 1 to 6 carbon atoms which may have a halogen atom represented by R ¹¹ include a fluorine atom, a chlorine atom, a bromine atom and an iodine atom. Examples of the alkyl group having 1 to 6 carbon atoms which may have a halogen atom represented by R ¹¹ include, for example, methyl group, ethyl group, n-propyl group, isopropyl group, n-butyl group and sec-butyl group. , Tert-butyl group, n-pentyl group, n-hexyl group, trifluoromethyl group, perfluoroethyl group, perfluoropropyl group, perfluoroisopropyl group, perfluorobutyl group, perfluorosec-butyl group, perfluorotert-butyl group, perfluoro Examples thereof include a pentyl group, a perfluorohexyl group, a perchloromethyl group, a perbromomethyl group, and a periodomethyl group. An alkyl group having 1 to 4 carbon atoms is preferable, and a methyl group or an ethyl group is more preferable.
Examples of the halogen atom represented by R ¹¹ include a fluorine atom, a chlorine atom, a bromine atom, and an iodine atom.
Among them, R ¹¹ is preferably a hydrogen atom or a methyl group.

The fluorinated hydrocarbon group having 1 to 10 carbon atoms represented by R ¹² is not particularly limited, and examples thereof include an aliphatic hydrocarbon group having 1 to 10 carbon atoms having a fluorine atom and a carbon number having a fluorine atom. Examples thereof include 1 to 10 alicyclic hydrocarbon groups.
Examples of the aliphatic hydrocarbon group having 1 to 10 carbon atoms having a fluorine atom include an alkyl group having 1 to 10 carbon atoms having a fluorine atom, and specifically, difluoromethyl group, trifluoromethyl group, 1, 1-difluoroethyl group, 2,2-difluoroethyl group, 1,1,1-trifluoroethyl group, 2,2,2-trifluoroethyl group, perfluoroethyl group, 1,1,2,2-tetrafluoro Propyl group, 1,1,1,2,2-pentafluoropropyl group, 1,1,2,2,3,3-hexafluoropropyl group, perfluoropropyl group, perfluoroethylmethyl group, 1- (trifluoromethyl ) -1,2,2,2-Tetrafluoroethyl group, 1- (trifluoromethyl) -2,2,2-trifluoroethyl group, 1,1,2,2-tetrafluorobutyl group, 1,1 , 2,2,3,3-hexafluorobutyl group, 1,1,1,2,2,3,3-peptafluorobutyl group, 1,1,2,2,3,3,4,4- Octafluorobutyl group, perfluorobutyl group, 1,1-bis (trifluoro) methyl-2,2,2-trifluoroethyl group, 2- (perfluoropropyl) ethyl group, 1,1,2,2,3, 3,4,4-octafluoropentyl group, perfluoropentyl group, 1,1,2,2,3,3,4,4,5,5-decafluoropentyl group, 1,1-bis (trifluoromethyl) -2,2,3,3,3-pentafluoropropyl group, 2- (perfluorobutyl) ethyl group, 1,1,1,2,2,3,3,4,4-nonafluoropentyl group, 1, 1,2,2,3,3,4,4,5,5-decafluorohexyl group, 1,1,2,2,3,3,4,4,5,5,6,6-dodecafluorohexyl group Group, perfluorohexyl group, perfluoropentylmethyl group, and perfluorohexyl group.
Examples of the alicyclic hydrocarbon group having 1 to 10 carbon atoms having a fluorine atom include a cycloalkyl group having 1 to 10 carbon atoms having a fluorine atom, and specific examples thereof include a perfluorocyclohexyl group and a perfluoroadamantyl group. Is mentioned.

The divalent aliphatic hydrocarbon group having 1 to 18 carbon atoms and optionally having a fluorine atom represented by AT ¹ in the formula (IIA) is, for example, a carbon optionally having a fluorine atom. Examples thereof include an alkanediyl group having 1 to 18 carbon atoms and a divalent cyclic aliphatic hydrocarbon group having 1 to 18 carbon atoms, which may have a fluorine atom.
The alkanediyl group having 1 to 18 carbon atoms which may have a fluorine atom preferably has 1 to 10 carbon atoms, more preferably 1 to 6 carbon atoms, and further preferably 2 to 3 carbon atoms.
Specific examples of the alkanediyl group of A ^T1 ~ 1 carbon atoms which may have a fluorine atom represented by 18, methylene bridge, ethanediyl group, propanediyl, butanediyl group, and is represented by R ¹² And a divalent group formed by removing one hydrogen atom or a fluorine atom from the group exemplified as the fluorinated hydrocarbon group having 1 to 10 carbon atoms.
Among them, the alkanediyl group having 1 to 18 carbon atoms which may have a fluorine atom is preferably a perfluoroalkanediyl group, and more preferably a perfluoroalkanediyl group having 2 to 3 carbon atoms.

The divalent cyclic aliphatic hydrocarbon group having 1 to 18 carbon atoms which may have a fluorine atom may be either monocyclic or polycyclic. Examples of the monocyclic divalent aliphatic hydrocarbon group having 1 to 18 carbon atoms include a cyclohexanediyl group and a perfluorocyclohexanediyl group. Examples of the polycyclic divalent aliphatic hydrocarbon group having 1 to 18 carbon atoms include an adamantanediyl group, a norbornanediyl group, and a perfluoroadamantanediyl group.

Examples of the aliphatic hydrocarbon group A ^T2 fluorine atom has optionally 1 carbon atoms which may be ~ 17 aliphatic hydrocarbon group which has 1-3 carbon atoms which may 12 have a fluorine atom is preferable, a fluorine An aliphatic hydrocarbon group having 3 to 10 carbon atoms which may have an atom is more preferable.
Examples of the aliphatic hydrocarbon group A ^T2 fluorine atom has carbon atoms that may 1 be ~ 17, for example, an alkyl group having fluorine atoms and 1 carbon atoms which may have a 17, and a fluorine atom Examples thereof include alicyclic hydrocarbon groups having 1 to 17 carbon atoms which may be possessed.
Specific examples of the alkyl groups of A ^T2 by fluorine atoms and 1 carbon atoms which may have a 17 represented is a methyl group, an ethyl group, n- propyl group, an isopropyl group, n- butyl group, sec- Examples thereof include a butyl group, a tert-butyl group, an n-pentyl group, an n-hexyl group, and groups exemplified as the fluorinated hydrocarbon group having 1 to 10 carbon atoms represented by R ¹² .
Further, examples of the alicyclic hydrocarbon group having 1 to 17 carbon atoms which may have a fluorine atom include a cycloalkyl group having 1 to 17 carbon atoms which may have a fluorine atom. Include a cyclohexyl group, a perfluorocyclohexyl group, and the like.

However, in the formula (IIA), at least one of A ^T1 and A ^T2 contains one or more fluorine atoms. Among ^them, it is preferred ^{that A T1} contains a fluorine atom.

In formula (I), R ¹² is preferably a fluorinated alkyl group having 1 to 6 carbon atoms or a group represented by formula (IIA), and more preferably a group represented by formula (IIA). ..

The alkyl group having 1 to 4 carbon atoms represented by R ¹³ and R ¹⁴ is preferably an alkyl group having 1 to 3 carbon atoms, more preferably a methyl group or an ethyl group, still more preferably a methyl group.

Examples of the alkanediyl group having 1 to 6 carbon atoms represented by A ¹¹ , A ¹² , A ¹³ , A ¹⁴ , and A ¹⁵ include methylene group, ethylene group, propane-1,3-diyl group, butane-1, 4-diyl group, pentane-1,5-diyl group, and linear alkanediyl group such as hexane-1,6-diyl group; ethane-1,1-diyl group, propane-1,2-diyl group, Butane-1,3-diyl group, 2-methylpropane-1,3-diyl group, 2-methylpropane-1,2-diyl group, pentane-1,4-diyl group, and 2-methylbutane-1,4 A branched alkanediyl group such as a diyl group;
Among them, A ¹¹ and A ¹² are preferably alkanediyl groups having 1 to 4 carbon atoms, and more preferably alkanediyl groups having 1 or 2 carbon atoms.

^{^{^{* -A 13 -X 11 - (A}}} 14 -X 12) a-A 15 - ^{^{The, * - A 13 -CO-O}} -A 15 -, * - A 13 -O-CO-A 15 -, or , * -A ¹³ -CO-OA ¹⁴ -CO-OA ¹⁵ -are preferable, and * -A ¹³ -CO-OA ¹⁵ -is more preferable.

Specific examples of the compound (II) are shown below. In addition, in each of the compounds represented by the following formulas (II-1) to (II-11), a compound in which a methyl group corresponding to R ¹¹ is replaced with a hydrogen atom is also mentioned as a specific example of the compound (II). Be done.

As the repeating unit D2, a repeating unit represented by the following formula (Y-2) is preferable.

The resin Y may contain the repeating unit D2 alone or in combination of two or more.

When the resin Y contains the repeating unit D2, the content of the repeating unit D2 contained in the resin Y (when there are a plurality of repeating units D2, the total thereof) is 10 mol with respect to all the repeating units of the resin Y. % Or more, preferably 20 mol% or more, more preferably 30 mol% or more. The upper limit is not particularly limited, but is, for example, 100 mol% or less, preferably 95 mol% or less, more preferably 80 mol% or less, further preferably 50 mol% or less, and particularly preferably 45 mol% or less.

The resin Y may contain a repeating unit other than the repeating unit D1 and the repeating unit D2. Other repeating units are not particularly limited, and examples thereof include a repeating unit having a group (acid-decomposable group) that is decomposed by the action of an acid to increase the polarity, and a repeating unit having a hydrophobic group.
Hereinafter, each of the repeating unit having an acid-decomposable group and the repeating unit having a hydrophobic group will be described in detail.

<Repeating unit having an acid-decomposable group>
The acid-decomposable group includes a structure in which a polar group is protected by a group that decomposes and leaves by the action of an acid (leaving group).
As the polar group, carboxy group, phenolic hydroxyl group, fluorinated alcohol group, sulfonic acid group, sulfonamide group, sulfonylimide group, (alkylsulfonyl) (alkylcarbonyl) methylene group, (alkylsulfonyl) (alkylcarbonyl) imide group , Bis (alkylcarbonyl) methylene group, bis (alkylcarbonyl) imide group, bis (alkylsulfonyl) methylene group, bis (alkylsulfonyl) imide group, tris (alkylcarbonyl) methylene group, tris (alkylsulfonyl) methylene group, etc. Acid groups (groups that dissociate in a 2.38 mass% tetramethylammonium hydroxide aqueous solution), alcoholic hydroxyl groups, and the like.

The alcoholic hydroxyl group is a hydroxyl group bonded to a hydrocarbon group and is a hydroxyl group other than a hydroxyl group (phenolic hydroxyl group) directly bonded to an aromatic ring, and the α-position of the hydroxyl group is electron withdrawing such as a fluorine atom. Aliphatic alcohols substituted with a sexual group (for example, a hexafluoroisopropanol group and the like) are excluded. The alcoholic hydroxyl group is preferably a hydroxyl group having a pKa (acid dissociation constant) of 12 to 20.

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

Preferred groups as the acid-decomposable group are groups in which the hydrogen atom of these groups is replaced with a group capable of leaving by the action of an acid (leaving group).
Examples of the group capable of leaving by the action of an acid (leaving group) include —C (R ₃₆ ) (R ₃₇ ) (R ₃₈ ), —C (R ₃₆ ) (R ₃₇ ) (OR ₃₉ ), and — Examples thereof include C (R ₀₁ ) (R ₀₂ ) (OR ₃₉ ).
In the formula, R ₃₆ to R ₃₉ each independently represent an alkyl group, a cycloalkyl group, an aryl group, an aralkyl group, or an alkenyl group. R ₃₆ and R ₃₇ may combine with each other to form a ring.
R ₀₁ and R ₀₂ each independently represent a hydrogen atom, an alkyl group, a cycloalkyl group, an aryl group, an aralkyl group, or an alkenyl group.

The alkyl group of R ₃₆ to R ₃₉ , R ₀₁ and R ₀₂ is preferably an alkyl group having 1 to 8 carbon atoms, and examples thereof include a methyl group, an ethyl group, a propyl group, an n-butyl group, a sec-butyl group and hexyl. Group and octyl group.
The cycloalkyl group 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 examples thereof include an adamantyl group, a norbornyl group, an isobornyl group, a camphanyl group, a dicyclopentyl group, an α-pinel group, a tricyclodecanyl group, and a tetracyclododecyl group. , And 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 a carbon number of 7 to 12, 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 combining R ₃₆ and R ₃₇ with each other is preferably a cycloalkyl group (monocyclic or polycyclic). The monocyclic cycloalkyl group is preferably a cyclopentyl group, a cyclohexyl group or the like, and the polycyclic cycloalkyl group is preferably a norbornyl group, a tetracyclodecanyl group, a tetracyclododecanyl group or an adamantyl group.

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

The repeating unit having an acid-decomposable group is preferably a repeating unit represented by the following formula (AI).

In 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 a single bond or -COO-Rt-. Rt is preferably a chain alkylene group having 1 to 5 carbon atoms, more preferably —CH ₂ —, — (CH ₂ ) ₂ — or — (CH ₂ ) ₃ —.
T is more preferably a single bond.

In 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 formula (AI), Rx ₁ to Rx ₃ each independently represent an alkyl group or a cycloalkyl group.
Any two of Rx ₁ to Rx ₃ may combine to form a ring structure.
The alkyl group of Rx ₁ , Rx ₂ , and Rx ₃ may be linear or branched, and may be a methyl group, an ethyl group, an n-propyl group, an isopropyl group, an n-butyl group. , Isobutyl group, t-butyl group and the like are preferable. The alkyl group preferably has 1 to 10 carbon atoms, more preferably has 1 to 5 carbon atoms, and further preferably has 1 to 3 carbon atoms. In the alkyl group of Rx ₁ , Rx ₂ , and Rx ₃ , a part of carbon-carbon bonds may be a double bond.
The cycloalkyl group 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 _{two of} Rx ₁ , Rx ₂ , and Rx ₃ may be a monocycle or a polycycle. Examples of the monocyclic ring include monocyclic cycloalkane rings such as cyclopentyl ring, cyclohexyl ring, cycloheptyl ring, and cyclooctane ring. Examples of polycycles include 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 two Rx ₁ , Rx ₂ , and Rx ₃ , the following rings are also preferable.

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

The resin Y may include one type of repeating unit having an acid-decomposable group, or may include two or more types in combination.

When the resin Y contains a repeating unit having an acid-decomposable group, the content of the repeating unit having an acid-decomposable group (when there are a plurality of repeating units having an acid-decomposable group, the total thereof) is It is, for example, 5 mol% or more, preferably 10 mol% or more, based on the repeating unit. The upper limit is not particularly limited, but is, for example, 40 mol% or less, preferably 30 mol% or less.

<Repeating unit having a hydrophobic group>
The resin Y is a fluorine atom, a group having a fluorine atom, a group having a silicon atom, a linear, branched, or cyclic alkyl group having 6 or more carbon atoms, a carbon atom, or a carbon atom from the viewpoint of uneven distribution in the film surface layer. An aryl group having 9 or more carbon atoms, an aralkyl group having 10 or more carbon atoms, an aryl group substituted with at least one linear or branched alkyl group having 3 or more carbon atoms, and at least one carbon number Repeating unit having one or more groups (hereinafter also referred to as "hydrophobic group") selected from the group consisting of aryl groups substituted with 5 or more cyclic alkyl groups (hereinafter "repeating unit having hydrophobic group"). Also referred to as “.”).

As the group having a fluorine atom, a linear, branched or cyclic alkyl group having a fluorine atom or an aryl group having a fluorine atom is preferable.
The linear, branched, or cyclic alkyl group having a fluorine atom is preferably a fluoroalkyl group having 1 to 6 carbon atoms (eg, hexafluoroisopropyl group).
Examples of the aryl group having a fluorine atom include a phenyl group substituted with a fluorine atom.

Examples of the group having a silicon atom include an alkylsilyl group.
Examples of the alkylsilyl group include a trimethylsilyl group, a triethylsilyl group, and a tert-butyldimethylsilyl group.

Examples of the linear, branched, or cyclic alkyl group having 6 or more carbon atoms include linear, branched, or cyclic alkyl groups having 6 to 20 carbon atoms. Examples thereof include a 2-ethylhexyl group, a norbornyl group, an adamantyl group and the like.

Examples of the aryl group having 9 or more carbon atoms include an aryl group having a polycyclic structure formed by combining two or more 5- or 6-membered monocyclic aromatic hydrocarbon rings.

As the aralkyl group having 10 or more carbon atoms, for example, an aralkyl group having 10 to 20 carbon atoms is preferable, and specifically, 1-naphthylmethyl group, 1- (1-naphthyl) ethyl group, triphenylmethyl group. , And a pyrenylmethyl group.

Examples of the aryl group substituted with at least one linear or branched alkyl group having 3 or more carbon atoms include, for example, a linear alkyl group having 3 to 20 carbon atoms (preferably 3 to 10 carbon atoms) or Examples thereof include a phenyl group substituted with a branched chain alkyl group.

Examples of the aryl group substituted with at least one cyclic alkyl group having 5 or more carbon atoms include a phenyl group substituted with a cyclic alkyl group having 5 to 20 carbon atoms (preferably 5 to 10 carbon atoms). Is mentioned.

The repeating unit having a hydrophobic group is preferably a repeating unit represented by the following formula (AII).

In formula (AII), T represents a single bond or a divalent linking group.
The divalent linking group represented by T in formula (AII) has the same meaning as the divalent linking group represented by T in formula (AI) described above, and the preferred embodiments are also the same.
T is preferably a single bond.

In formula (AII), Xb ₁ represents a hydrogen atom, a halogen atom, or a monovalent organic group.
The halogen atom and monovalent organic group represented by Xb ₁ in formula (AII) have the same meanings as the halogen atom and monovalent organic group represented by Xa ₁ in formula (AI), and are preferable. The mode is also the same.
Among them, Xb ₁ is preferably a hydrogen atom or an alkyl group.

In formula (AII), Y ₁ represents the above-mentioned hydrophobic group.

The resin Y may contain one kind of repeating unit having a hydrophobic group, or may contain two or more kinds in combination.

When the resin Y contains a repeating unit having a hydrophobic group, the content of the repeating unit having a hydrophobic group (when there are a plurality of repeating units having a hydrophobic group, the total thereof) is On the other hand, it is, for example, 5 mol% or more, preferably 10 mol% or more. The upper limit is not particularly limited, but is, for example, 60 mol% or less, preferably 50 mol% or less.

When the resin Y includes the repeating unit D1 described above, it is preferable that the resin Y does not substantially include the repeating unit having an acid-decomposable group. The term "substantially free" as used herein means that the content of the repeating unit containing the acid-decomposable group in the resin Y is 5 mol% or less based on all the repeating units of the resin Y. Therefore, the upper limit is preferably 3 mol% or less, more preferably 1 mol% or less, still more preferably 0 mol%.

Moreover, the number of repeating units constituting the resin Y is not particularly limited. The resin Y is preferably composed of, for example, 1 to 5 types of repeating units. The phrase "resin Y is composed of 1 to 5 kinds of repeating units" means that 1 to 5 kinds of repeating units are contained in a content of 5 mol% or more based on all repeating units of resin Y. The intention is to have been. Especially, when the resin Y contains the repeating unit D1 mentioned above, it is more preferable that the resin Y is composed of one kind or four or more kinds of repeating units. When the resin Y includes the repeating unit D2 described above, the resin Y is more preferably composed of three or more kinds of repeating units.
The resin Y can be synthesized by a known method.

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

The resin Y may be used alone or in combination of two or more.
In the composition of the present invention, the content of the resin Y is, for example, 0.1% by mass or more, preferably 1.0% by mass or more, and 2.0% by mass or more based on the total solid content. More preferable. The upper limit is not particularly limited, but is preferably 10.0 mass% or less, more preferably 6.0 mass% or less, and further preferably 5.0 mass% or less.

When the resin Y contains the repeating unit D1, the content of the resin Y is, for example, 2.0 parts by mass or more, and preferably 5.5 parts by mass or more, based on 100 parts by mass of the resin X. The upper limit is not particularly limited, but is, for example, 10.0 parts by mass or less.
When the resin Y contains the repeating unit D2, the content of the resin Y is, for example, 2.0 parts by mass or more, and preferably 5.0 parts by mass or more, based on 100 parts by mass of the resin X. The upper limit is not particularly limited, but is, for example, 10.0 parts by mass or less.

[Photo acid generator]
The composition of the present invention contains a compound that generates an acid upon irradiation with actinic rays or radiation (hereinafter, also referred to as “photoacid generator”).
In addition, the photo-acid generator referred to here is a photo-acid generator that is usually used for causing a deprotection reaction of a resin component (deprotection reaction of an acid-decomposable resin) or for causing a crosslinking reaction of a resin component. Applicable
As the photoacid generator, a compound that generates an organic acid by irradiation with actinic rays or radiation is preferable. Examples thereof include sulfonium salt compounds, iodonium salt compounds, diazonium salt compounds, phosphonium salt compounds, imide sulfonate compounds, oxime sulfonate compounds, diazodisulfone compounds, disulfone compounds, and o-nitrobenzyl sulfonate compounds.

As the photo-acid generator, known compounds that generate an acid upon irradiation with actinic rays or radiation can be used alone or as a mixture thereof, appropriately selected and used. For example, paragraphs [0125] to [0319] of US Patent Application Publication No. 2016 / 0070167A1, paragraphs [0086] to [0094] of US Patent Application Publication 2015 / 0004544A1, and US Patent Application Publication 2016 / Known compounds disclosed in paragraphs [0323] to [0402] of the specification of 0237190A1 can be preferably used as the photoacid generator.

As the photoacid generator, for example, compounds represented by the following formula (ZI), formula (ZII) or formula (ZIII) are preferable.

In the above formula (ZI),
R ₂₀₁ , R ₂₀₂ and R ₂₀₃ each independently represent an organic group.
The carbon number of the organic group as R ₂₀₁ , R ₂₀₂ and R ₂₀₃ is generally 1 to 30, preferably 1 to 20.
Two of R ₂₀₁ to R ₂₀₃ may combine to form a ring structure, and the ring may contain an oxygen atom, a sulfur atom, an ester bond, an amide bond, or a carbonyl group. Examples of the group formed by combining two _{members out} of R ₂₀₁ to R ₂₀₃ include an alkylene group (eg, butylene group, pentylene group, etc.), and —CH ₂ —CH ₂ —O—CH ₂ —CH ₂ — Can be mentioned.
Z ⁻ represents an anion.

Suitable examples of the cation in formula (ZI) include the corresponding groups in compound (ZI-1), compound (ZI-2), compound (ZI-3), and compound (ZI-4) described below. ..
The photo-acid generator may be a compound having a plurality of structures represented by formula (ZI). For example, at least one of _R 201 _{~ R 203} of the compound represented by formula (ZI), at least one and is a single bond or a linking of _R 201 _{~ R 203} of another compound represented by formula (ZI) It may be a compound having a structure bonded via a group.

First, the compound (ZI-1) will be described.
The compound (ZI-1) is an arylsulfonium compound in which at least one of R ₂₀₁ to R ₂₀₃ in formula (ZI) is an aryl group, that is, a compound having arylsulfonium as a cation.
In the arylsulfonium compound, all of R ₂₀₁ to R ₂₀₃ may be 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 arylsulfonium compound include a triarylsulfonium compound, a diarylalkylsulfonium compound, an aryldialkylsulfonium compound, a diarylcycloalkylsulfonium compound, and an aryldicycloalkylsulfonium compound.

The aryl group contained in the arylsulfonium compound is preferably a phenyl group or a naphthyl group, more preferably a phenyl group. The aryl group may be an aryl group having a heterocyclic structure having an oxygen atom, a nitrogen atom, a sulfur atom or the like. Examples of the heterocyclic structure include a pyrrole residue, a furan residue, a thiophene residue, an indole residue, a benzofuran residue, and a benzothiophene residue. When the arylsulfonium compound has two or more aryl groups, the two or more aryl groups may be the same or different.
The alkyl group or cycloalkyl group which the arylsulfonium compound optionally has is a linear alkyl group having 1 to 15 carbon atoms, a branched alkyl group having 3 to 15 carbon atoms, or 3 to 15 carbon atoms. Is preferred, 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 represented by R ₂₀₁ to R ₂₀₃ are each independently an alkyl group (for example, having 1 to 15 carbon atoms), a cycloalkyl group (for example, having 3 to 15 carbon atoms), or an aryl group. It may have a substituent (eg, having 6 to 14 carbon atoms), an alkoxy group (eg, having 1 to 15 carbon atoms), a halogen atom, a hydroxyl group, or a phenylthio group.

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

The alkyl group and cycloalkyl group of R ₂₀₁ to R ₂₀₃ include a straight chain alkyl group having 1 to 10 carbon atoms or a branched chain alkyl group having 3 to 10 carbon atoms (eg, methyl group, ethyl group, propyl group, 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).
R ₂₀₁ to R ₂₀₃ may be further substituted with a halogen atom, an alkoxy group (for example, having 1 to 5 carbon atoms), a hydroxyl group, a cyano group, or a nitro group.

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

In formula (ZI-3),
R _1c to R _5c are each independently a hydrogen atom, an alkyl group, a cycloalkyl group, an aryl group, an alkoxy group, an aryloxy group, an alkoxycarbonyl group, an alkylcarbonyloxy group, a cycloalkylcarbonyloxy group, a halogen atom, a hydroxyl group. Represents a nitro group, an alkylthio group, or an arylthio group.
R _6c and R _7c each independently represent a hydrogen atom, an alkyl group, a cycloalkyl group, a halogen atom, a cyano group, or an aryl group.
R _x and R _y each independently represent an alkyl group, a cycloalkyl group, a 2-oxoalkyl group, a 2-oxocycloalkyl group, an alkoxycarbonylalkyl group, an allyl group, or a vinyl group.

Any two or more of R _1c to R _5c , R _5c and R _6c , R _6c and R _7c , R _5c and R _x , and R _x and R _y may be bonded to each other to form a ring structure. Of course, 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 an aromatic or non-aromatic hydrocarbon ring, an aromatic or non-aromatic heterocycle, and a polycyclic fused ring formed by combining two or more of these rings. The ring structure includes 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 _members out of R _1c to R _5c , R _6c and R _7c , and R _x and R _y include a butylene group and a pentylene group.
The group formed by combining R _5c and R _6c or R _5c and R _x is preferably a single bond or an alkylene group. Examples of the alkylene group include a methylene group and an ethylene group.
Zc ^- represents an anion.

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

In formula (ZI-4),
l represents an integer of 0 to 2.
r represents an integer of 0 to 8.
R ₁₃ represents a group having a hydrogen atom, a fluorine atom, a hydroxyl group, an alkyl group, a cycloalkyl group, an alkoxy group, an alkoxycarbonyl group, or a cycloalkyl group. These groups may have a substituent.
R ₁₄ represents a group having a hydroxyl group, an alkyl group, a cycloalkyl group, an alkoxy group, an alkoxycarbonyl group, an alkylcarbonyl group, an alkylsulfonyl group, a cycloalkylsulfonyl group, or a cycloalkyl group. These groups may have a substituent. When a plurality of R _14's are present, each independently represents the above group such as a hydroxyl group.
R _15's each independently represent an alkyl group, a cycloalkyl group, or a naphthyl group. These groups may have a substituent. Two R _15's may combine with each other to form a ring. When two R _{15 s} are bonded to each other to form a ring, the ring skeleton may contain a hetero atom such as an oxygen atom or a nitrogen atom. In one aspect, it is preferable that two R _15's are alkylene groups and they are bonded to each other to form a ring structure.
Z ⁻ represents an anion.

In the formula (ZI-4), the alkyl group represented by R ₁₃ , R ₁₄ and R ₁₅ is linear or branched. The alkyl group preferably has 1 to 10 carbon atoms. The alkyl group is preferably a methyl group, an ethyl group, an n-butyl group or a t-butyl group.

Next, formulas (ZII) and (ZIII) will be described.
In formulas (ZII) and (ZIII), R ₂₀₄ to R ₂₀₇ each independently represent an aryl group, an alkyl group or a cycloalkyl group.
The aryl group represented by R ₂₀₄ to R ₂₀₇ is preferably a phenyl group or a naphthyl group, more preferably a phenyl group. The aryl group represented by R ₂₀₄ to R ₂₀₇ may be an aryl group having a heterocyclic structure having an oxygen atom, a nitrogen atom, a sulfur atom or the like. Examples of the skeleton of the aryl group having a heterocyclic structure include pyrrole, furan, thiophene, indole, benzofuran, and benzothiophene.
The alkyl group and cycloalkyl group represented by R ₂₀₄ to R ₂₀₇ include a straight chain alkyl group having 1 to 10 carbon atoms, a branched chain alkyl group having 3 to 10 carbon atoms (for example, a methyl group, an ethyl group, Propyl group, butyl group, pentyl group, etc.) or a cycloalkyl group having 3 to 10 carbon atoms (eg cyclopentyl group, cyclohexyl group, norbornyl group, etc.) is preferable.

The aryl group, alkyl group and cycloalkyl group represented by R ₂₀₄ to R ₂₀₇ may each independently have a substituent. Examples of the substituent that the aryl group, alkyl group, and cycloalkyl group represented by R ₂₀₄ to R ₂₀₇ may have include, for example, an alkyl group (for example, having 1 to 15 carbon atoms) and a cycloalkyl group (for example, for carbon Examples thereof include an aryl group (for example, having 6 to 15 carbon atoms), an alkoxy group (for example, having 1 to 15 carbon atoms), a halogen atom, a hydroxyl group, and a phenylthio group.
Z ⁻ represents an anion.

Z in formula (ZI) ^-, Z in formula (ZII) ^-, Zc in formula (ZI-3) ^-, and Z in formula (ZI-4) ^- as the anion represented by the following formula (3) preferable.

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

Xf represents a fluorine atom or an alkyl group substituted with at least one fluorine atom. The alkyl group preferably has 1 to 10 carbon atoms, more preferably 1 to 4 carbon atoms. Further, the alkyl group substituted with at least one fluorine atom is preferably a perfluoroalkyl group.
Xf is preferably a fluorine atom or a perfluoroalkyl group having 1 to 4 carbon atoms, and more preferably a fluorine atom or CF ₃ . In particular, it is more preferable that both Xf's 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 a plurality of R ₄ and R ₅ are present, R ₄ and R ₅ may be the same or different.
The alkyl group represented by R ₄ and R ₅ may have a substituent 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 formula (3).

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

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

The aryl group may be monocyclic or polycyclic. Examples of this aryl group include a phenyl group, a naphthyl group, a phenanthryl group, and an anthryl group.
The heterocyclic group may be monocyclic or polycyclic. Polycyclic compounds can suppress the diffusion of acid more. Further, the heterocyclic group may have aromaticity 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 heterocycle having no aromaticity include a tetrahydropyran ring, a lactone ring, a sultone ring, and a decahydroisoquinoline ring. A furan ring, a thiophene ring, a pyridine ring, or a decahydroisoquinoline ring is particularly preferable as the heterocycle in the heterocyclic group.

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

Examples of the anion represented by the formula _{^{_{(3), SO 3 - -CF}}} 2 -CH 2 -OCO- (L) q'-W, SO 3 - -CF 2 -CHF-CH 2 -OCO- (L) q _{^{_{'-W, SO 3 - -CF 2}}} -COO- (L) q'-W, SO 3 - -CF 2 -CF 2 -CH 2 -CH 2 - (L) q-W, or, SO ₃ ^- - CF ₂ —CH (CF ₃ ) —OCO— (L) q′-W is preferred. Here, L, q, and W are the same as those in Expression (3). q'represents an integer of 0 to 10.

In one embodiment, Z in formula (ZI) ^-, Z in formula (ZII) ^-, Zc in formula (ZI-3) ^-, and Z in formula (ZI-4) ^- The, by the following equation (4) The anions represented are also preferred.

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

Z in formula (ZI) ^-, Z in formula (ZII) ^-, Zc in formula (ZI-3) ^-, and Z in formula (ZI-4) ^- as the anion represented by the following formula (5) preferable.

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

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

Z in formula (ZI) ^-, Z in formula (ZII) ^-, Zc in formula (ZI-3) ^-, and Z in formula (ZI-4) ^- The aromatic represented by the following formula (SA1) Group sulfonate anions are also preferred.

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

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

D represents a single bond or a divalent linking group. Examples of the divalent linking group include an ether group, a thioether group, a carbonyl group, a sulfoxide group, a sulfone group, a sulfonate 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.

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

Anion Z in formula (ZI) ^-, anions Z in the formula (ZII) ^-, Zc in formula (ZI-3) ^-, and Z in formula (ZI-4) ^- shows the preferred embodiment below.

Can be used as a photo-acid generator by combining the above cations and anions arbitrarily.

The composition of the present invention is, among others, one or more photoacids selected from the group consisting of the following formulas (P-1) to (P-8), in that the receding contact angle of the resist film formed is further increased. It is preferable to include a generator.

Another example of the photo-acid generator that can be contained in the composition of the present invention is shown below. In addition, you may use these together.

The photo-acid generator may be in the form of a low molecular weight compound or may be incorporated in a part of the polymer. Further, as the photoacid generator, a photoacid generator in the form of a low molecular compound and a photoacid generator in the form of being incorporated in a part of the polymer may be used in combination.
The photoacid generator is preferably in the form of a low molecular weight compound.
When the photoacid generator is in the form of a low molecular weight compound, the molecular weight is preferably 3,000 or less, more preferably 2,000 or less, still more preferably 1,000 or less.
When the photo-acid generator is in the form of being incorporated in a part of the polymer, it may be incorporated in a part of the resin X described above, or may be incorporated in a resin different from the resin X.
The photo-acid generator may be used alone or in combination of two or more.
In the composition, the content of the photo-acid generator (when plural kinds are present, the total thereof) is preferably 0.1 to 35.0% by mass, based on the total solid content of the composition, and 0.5 to 25. 0.0 mass% is more preferable, and 3.0 to 20.0 mass% is further preferable.
When the compound represented by the above formula (ZI-3) or (ZI-4) is contained as the photo-acid generator, the content of the photo-acid generator contained in the composition (when a plurality of types are present, the total amount thereof is included). ) Is preferably 5.0 to 35.0% by mass, and more preferably 7.0 to 30.0% by mass, based on the total solid content of the composition.

〔solvent〕
The composition of the present invention contains a solvent.
In the composition of the present invention, a known resist solvent can be appropriately used. For example, paragraphs [0665] to [0670] of U.S. Patent Application Publication 2016 / 0070167A1, paragraphs [0210] to [0235] of U.S. Patent Application Publication 2015 / 0004544A1, and U.S. Patent Application Publication 2016 / 0237190A1. Known solvents disclosed in paragraphs [0424] to [0426] of the specification and paragraphs [0357] to [0366] of US Patent Application Publication No. 2016 / 0274458A1 can be 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, cyclic lactone (preferably having 4 to 10 carbon atoms), Examples of the organic solvent include a monoketone compound which may have a ring (preferably having 4 to 10 carbon atoms), alkylene carbonate, alkyl alkoxyacetate, and alkyl pyruvate.

As the organic solvent, a mixed solvent obtained by mixing a solvent having a hydroxyl group in the structure with a solvent having no hydroxyl group may be used.
As the solvent having a hydroxyl group, and the solvent having no hydroxyl group, the above-exemplified compounds can be appropriately selected, but as the solvent having a hydroxyl group, alkylene glycol monoalkyl ether, alkyl lactate or the like is preferable, and propylene glycol monomethyl ether ( PGME), propylene glycol monoethyl ether (PGEE), methyl 2-hydroxyisobutyrate, or ethyl lactate is more preferred. The solvent having no hydroxyl group is preferably an alkylene glycol monoalkyl ether acetate, an alkylalkoxypropionate, a monoketone compound which may have a ring, a cyclic lactone, an alkyl acetate or the like, among which propylene glycol. Monomethyl ether acetate (PGMEA), ethyl ethoxypropionate, 2-heptanone, γ-butyrolactone, cyclohexanone, cyclopentanone or butyl acetate is more preferable, and propylene glycol monomethyl ether acetate, γ-butyrolactone, ethyl ethoxypropionate, 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 from the viewpoint of coating uniformity.
The solvent preferably contains propylene glycol monomethyl ether acetate, and may be a single solvent of propylene glycol monomethyl ether acetate or a mixed solvent of two or more kinds containing propylene glycol monomethyl ether acetate.

[Acid diffusion control agent]
The composition of the present invention may contain an acid diffusion controller as long as the effect of the present invention is not impaired.
The acid diffusion control agent acts as a quencher that traps the acid generated from the photo-acid generator or the like during exposure and suppresses the reaction of the acid-decomposable resin in the unexposed area due to excess acid generated. Examples of the acid diffusion control agent are basic compounds (CA), basic compounds (CB) whose basicity is reduced or eliminated by irradiation with actinic rays or radiation, and weak acids relatively to the photoacid generator. An onium salt (CC), a low molecular weight compound (CD) having a nitrogen atom and having a group capable of leaving by the action of an acid, or an onium salt compound (CE) having a nitrogen atom in the cation portion as an acid diffusion controller Can be used. In the composition of the present invention, a known acid diffusion control agent can be appropriately used. For example, paragraphs [0627] to [0664] of U.S. Patent Application Publication No. 2016 / 0070167A1, paragraphs [0095] to [0187] of U.S. Patent Application Publication 2015 / 0004544A1, and U.S. Patent Application Publication No. 2016 / 0237190A1. The known compounds disclosed in paragraphs [0403] to [0423] of the specification and paragraphs [0259] to [0328] of US Patent Application Publication No. 2016 / 0274458A1 can be suitably used as the acid diffusion controller. ..

The basic compound (CA) is preferably a compound having a structure represented by the following formulas (A) to (E).

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

The alkyl group in formulas (A) and (E) may have a substituent or may be unsubstituted.
Of the above alkyl groups, the alkyl group having a substituent is preferably an aminoalkyl group having 1 to 20 carbon atoms, a hydroxyalkyl group having 1 to 20 carbon atoms, or a cyanoalkyl group having 1 to 20 carbon atoms.
The alkyl groups in formulas (A) and (E) are more preferably unsubstituted.

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

The basic compound (CB) (hereinafter, also referred to as “compound (CB)”) whose basicity decreases or disappears by irradiation with actinic rays or radiation has a proton acceptor functional group and contains actinic rays or It is a compound that is decomposed by irradiation with radiation and its proton acceptor property is reduced or disappears, or the proton acceptor property is changed to acidic.

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

Examples of preferable partial structure of the proton acceptor functional group include a crown ether structure, an azacrown ether structure, a primary to tertiary amine structure, a pyridine structure, an imidazole structure, and a pyrazine structure.

The compound (CB) decomposes upon irradiation with actinic rays or radiation to reduce or disappear the proton acceptor property, or generate a compound in which the proton acceptor property is changed to acidic. Here, the decrease or disappearance of the proton acceptor property, or the change from the proton acceptor property to acidic is a change in the proton acceptor property due to the addition of a proton to the proton acceptor functional group, and Means that, when a proton adduct is produced from a compound (CB) having a proton acceptor functional group and a proton, the equilibrium constant in the chemical equilibrium decreases.
The proton acceptor property can be confirmed by measuring pH.

The acid dissociation constant pKa of the compound generated by decomposition of the compound (CB) upon irradiation with actinic rays or radiation preferably satisfies pKa <-1, more preferably -13 <pKa <-1. It is more preferable that 13 <pKa <-3 is satisfied.

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

In the composition of the present invention, an onium salt (CC), which is a weak acid relative to the photoacid generator, can be used as an acid diffusion controller.
When a photoacid generator and an onium salt that generates an acid that is a weak acid relative to the acid generated from the photoacid generator are mixed and used, the photoacid generator is exposed to actinic rays or radiation. When the acid generated from collides with an onium salt having an unreacted weak acid anion, salt exchange releases the weak acid to produce an onium salt having a strong acid anion. In this process, the strong acid is exchanged with a weak acid having a lower catalytic activity, so that the acid is apparently deactivated and the acid diffusion can be controlled.

As the onium salt which is a weak acid relative to the photoacid generator, compounds represented by the following formulas (d1-1) to (d1-3) are preferable.

In the formula, R ⁵¹ is a hydrocarbon group which may have a substituent, Z ^2c is a hydrocarbon group having 1 to 30 carbon atoms which may have a substituent (provided that the carbon atom adjacent to S is a carbon atom). Is a fluorine atom which is not substituted), R ⁵² is an organic group, Y ³ is a linear, branched or cyclic alkylene group or arylene group, and Rf is a fluorine atom. And M ⁺ are each independently an ammonium cation, a sulfonium cation, or an iodonium cation.

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

An onium salt (CC), which is a weak acid relative to a photoacid generator, is a compound having a cation site and an anion site in the same molecule, and the cation site and the anion site are linked by a covalent bond. (Hereinafter, also referred to as “compound (CCA)”).
The compound (CCA) is preferably a compound represented by any of the following formulas (C-1) to (C-3).

In formulas (C-1) to (C-3),
R ₁ , R ₂ , and R ₃ each independently represent a substituent having 1 or more carbon atoms.
L ₁ represents a divalent linking group or a single bond that links the cation site and the anion site.
—X ⁻ represents an anion moiety selected from —COO ⁻ , —SO ₃ ⁻ , —SO ₂ ⁻ , and —N ⁻ —R ₄ . R ₄ is a carbonyl group (-C (= O)-), a sulfonyl group (-S (= O) _2- ), and a sulfinyl group (-S (= O)-) at a connecting site with an adjacent N atom. Represents a monovalent substituent having at least one of
R ₁ , R ₂ , R ₃ , R ₄ , and L ₁ may combine with each other to form a ring structure. In the formula (C-3), two of R ₁ to R ₃ may be combined to represent one divalent substituent, which may be bonded to the N atom by a double bond.

Examples of the substituent having 1 or more carbon atoms in R ₁ to R ₃ include an alkyl group, a cycloalkyl group, an aryl group, an alkyloxycarbonyl group, a cycloalkyloxycarbonyl group, an aryloxycarbonyl group, an alkylaminocarbonyl group and a cycloalkylamino. Examples thereof include a carbonyl group and an arylaminocarbonyl group. Of these, an alkyl group, a cycloalkyl group, or an aryl group is preferable.

L ₁ as a divalent linking group is a linear or branched alkylene group, a cycloalkylene group, an arylene group, a carbonyl group, an ether bond, an ester bond, an amide bond, a urethane bond, a urea bond, or these two types. Examples thereof include groups formed by combining the above. L ₁ is preferably an alkylene group, an arylene group, an ether bond, an ester bond, or a group formed by combining two or more of these.

The low molecular weight compound (CD) having a nitrogen atom and having a group capable of leaving by the action of an acid (hereinafter, also referred to as “compound (CD)”) has a group capable of leaving by the action of an acid on a nitrogen atom. It is preferably an amine derivative having
The group capable of leaving by the action of an acid is preferably an acetal group, a carbonate group, a carbamate group, a tertiary ester group, a tertiary hydroxyl group, or a hemiaminal ether group, and more preferably a carbamate group or a hemiaminal ether group. ..
The molecular weight of the compound (CD) is preferably 100 to 1000, more preferably 100 to 700, still more preferably 100 to 500.
The compound (CD) may have a carbamate group having a protecting group on the nitrogen atom. The protective group constituting the carbamate group is represented by the following formula (d-1).

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

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

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

In equation (6),
l represents an integer of 0 to 2, m represents an integer of 1 to 3, and satisfies l + m = 3.
Ra represents a hydrogen atom, an alkyl group, a cycloalkyl group, an aryl group or an aralkyl group. When 1 is 2, two Ras may be the same or different, and the two Ras may be connected to each other to form a heterocycle with the nitrogen atom in the formula. This heterocycle may contain a heteroatom other than the nitrogen atom in the formula.
Rb has the same meaning as Rb in the above formula (d-1), and the preferred examples are also the same.
In the formula (6), the alkyl group as Ra, the cycloalkyl group, the aryl group, and the aralkyl group may be independently substituted with the alkyl group as Rb, the cycloalkyl group, the aryl group, and the aralkyl group. The group may be substituted with the same groups as those mentioned above.

Specific examples of the alkyl group, cycloalkyl group, aryl group, and aralkyl group for Ra (these groups may be substituted with the above groups) include the same groups as those described above for Rb. Be done.
Specific examples of the particularly preferred compound (CD) in the present invention include, but are not limited to, the compounds disclosed in paragraph [0475] of US Patent Application Publication 2012 / 0135348A1.

The onium salt compound (CE) having a nitrogen atom in the cation moiety (hereinafter, also referred to as “compound (CE)”) is preferably a compound having a basic moiety containing a nitrogen atom in the cation moiety. The basic moiety is preferably an amino group, and more preferably an aliphatic amino group. It is further preferred that all of the atoms adjacent to the nitrogen atom in the basic site are hydrogen atoms or carbon atoms. Further, from the viewpoint of improving basicity, it is preferable that an electron-withdrawing functional group (a carbonyl group, a sulfonyl group, a cyano group, a halogen atom or the like) is not directly bonded to a nitrogen atom.
Specific preferred examples of the compound (CE) include, but are not limited to, the compounds disclosed in paragraph [0203] of US Patent Application Publication No. 2015 / 03094080A1.

Preferred examples of acid diffusion control agents are shown below.

In the composition of the present invention, the acid diffusion controlling agent may be used alone or in combination of two or more kinds.
When the composition contains an acid diffusion controlling agent, the content of the acid diffusion controlling agent (when plural kinds are present, the total thereof) is 0.1 to 10.0% by mass based on the total solid content of the composition. Is preferred, and 0.1 to 7.0 mass% is more preferred.

[Hydrophobic resin]
The composition of the present invention may include a hydrophobic resin. The hydrophobic resin mentioned here does not include the resin X and the resin Y described above.
When the composition of the present invention contains a hydrophobic resin, it is easy to control the static / dynamic contact angle on the surface of the resist film. This makes it possible to improve the developing characteristics, suppress outgassing, improve the immersion liquid following property in the immersion exposure, and reduce the immersion defects.
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 a polar / nonpolar substance is uniformly mixed. Need not contribute to

The hydrophobic resin is at least one 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 in the film surface layer. A resin having a repeating unit containing a seed is preferable.
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 or may be contained in the side chain. May be.

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

The hydrophobic resin preferably has at least one group selected from the following groups (x) to (z).
(X) Acid group (y) Group that is decomposed by the action of an alkali developing solution to increase its solubility in the alkali developing solution (hereinafter, also referred to as a polar conversion group).
(Z) Group decomposable by the action of acid

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

Examples of the group (y) that is decomposed by the action of the alkaline developer to increase the solubility in the alkaline developer include a lactone group, a carboxylic acid ester group (—COO—), an acid anhydride group (—C (O) OC). (O)-), acid imide group (-NHCONH-), carboxylic acid thioester group (-COS-), carbonate ester group (-OC (O) O-), sulfate ester group (-OSO ₂ O-), and Examples thereof include a sulfonic acid ester group (—SO ₂ O—), and a lactone group or a carboxylic acid ester group (—COO—) is preferable.
The repeating unit containing these groups is, for example, a repeating unit in which these groups are directly bonded to the main chain of the resin, and examples thereof include repeating units of acrylic acid ester and methacrylic acid ester. In this repeating unit, these groups may be bonded to the main chain of the resin via a linking group. Alternatively, this repeating unit may be introduced at the terminal of the resin by using a polymerization initiator or a chain transfer agent having these groups during the polymerization.

The content of the repeating unit having a group (y), which is decomposed by the action of the alkaline developer to increase 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 further preferable.

The repeating unit having a group (z) that is decomposed by the action of an acid in the hydrophobic resin is the same as the repeating unit having an acid-decomposable group that can be contained in the resin Y described above. The repeating unit having a group (z) that decomposes by the action of an acid may have at least one of a fluorine atom and a silicon atom. The content of the repeating unit having a group (z) that decomposes by the action of an acid is preferably 1 to 80 mol%, more preferably 10 to 80 mol%, and further preferably 20 to 20 mol% based on all the repeating units in the hydrophobic resin. 60 mol% is more preferable.
The hydrophobic resin may further have a repeating unit other than the above-mentioned repeating unit.

The repeating unit having 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. Further, the repeating unit having 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 CH ₃ partial structure in the side chain portion, a form in which the hydrophobic resin does not substantially contain a fluorine atom and a silicon atom is also preferable. Further, the hydrophobic resin is preferably substantially composed of only the repeating unit composed of only atoms selected from carbon atom, oxygen atom, hydrogen atom, nitrogen atom and sulfur atom.

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

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

As the hydrophobic resin, a known resin can be used alone or as a mixture thereof, appropriately selected and used. For example, known resins disclosed in paragraphs [0451] to [0704] of US Patent Application Publication No. 2015 / 0168830A1 and paragraphs [0340] to [0356] of US Patent Application Publication 2016 / 0274458A1. Can be suitably used as the hydrophobic resin. Further, the repeating units disclosed in paragraphs [0177] to [0258] of US Patent Application Publication No. 2016 / 0237190A1 are also preferable as the repeating units constituting the hydrophobic resin.

Preferred examples of the monomer corresponding to the repeating unit that constitutes the hydrophobic resin are shown below.

Specific examples of the hydrophobic resin that can be contained in the composition of the present invention are shown below.

The hydrophobic resins may be used alone or in combination of two or more.
It is preferable to mix and use two or more kinds of hydrophobic resins having different surface energies, from the viewpoint of achieving both the immersion liquid following property in the immersion exposure and the developing property.
When a hydrophobic resin is contained in the composition, the content of the hydrophobic resin is preferably 0.01 to 10.0% by mass, and 0.05 to 8.0% by mass based on the total solid content in the composition. % Is more preferable.

[Surfactant]
The composition of the present invention may include a surfactant.
The surfactant is preferably a fluorine-based and / or silicon-based surfactant (specifically, a fluorine-based surfactant, a silicon-based surfactant, or a surfactant having both a fluorine atom and a silicon atom). ..

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

The surfactant 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 (when a plurality of the compounds is contained, the total content thereof) is 0.0001 to 2 mass based on the total solid content of the composition. % Is preferable, and 0.0005 to 1 mass% is more preferable.
On the other hand, when the content of the surfactant is 10 mass ppm or more based on the total solid content of the composition, the uneven distribution of the surface of the hydrophobic resin increases. As a result, the surface of the resist film can be made more hydrophobic, and the water following property during immersion exposure is improved.

[Other additives]
The composition of the present invention further comprises a resin other than those described above, a surfactant, a cross-linking agent, an acid proliferating agent, a dye, a plasticizer, a photosensitizer, a light absorber, an alkali-soluble resin, a dissolution inhibitor, or a dissolution agent. It may contain a promoter and the like.

[Preparation method]

The solid content concentration of the composition of the present invention is preferably 1.0 to 10% by mass, more preferably 2.0 to 5.7% by mass, and further preferably 2.0 to 5.3% by mass. That is, when the composition contains a solvent, the content of the solvent in the composition is preferably adjusted so as to satisfy the preferable range of the solid content concentration. The solid content concentration is a mass percentage of the mass of the resist components other than the solvent with respect to the total mass of the composition.
It is possible to adjust the thickness of the resist film comprising the composition of the present invention by setting the solid content concentration in the composition to an appropriate range so as to have an appropriate viscosity and improving the coatability or film-forming property.

The composition of the present invention is preferably used by dissolving the above-mentioned components in a predetermined organic solvent (preferably the above-mentioned mixed solvent), filtering this, and coating it on a predetermined support (substrate).
The pore size of the filter used for filter filtration is preferably 0.1 μm or less, more preferably 0.05 μm or less, still more preferably 0.03 μm or less. When the solid content concentration of the composition is high (for example, 25% by mass or more), the pore size of the filter used for filter filtration is preferably 3 μm or less, more preferably 0.5 μm or less, and further preferably 0.3 μm or less. This filter is preferably a filter made of polytetrafluoroethylene, polyethylene, or nylon. In the 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 are 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 subjected to deaeration treatment before and after filtration with a filter.

[Physical properties]
The receding contact angle (RCA) of the film formed from the composition of the present invention with respect to water is 73 ° or more, preferably 76 ° or more, more preferably 80 ° or more, and further preferably 81 ° or more. The upper limit is not particularly limited, but is often 90 ° or less.
In the present specification, "receding contact angle of film with respect to water" means the receding contact angle of a film formed under the following conditions.
<Film forming conditions>
The composition of the present invention is applied on a silicon wafer by spin coating and then baked at 100 ° C. for 60 seconds to form a film having a thickness of 100 nm. Then, after dropping 50 μl of a water drop onto the film, the silicon wafer is tilted, and the receding contact angle of the water drop is measured under the environment of room temperature of 23 ° C. and relative humidity of 45%.
The receding contact angle (RCA) can be controlled to 73 ° or more by adjusting, for example, the type and the molar ratio of the repeating unit in the resin Y and the content of the resin Y in the composition.

[Use]
The composition of the present invention relates to an actinic ray-sensitive or radiation-sensitive resin composition which reacts upon irradiation with actinic rays or radiation to change its properties. More specifically, the composition of the present invention comprises a semiconductor manufacturing process such as IC (Integrated Circuit), a circuit board such as liquid crystal or a thermal head, a mold structure for imprinting, other photofabrication process, or The present invention relates to an actinic ray-sensitive or radiation-sensitive resin composition used for producing a lithographic printing plate or 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 Mechanical Systems) and the like.

[Pattern forming method, resist film]
The present invention also relates to a pattern forming method using the above actinic ray-sensitive or radiation-sensitive resin composition. The pattern forming method of the present invention will be described below. Further, the resist film of the present invention will be described together with the description of the pattern forming method.

The pattern forming method of the present invention is
(I) A step of forming a resist film (actinic ray-sensitive or radiation-sensitive film) on a support using the above actinic ray-sensitive or radiation-sensitive resin composition (resist film forming step (film forming step) ),
(Ii) a step of exposing (irradiating with actinic rays or radiation) the resist film (exposure step); and
(Iii) a step of developing the exposed resist film with a developer (developing step),
Have.

The pattern forming method of the present invention is not particularly limited as long as it includes the steps (i) to (iii) described above, and may further include the following steps.
In the pattern forming method of the present invention, it is preferable that the exposure method in the exposure step (ii) is immersion exposure at a scan speed of 700 mm / s or more.
The pattern forming method of the present invention preferably includes (iv) pre-heating (PB: PreBake) step before the (ii) exposure step.
The pattern forming method of the present invention preferably includes (v) post-exposure bake (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) the exposure step a plurality of times.
The pattern forming method of the present invention may include (iv) the preheating step a plurality of times.
The pattern forming method of the present invention may include (v) the 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 (film forming step), (ii) exposing step, and (iii) developing step can be performed by a generally known method.

From the viewpoint of improving resolution, the film thickness of the resist film is preferably 110 nm or less, more preferably 95 nm or less.
If necessary, a resist underlayer film (eg, SOG (Spin On Glass), SOC (Spin On Carbon), and antireflection film) may be formed between the resist film and the support. As a material forming 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. A known material can be appropriately used for the protective film. For example, U.S. Patent Application Publication No. 2007/0178407, U.S. Patent Application Publication No. 2008/0085466, U.S. Patent Application Publication No. 2007/0275326, U.S. Patent Application Publication No. 2016/0299432, The protective film forming composition disclosed in US Patent Application Publication No. 2013/0244438 and International Patent Application Publication No. 2016 / 157988A can be preferably used. The protective film forming composition preferably contains the above-mentioned acid diffusion control agent.
A protective film may be formed on the resist film containing the hydrophobic resin described above.

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

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

The wavelength of the light source used in the exposure step is not limited, but examples thereof include infrared light, visible light, ultraviolet light, far ultraviolet light, extreme ultraviolet light (EUV), X-ray, and electron beam. Of these, far-ultraviolet light is preferable, and its wavelength 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), F ₂ excimer laser (157 nm), X-ray, EUV (13 nm), electron beam or the like is preferable, and KrF excimer laser, ArF excimer laser, EUV or electron beam is more preferable, and ArF excimer laser is further preferable.

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

As the alkali developer, a quaternary ammonium salt typified by tetramethylammonium hydroxide is usually used, but in addition to this, an alkaline aqueous solution of an inorganic alkali, a primary to tertiary amine, an alcohol amine, a cyclic amine, or the like can also be used. It can be used.
Furthermore, the alkaline developer may contain an appropriate amount of alcohols and / or a surfactant. The alkali concentration of the alkali developer is usually 0.1 to 20% by mass. The pH of the alkaline developer is usually 10 to 15.
The time for developing with an alkaline developer is usually 10 to 300 seconds.
The alkali concentration, pH, and development time of the alkali developing solution 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. Preferably.

Examples of the ketone solvent include 1-octanone, 2-octanone, 1-nonanone, 2-nonanone, acetone, 2-heptanone (methyl amyl ketone), 4-heptanone, 1-hexanone, 2-hexanone, diisobutyl ketone, Examples thereof include cyclohexanone, methylcyclohexanone, phenylacetone, methylethylketone, methylisobutylketone, acetylacetone, acetonylacetone, ionone, diacetonyl alcohol, acetylcarbinol, acetophenone, methylnaphthylketone, isophorone, and propylene carbonate.

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, diethylene glycol monoethyl acetate. Ether acetate, ethyl-3-ethoxypropionate, 3-methoxybutyl acetate, 3-methyl-3-methoxybutyl acetate, methyl formate, ethyl formate, butyl formate, propyl formate, ethyl lactate, butyl lactate, propyl lactate, butane Examples thereof include butyl acid salt, 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 a solvent other than the above or water may be mixed. 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 developing solution 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 based on the total amount of the developing solution. % Is particularly preferred.

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, and more preferably 0.01 to 0.5% by mass, based on the total amount of the developer.

The organic developer may contain an acid diffusion controller.

Examples of the developing method include a method of dipping the substrate in a tank filled with the 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 resting for a certain period of time (paddle method), and a substrate. Examples include a method of spraying the developing solution on the surface (spray method) and a method of continuously discharging the developing solution while scanning the developing solution discharge nozzle at a constant speed on a substrate rotating at a constant speed (dynamic dispensing method). Be done.

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

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

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

The rinse solution used in the rinse step after the developing step using the developer containing the organic solvent is not particularly limited as long as it does not dissolve the pattern, and a solution containing a general organic solvent can be used. As the rinse liquid, a rinse liquid 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. Preferably.
Specific examples of the hydrocarbon-based solvent, the ketone-based solvent, the ester-based solvent, the alcohol-based solvent, the amide-based solvent, and the ether-based solvent include the same solvents as those described in the developer containing the organic solvent.
As the rinse liquid used in the rinse step in this case, a rinse 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.
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 methyl isobutyl carbinol.

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

In the rinse step, the developed substrate is washed with a rinse solution. The method of cleaning treatment is not particularly limited, but for example, a method of continuously discharging the rinse liquid onto the substrate rotating at a constant speed (spin coating method), or immersing the substrate in a bath filled with the rinse liquid for a certain period of time A method (dip method), a method of spraying a rinsing liquid on the substrate surface (spray method), or the like can be used. Among them, a method of performing a cleaning treatment by a spin coating method, rotating the substrate at a rotation speed of 2,000 to 4,000 rpm after the cleaning, and removing the rinse liquid from the substrate is preferable. It is also preferable to include a heating step (Post Bake) after the rinse 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 rinse 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 actinic ray-sensitive or radiation-sensitive resin composition of the present invention, and various materials used in the pattern forming method of the present invention (for example, a resist solvent, a developer, a rinse solution, an antireflection film-forming composition, or a top layer). It is preferable that the coating forming composition) does not contain impurities such as metal components, isomers, and residual monomers. The content of these impurities contained in the above various materials is preferably 1 mass ppm or less, more preferably 100 mass ppt or less, further preferably 10 mass ppt or less, and substantially no content (detection by a measuring device) Below the limit) is particularly preferable.

Examples of methods for removing impurities such as metals from the above various materials include filtration using a filter. The pore size of the filter is preferably 10 nm or less, more preferably 5 nm or less, still more preferably 3 nm or less. As the material of the filter, a filter made of polytetrafluoroethylene, polyethylene, or nylon is preferable. As the filter, a filter previously washed with an organic solvent may be used. In the filter filtration step, plural kinds of filters may be connected in series or in parallel and used. When using a plurality of types of filters, filters having different pore sizes and / or materials may be used in combination. Further, various materials may be filtered a plurality of times, and the step of filtering a plurality of times may be a circulation filtration step. As the filter, a filter with reduced eluate as disclosed in Japanese Patent Application Publication No. 2016-201426 (JP-A-2016-201426) is preferable.
In addition to filter filtration, an adsorbent may be used to remove impurities, and 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 the materials disclosed in Japanese Patent Application Publication No. 2016-206500 (JP-A-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 forming various materials, a filter for the raw materials forming various materials is filtered, Alternatively, a method may be mentioned in which the inside of the apparatus is lined with Teflon (registered trademark) or the like to carry out distillation under conditions in which contamination is suppressed as much as possible. It is also preferable to perform glass lining treatment in all steps of the manufacturing facility for synthesizing various materials (binder, photo-acid generator, etc.) of the resist component in order to reduce metal to the ppt order. Preferable conditions for the filter filtration performed on the raw materials constituting various materials are the same as the above-mentioned conditions.

In order to prevent impurities from being mixed in the above-mentioned various materials, US Patent Application Publication No. 2015/0227049, Japanese Patent Application Publication No. 2015-123351 (JP-A-2015-123351), and Japanese Patent Application Publication No. It is preferably stored in a container described in Japanese Patent Application Publication No. 2017-13804 (JP-A-2017-13804).

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

[Method of manufacturing electronic device]
The present invention also relates to a method for manufacturing an electronic device, including the pattern forming method described above. The electronic device manufactured by the method for manufacturing an electronic device of the present invention is suitably mounted on an electric / electronic device (for example, a home electric appliance, an OA (Office Automation) related device, a media related device, an optical device, a communication device, or the like). To be done.

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

[Various ingredients]
[Acid-decomposable resin]
Table 1 shows the structures of the acid-decomposable resins (resins A-1 to A-40) shown in Table 3.
The weight average molecular weight (Mw) and dispersity (Mw / Mn) of the acid-decomposable resin were measured by GPC (carrier: tetrahydrofuran (THF)) (polystyrene-equivalent amount). In addition, the composition ratio (mol% ratio) of the resin was measured by ¹³ C-NMR (nuclear magnetic resonance).
The resins A-1 to A-39 correspond to the resin X. The resins A-1, A-3, A-4, A-6, A-8, A-12, A-13, A-14, A-16, and A-19 are the same as the above-mentioned resin X- 1 to X-10 respectively.

The various monomers shown in Table 1 are shown below.

[Hydrophobic resin]
Table 2 shows the structures of the hydrophobic resins (resins E-1 to E-20) shown in Table 3.
The weight average molecular weight (Mw) and dispersity (Mw / Mn) of the hydrophobic resin were measured by GPC (carrier: tetrahydrofuran (THF)) (polystyrene-equivalent amount). The composition ratio (mol% ratio) of the resin was measured by ¹³ C-NMR.
The resins E-1 to E-15 correspond to the resin Y. Specifically, the resins E-1 to E-7 contain the repeating unit D1 containing the group represented by the above formula (I), and the resins E-8 to E-11 are the same as the above formula (II). The resin E-12 to E-15 contains a repeating unit D2 derived from a monomer represented by the formula (I) and a repeating unit D1 containing a group represented by the formula (I). And a repeating unit D2 derived from the monomer.
The repeating unit derived from the monomer (Z-2) shown below corresponds to the repeating unit represented by the above formula (Y-1), and the repeating unit derived from the monomer (I-5) shown below. Corresponds to the repeating unit represented by the above formula (Y-2).

The various monomers shown in Table 2 are shown below.

[Photo acid generator]
The structures of the photo-acid generators (P-1 to P-8 and PX-1) shown in Table 3 are shown below.

[Acid diffusion control agent]
The structures of the acid diffusion control agents (D-1 to D-4) shown in Table 3 are shown below.

〔solvent〕
The solvents shown in Table 3 are shown below.
F-1: Propylene glycol monomethyl ether acetate (PGMEA)
F-2: cyclohexanone F-3: γ-butyrolactone F-4: propylene glycol monomethyl ether (PGME)
F-5: 2-heptanone

[Preparation of actinic ray-sensitive or radiation-sensitive resin composition]
The actinic ray-sensitive or radiation-sensitive resin composition (hereinafter, also referred to as a resist composition) is prepared by mixing the various components shown in Table 3 and filtering the obtained mixed solution with a polyethylene filter having a pore size of 0.03 μm. Was prepared). The resist composition obtained was used in Examples and Comparative Examples.

[Evaluation of receding contact angle (RCA)]
Each resist composition shown in Table 3 was applied onto a 4-inch silicon wafer by spin coating, and then baked at 100 ° C. for 60 seconds to form a film having a thickness of 100 nm. Then, after dropping 50 μl of a water drop on the obtained film, the silicon wafer was tilted, and the contact angle (°) was measured with the receding contact angle (RCA) being the angle on the rear side of the water drop from which the water drop slides. The measurement environment is room temperature of 23 ° C. and relative humidity of 45%.
The results are shown in Table 4.

[Pattern formation (A) and evaluation]
[Formation of resist film]
An antireflection film ARC29SR (manufactured by Nissan Chemical Industries, Ltd.) was applied onto a silicon wafer (12-inch diameter) and baked at 205 ° C. for 60 seconds to form an antireflection film having a film thickness of 86 nm. The resist composition shown in the above Table 3 was applied thereon and baked at 100 ° C. for 60 seconds to form a resist film having a film thickness of 100 nm.

[ArF exposure]
Then, the obtained resist film was subjected to an ArF excimer laser immersion scanner (XT1950i manufactured by ASML, NA1.35, Dipole, outer sigma 0.981, inner sigma 0.895, Y deflection) at a line width of 45 nm of 1 :. Immersion exposure was performed at a scan speed of 800 mm / s through a 6% halftone mask having a 1-line and space pattern. Ultrapure water was used as the immersion liquid.

[Alkaline development]
Then, after heating at 90 ° C. for 60 seconds, it is developed with a tetramethylammonium hydroxide aqueous solution (2.38% by mass) for 30 seconds, rinsed with pure water, and then spin-dried to a line width of 45 nm in a 1: 1 line and line. Got a space pattern.

The minimum exposure that can form the 45 nm 1: 1 line and space pattern was defined as the effective sensitivity. Then, by the following procedure, the change in line width after application (before exposure) and the change in line width after exposure were evaluated.

[Evaluation of line width change after application (pre-exposure) leaving and line width change after exposure after exposure]
[Evaluation of line width change after coating (before exposure) and leaving]
<Pattern formation (B)>
After performing [resist film formation] by the same method as the pattern formation (A) described above, the obtained wafer with a resist film was stored in the atmosphere for 24 hours. Then, [ArF exposure] and [alkali development] were carried out at the above-mentioned effective sensitivity in the same manner as in the above-mentioned pattern formation (A) to obtain a 1: 1 line and space pattern having a line width of 45 nm.

(Evaluation)
The obtained 1: 1 line-and-space pattern with a line width of 45 nm was observed from above the pattern with a scanning electron microscope (“CG-4100” manufactured by Hitachi High-Technologies Corporation), and the line width was measured at 50 points, and the average was obtained. The value was defined as "average line width value (nm) after coating (before exposure) and leaving". Then, the "line width change amount (nm) after application (before exposure) after leaving" was determined by the following formula (1), and evaluation was performed according to the evaluation criteria described later.
In the formula (1) below, the “average line width value (nm) of normal processing” means that the pattern formation is performed without applying after coating (before exposure) and after exposure. The average line width value (nm) is intended. That is, the 1: 1 line-and-space pattern with a line width of 45 nm obtained by the above-mentioned pattern formation (A) was observed from above the pattern with a scanning electron microscope (“CG-4100” manufactured by Hitachi High-Technologies Corporation), The average value when measuring the line width at 50 points is intended.

Formula (1): Amount of change in line width after application (before exposure) and drawing (nm) = (Average line width value after application (before exposure) and drawing (nm))-(Average line width in normal processing) Value (nm))

(Evaluation criteria)
"A": Line width change is 1.0 nm or less "B": Line width change is more than 1.0 nm and 2.0 nm or less "C": Line width change is more than 2.0 nm and 3.0 nm or less "D": Line width The change is over 3.0 nm. The results are shown in Table 4.

[Evaluation of line width change after exposure after drawing]
<Pattern formation (C)>
After performing [resist film formation] and [ArF exposure] by the same method as the above-described pattern formation (A), the obtained resist-coated wafer was stored in the atmosphere for 24 hours. Then, by performing [alkali development] in the same manner as in the above-mentioned pattern formation (A), a 1: 1 line and space pattern having a line width of 45 nm was obtained.

(Evaluation)
The obtained 1: 1 line-and-space pattern with a line width of 45 nm was observed from above the pattern with a scanning electron microscope (“CG-4100” manufactured by Hitachi High-Technologies Corporation), and the line width was measured at 50 points, and the average was obtained. The value was defined as "average line width value (nm) after exposure and leaving". Then, the “line width change amount (nm) after drawing after exposure” was obtained by the following formula (2), and evaluation was performed according to the evaluation criteria described later. In addition, "the average line width value (nm) of the normal process" in the following formula (2) is synonymous with "the average line width value (nm) of the normal process" in the above formula (1).

Formula (2): Line width change amount after exposure after exposure (nm) = (Average line width value after exposure after exposure (nm))-(Average line width value for normal processing (nm))

From the results in Table 1, it is clear that the resist compositions of Examples can form a resist film in which the change in the line width of the pattern due to the post-application (before the exposure) and the post-exposure after the deposition is suppressed. ..
Further, from the results of Table 1, when the RCA of the film formed by the resist composition is 76 ° or more, the change in the line width of the pattern due to the post-application (before the exposure) and the post-exposure after-exposure is further suppressed. It is clear that the formed resist film can be formed (at least one of the evaluation results of the line width change of the pattern due to the post-application (pre-exposure) and the post-exposure post-setting is “B” or more) .. In particular, when the RCA of the film formed by the resist composition is 81 ° or more, it is possible to obtain a resist film in which the change in the line width of the pattern after application (before exposure) and the change in the pattern due to the exposure after exposure is further suppressed. It is clear that it can be formed (at least one of the evaluation results of the change in the line width of the pattern due to the pulling after coating (before exposure) and the pulling after exposure is “A” evaluation).
On the other hand, it is clear that the resist composition of Comparative Example does not meet the predetermined requirements.

Claims

An actinic ray-sensitive or radiation-sensitive resin composition comprising a resin X, a resin Y, a compound that generates an acid upon irradiation with actinic rays or radiation, and a solvent,
The resin X is a resin whose solubility in an alkaline developer is increased by the action of an acid, and is one kind selected from a repeating unit A derived from one or more kinds of monomers selected from the following monomer group A and one kind selected from the following monomer group B: A repeating unit B derived from the above monomer,
The resin Y contains at least one repeating unit of a repeating unit D1 containing a group represented by the following formula (I) and a repeating unit D2 derived from a monomer represented by the following formula (II),
An actinic ray-sensitive or radiation-sensitive resin composition, wherein a film formed by using the actinic ray-sensitive or radiation-sensitive resin composition has a receding contact angle with water of 73 ° or more.
Monomer group A:

Monomer group B:

Formula (I):

In formula (I), R 1 represents a monovalent alkali-dissociable group having 1 to 20 carbon atoms. M represents a divalent hydrocarbon group having 1 to 20 carbon atoms. L represents a divalent organic group having 1 to 20 carbon atoms and having a carbon atom bonded to an adjacent carbonyl group. The L and the M may be bonded to each other to form an alicyclic structure or an aliphatic heterocyclic structure having 3 to 20 ring members. * Represents a bond.
Formula (II):

In the formula (II), R 11 represents a hydrogen atom, an alkyl group having 1 to 6 carbon atoms which may have a halogen atom, or a halogen atom. R 12 represents a fluorinated hydrocarbon group having 1 to 10 carbon atoms or a group represented by the formula (IIA). R 13 and R 14 each independently represent an alkyl group having 1 to 4 carbon atoms. A 11 and A 12 are each independently alkanediyl group having 1 to 6 carbon atoms, or * -A 13 -X 11 - (A 14 -X 12) a-A 15 - represents a. * Represents a bond with an oxygen atom. However, in A 11 and A 12 , the carbon atom bonded to the oxygen atom is not a tertiary carbon atom. A 13 , A 14 and A 15 each independently represent an alkanediyl group having 1 to 6 carbon atoms. X 11 and X 12 each independently represent an oxygen atom, —CO—O—, or —O—CO—. a represents 0 or 1.
Formula (IIA):

Wherein (IIA), A T1 represents a divalent aliphatic hydrocarbon group which has ~ 1 carbon atoms which may 18 have a fluorine atom. X T1 represents —CO—O— or —O—CO—. A T2 represents an aliphatic hydrocarbon group having 1 to 17 carbon atoms, which may have a fluorine atom. However, at least one of A T1 and A T2 contains one or more fluorine atoms. * Represents a bond with the carbonyl group.
The actinic ray-sensitive or radiation-sensitive resin composition according to claim 1, wherein the monomer group A is the following monomer group A1.
Monomer group A1:
The actinic ray-sensitive or radiation-sensitive resin composition according to claim 1 or 2, wherein the monomer group B is the following monomer group B1.
Monomer group B1:
The actinic ray-sensitive or radiation-sensitive resin according to any one of claims 1 to 3, wherein the resin X further contains a repeating unit C derived from one or more kinds of monomers selected from the following monomer group C. Composition.
Monomer group C:
The actinic ray-sensitive or radiation-sensitive resin composition according to claim 4, wherein the repeating unit C is a repeating unit derived from a monomer represented by the following formula (c-2).
6. The actinic ray-sensitive or radiation-sensitive resin composition according to claim 1, wherein the resin X is a resin represented by the following formulas (X-1) to (X-10). ..
7. The compound that generates an acid upon irradiation with actinic rays or radiation is one or more selected from the group consisting of the following formulas (P-1) to (P-8). The actinic ray-sensitive or radiation-sensitive resin composition as described in 1.
8. The repeating unit D1 contains a repeating unit represented by the following formula (Y-1), and the repeating unit D2 contains a repeating unit represented by the following formula (Y-2). Item 2. The actinic ray-sensitive or radiation-sensitive resin composition according to item 1.
The actinic ray-sensitive or radiation-sensitive resin composition according to any one of claims 1 to 8, wherein the receding contact angle is 81 ° or more.
The actinic ray-sensitive or radiation-sensitive resin composition according to any one of claims 1 to 9, which further comprises an acid diffusion controller.
A resist film obtained by using the actinic ray-sensitive or radiation-sensitive resin composition according to any one of claims 1 to 10.
A resist film forming step of forming a resist film using the actinic ray-sensitive or radiation-sensitive resin composition according to any one of claims 1 to 10,
An exposure step of exposing the resist film,
And a developing step of developing the exposed resist film with a developing solution.
The pattern forming method according to claim 12, wherein the exposure step is a liquid immersion exposure step at a scan speed of 700 mm / s or more.
A method for manufacturing an electronic device, including the pattern forming method according to claim 12.