JP2022125078A - Actinic ray-sensitive or radiation-sensitive resin composition, resist film, pattern formation method, and method for manufacturing electronic device - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide an actinic ray-sensitive or radiation-sensitive resin composition which enables formation of a pattern having a high aspect ratio and a narrow pitch; and to provide a resist film, a pattern formation method, and a method for manufacturing an electronic device.

SOLUTION: An actinic ray-sensitive or radiation-sensitive resin composition contains an ether compound, a resin having a repeating unit having a phenolic polar group and a repeating unit having an acid-decomposable group, a photoacid generator, an acid diffusion control agent that is a compound different from the ether compound, and a solvent, wherein the ether compound is a compound having a group represented by the following general formula (O1); a mass ratio of the content of the ether compound to the content of the acid diffusion control agent is 0.2 or more; a mass ratio of the content of the ether compound to the content of the resin B is 0.1 or less; and a solid content concentration is more than 20 mass%. General expression (O1): *x-(-O-AL-)_a-*y.

SELECTED DRAWING: None

COPYRIGHT: (C)2022,JPO&INPIT

Description

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

After resists for KrF excimer lasers (248 nm), an image forming method called chemical amplification has been used as an image forming method for resists in order to compensate for sensitivity reduction due to light absorption. For example, as a positive chemically amplified image forming method, the photoacid generator in the exposed area is decomposed by exposure to an excimer laser, an electron beam, extreme ultraviolet light, or the like to generate an acid, followed by post-exposure baking (PEB). : Post Exposure Bake), using the generated acid as a reaction catalyst to convert alkali-insoluble groups into alkali-soluble groups, and removing the exposed areas with an alkaline developer.

For example, Patent Document 1 discloses a pattern forming method comprising a step of forming a film having a thickness T on a substrate using a predetermined actinic ray-sensitive or radiation-sensitive resin composition. For example, it is assumed to be 800 nm or more.

International publication WO2017/057226

Until now, ion implantation has been carried out on semiconductors in the manufacturing process of image sensors and the like. In recent years, due to the demand for higher resolution of this ion implantation, the resist film has been made thicker, and the pattern obtained has a higher aspect ratio (the ratio of the height to the width of the formed line is large). Even in this case, it is required that the pattern can be formed at a narrow pitch (interval).
When the present inventors examined the actinic ray-sensitive or radiation-sensitive resin composition described in Patent Document 1, there was room for improvement in the pitch of the pattern when the aspect ratio of the pattern was increased. I found out that there is

Accordingly, an object of the present invention is to provide an actinic ray-sensitive or radiation-sensitive resin composition capable of forming a pattern having a high aspect ratio and a narrow pitch.
Another object of the present invention is to provide a resist film, a pattern forming method, and an electronic device manufacturing method.

As a result of intensive studies aimed at achieving the above object, the present inventors have found that the above object can be solved by a given actinic ray-sensitive or radiation-sensitive resin composition containing an ether compound, and completed the present invention. let me
That is, the inventors have found that the above object can be achieved by the following configuration.

[1]
an ether compound;
a resin having a repeating unit having a phenolic polar group and a repeating unit having an acid-decomposable group;
a photoacid generator;
an acid diffusion controller that is a compound different from the ether compound;
An actinic ray-sensitive or radiation-sensitive resin composition containing a solvent,
The mass ratio of the content of the ether compound to the content of the acid diffusion control agent is 0.2 or more,
The mass ratio of the content of the ether compound to the content of the resin is 0.1 or less,
An actinic ray-sensitive or radiation-sensitive resin composition having a solid content concentration of more than 20% by mass.
[2]
The actinic ray-sensitive or radiation-sensitive resin composition according to [1], wherein the ether compound contains a nitrogen atom.
[3]
The actinic ray-sensitive or radiation-sensitive resin composition according to [1] or [2], wherein the ether compound is a compound represented by general formula (X1) described below.
[4]
The actinic ray-sensitive or radiation-sensitive resin composition according to [3], wherein at least one R ^q1 in general formula (X1) described later is a benzene ring group.
[5]
The actinic ray-sensitive or radiation-sensitive resin composition according to any one of [1] to [4], wherein the content of repeating units having a benzene ring group is less than 65 mol% in all repeating units of the resin. thing.
[6]
The actinic ray-sensitive or radiation-sensitive resin composition according to any one of [1] to [5], wherein the resin further has a repeating unit represented by general formula (VW) described later.
[7]
The photoacid generator is one or more compounds selected from the group consisting of a compound represented by general formula (ZI-3) described later and a compound represented by general formula (ZI-4) described later. The actinic ray-sensitive or radiation-sensitive resin composition according to any one of [1] to [6].
[8]
A resist film formed using the actinic ray-sensitive or radiation-sensitive resin composition according to any one of [1] to [7].
[9]
A step of forming a resist film using the actinic ray-sensitive or radiation-sensitive resin composition according to any one of [1] to [7];
exposing the resist film;
and developing the exposed resist film using a developer.
[10]
A method for manufacturing an electronic device, comprising the pattern forming method according to [9].

According to the present invention, it is possible to provide an actinic ray-sensitive or radiation-sensitive resin composition capable of forming a pattern having a high aspect ratio and a narrow pitch.
Further, according to the present invention, it is possible to provide a resist film, a pattern forming method, and an electronic device manufacturing method.

The present invention will be described in detail below.
The description of the constituent elements described below may be made based on representative embodiments of the present invention, but the present invention is not limited to such embodiments.
The term "actinic ray" or "radiation" as used herein refers to, for example, the emission line spectrum of a mercury lamp, far ultraviolet rays represented by excimer lasers, extreme ultraviolet rays (EUV light: Extreme Ultraviolet), X-rays, and electron beams (EB : Electron Beam) and the like. As used herein, "light" means actinic rays or radiation.
The term "exposure" as used herein means, unless otherwise specified, not only exposure by the emission line spectrum of a mercury lamp, far ultraviolet rays represented by excimer lasers, extreme ultraviolet rays, X-rays, and EUV light, but also electron beams, and It also includes drawing with particle beams such as ion beams.
In the present specification, the term "~" is used to include the numerical values before and after it as lower and upper limits.

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

As used herein, pKa (acid dissociation constant pKa) represents the acid dissociation constant pKa in an aqueous solution. ). A lower acid dissociation constant pKa indicates a higher acid strength. Specifically, the acid dissociation constant pKa in an aqueous solution can be measured by measuring the acid dissociation constant at 25° C. using an infinitely diluted aqueous solution. Alternatively, a value based on a database of Hammett's substituent constants and known literature values can be obtained by calculation using Software Package 1 described below. All pKa values described herein are calculated using this software package.

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

Regarding the notation of groups (atomic groups) in this specification, the notations that do not describe substitution and unsubstituted include not only groups having no substituents but also groups having substituents. For example, an "alkyl group" includes not only an alkyl group having no substituent (unsubstituted alkyl group) but also an alkyl group having a substituent (substituted alkyl group). Also, the term "organic group" as used herein refers to a group containing at least one carbon atom.

Moreover, in the present specification, the type of substituent, the position of the substituent, and the number of substituents are not particularly limited when it is said that it may have a substituent. The number of substituents can be, for example, one, two, three, or more. Examples of substituents include monovalent nonmetallic atomic groups excluding hydrogen atoms, which can be selected from the following substituent group T, for example.
(substituent T)
The substituent T includes halogen atoms such as a fluorine atom, a chlorine atom, a bromine atom, and an iodine atom; alkoxy groups such as a methoxy group, an ethoxy group, and a tert-butoxy group; aryloxy 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 acyl groups such as groups, methacryloyl groups, and methoxalyl groups; alkylsulfanyl groups such as methylsulfanyl groups and tert-butylsulfanyl groups; arylsulfanyl groups such as phenylsulfanyl groups and p-tolylsulfanyl groups; alkyl groups; aryl group; heteroaryl group; hydroxyl group; carboxy group; formyl group; sulfo group; cyano group; arylamino groups; and combinations thereof.

[Actinic ray-sensitive or radiation-sensitive resin composition]
The actinic ray-sensitive or radiation-sensitive resin composition (hereinafter also simply referred to as "resist composition") of the present invention comprises an ether compound, a repeating unit having a phenolic polar group, and a repeating unit having an acid-decomposable group. resin, a photoacid generator, an acid diffusion controller which is a compound different from the ether compound, and a solvent.
Further, in the resist composition, the mass ratio of the content of the ether compound to the content of the acid diffusion control agent is 0.2 or more.
Similarly, the mass ratio of the content of the ether compound to the content of the resin in the resist composition is 0.1 or less.
Furthermore, the solid content concentration is greater than 20% by mass.

Although the mechanism by which the resist composition having such a structure can solve the problems of the present invention is not necessarily clear, the present inventors believe as follows.
The presence of a certain proportion of an ether compound in the resist composition improves the adhesion of the resist film to the substrate, etc., and suppresses pattern collapse even when a pattern with a high aspect ratio is formed. It is believed that the improvement in the contrast and the like of the pattern resolved in the process of development contributes to the solution of the problems of the present invention.
Further, the resist composition of the present invention has a solid content concentration of more than 20% by mass, and furthermore, the resin has a repeating unit having a phenolic polar group, thereby obtaining a pattern having a high aspect ratio. It is believed that the suitability for forming thick resist films used for this purpose is improving.
In addition, the pattern obtained using the resist composition of the present invention is also excellent in cross-sectional shape (rectangularity) of the pattern.

Components contained in the resist composition of the present invention are described in detail below. The resist composition of the present invention may be either a positive resist composition or a negative resist composition. Moreover, it may be a resist composition for alkali development or a resist composition for organic solvent development. Among them, it is preferably a positive resist composition and a resist composition for alkali development.
The resist composition of the present invention is typically a chemically amplified resist composition.

<Ether compound>
The resist composition of the invention contains an ether compound.
The molecular weight of the ether compound is preferably 100-2000, more preferably 150-1000, and even more preferably 200-600.
An ether compound is a compound having an ether group (--O--).
The ether group is attached to each carbon atom at two attachment positions,
However, the ether group possessed by the ether compound is not intended to be a group that forms an ester group by directly bonding to a carbonyl carbon (a carbon atom forming -C(=O)-).

The ether compound is preferably, for example, a compound having a group represented by general formula (O1) below.
*x-(-O-AL-) _a- *y (O1)

In general formula (O1), *x and *y represent bonding positions with groups other than the group represented by general formula (O1).

AL represents an alkylene group. The above alkylene group may be branched or linear. Moreover, it may or may not have a cyclic structure.
The alkylene group preferably has 1 to 10 carbon atoms, more preferably 1 to 5 carbon atoms, and still more preferably 2 to 3 carbon atoms.
The substituents that the alkylene group may have are not particularly limited, and are preferably unsubstituted. In addition, the preferable number of carbon atoms described above is a number that does not include the number of carbon atoms contained in the substituent.
Among them, the alkylene group is preferably -CH ₂ -CH ₂ - or -CH ₂ -CH ₂ -CH ₂ -.
When multiple ALs are present, the multiple ALs may be the same or different.

a represents an integer of 1 or more. a is preferably 1 to 10, more preferably 1 to 6, even more preferably 1 to 4.

The group represented by the general formula (O1) and the group bonded with *x are not particularly limited, and examples thereof include a hydrogen atom, an alkylene group, an aromatic ring group (preferably having 6 to 15 carbon atoms; Alternatively, an alkyl group (preferably having 1 to 5 carbon atoms) may be mentioned.
Further, when a is 1, the atom bonded to the group represented by general formula (O1) with *x is a carbon atom other than carbonyl carbon. Carbon atoms other than the carbonyl carbon include, for example, carbon atoms constituting an aromatic ring group (preferably having 6 to 15 carbon atoms, preferably an aromatic hydrocarbon group, more preferably a benzene ring group), an alkyl group (preferably A carbon atom constituting 1 to 5 carbon atoms or a carbon atom constituting an alkylene group is preferable.

There are no particular restrictions on the group that bonds to the group represented by the general formula (O1) with *y. , and —NR _p R _q .
R _p and R _q each independently represent a hydrogen atom or a substituent. R _p and R _q may combine with each other to form a ring. R _p or R _q becomes a divalent linking group (eg, an alkylene group (preferably having 1 to 5 carbon atoms)), and is bonded to the group represented by general formula (O1) with *x to form the general formula ( A ring containing the group represented by O1) may be formed.
Each of R _p , R _q , and the ring formed by combining R _p and R _q may have a group represented by general formula (O1). Further, the divalent linking group R _p or R _q may have a group represented by general formula (O1).

In addition, in the group represented by the general formula (O1), at least one of a group that bonds with *x is a group other than a hydrogen atom and a group that bonds with *y is a group other than a hydroxyl group. It is preferable to meet the requirements of

The number of groups represented by general formula (O1) in the ether compound is preferably 1 or more, more preferably 1 to 5, even more preferably 1 to 3.
When the ether compound has a plurality of groups represented by general formula (O1), they may be the same or different.
The number of groups represented by general formula (O1) in the ether compound is the number obtained by counting the number of groups represented by general formula (O1) present in each compound as small as possible. be. For example, an ether compound represented by “phenyl group —O—CH ₂ —CH ₂ —O—CH ₂ —CH ₂ —O—CH ₂ —CH ₂ —O-phenyl group” has the general formula It has one group represented by (O1).

The ether compound is preferably a nitrogen-containing compound. That is, the ether compound is preferably a compound containing an ether group and a nitrogen atom. The number of nitrogen atoms possessed by the ether compound, which is a nitrogen-containing compound, is not particularly limited, and is preferably 1 to 5, for example.

Among them, the ether compound is preferably a compound represented by general formula (X1).
[R ^q1 -(-O-AL-) _m ] _n -N-R ^q2 _3-n (X1)

In general formula (X1), m represents an integer of 1-10. m is preferably 1 to 6, more preferably 1 to 4.
When there are multiple m, that is, when n is an integer of 2 or more, the multiple m may be the same or different.

n represents an integer of 1 to 3;

AL represents an alkylene group. The form that AL in general formula (X1) can take is the same as the form that AL in general formula (O1) can take.
When multiple ALs are present, the multiple ALs may be the same or different.

R ^q1 represents a hydrogen atom or a substituent. The substituent of R ^q1 is, for example, preferably an organic group, an aromatic ring group (preferably having 6 to 15 carbon atoms, preferably an aryl group, more preferably a benzene ring group), or an alkyl group (preferably having 1 to 5) are more preferred.
The substituent of the aromatic ring group in R ^q1 is preferably, for example, an alkoxy group (preferably having 1 to 5 carbon atoms).
When multiple R ^q1 are present, the multiple R ^q1 may be the same or different.
At least one R ^q1 among R ^q1 which may exist in plurality is preferably a benzene ring group.

In addition, when one or more of m, which may be present in plurality, is 1, and a group represented by [R ^q1 -(-O-AL-)] is present in the general formula (X1). , R ^q1 in such a group is more preferably an organic group, an aromatic ring group (preferably having 6 to 15 carbon atoms, preferably an aryl group, more preferably a benzene ring group), or an alkyl group (preferably more preferably has 1 to 5 carbon atoms).
In such [R ^q1 -(-O-AL-)], the atom directly bonded to (-O-AL-) in R ^q1 is an atom other than a hydrogen atom and a carbonyl carbon atom. Atoms are preferred, and carbon atoms other than carbonyl carbon are more preferred. Carbon atoms other than the carbonyl carbon include, for example, carbon atoms constituting an aromatic ring group (preferably having 6 to 15 carbon atoms, preferably an aromatic hydrocarbon ring group, more preferably a benzene ring group), or an alkyl group. (preferably 1 to 5 carbon atoms) are preferred.

R ^q2 represents a hydrogen atom or a substituent. The substituent of R ^q2 is not particularly limited, and for example, an organic group having 1 to 20 carbon atoms is preferable, and an alkyl ester alkyl group having 1 to 17 carbon atoms is more preferable.
When multiple R ^q2 are present, the multiple R ^q2 may be the same or different.

When n is 1 or 2, R ^q1 and R ^q2 may combine with each other to form a ring.
The group formed by combining R ^q1 and R ^q2 is preferably an alkylene group (preferably having 1 to 5 carbon atoms).
Among them, when one or more of m is 1, R ^q1 in [R ^q1 -(-O-AL-)] present in the general formula (X1) is bonded to R ^q2 Forming a ring is preferred. In this case, in the group formed by bonding R ^q1 and R ^q2 together, the atom directly bonded to (—O—AL—) is a carbon atom other than a carbonyl carbon (e.g., a carbon atom constituting an alkylene group ) is preferred.

When multiple [R ^q1 -(-O-AL-) _m ] are present in the general formula (X1), the multiple [R ^q1 -(-O-AL-) _m ] may be the same or different. good.
In general formula (X1), at least one R ^q1 is preferably an aromatic ring group (preferably having 6 to 15 carbon atoms), preferably an aryl group (preferably having 6 to 15 carbon atoms), phenyl more preferably a group.

In addition, it is preferable that the ether compound does not have a fluorine atom.

In the resist composition, the mass ratio R1 of the content of the ether compound to the content of the acid diffusion control agent (content of ether compound/content of acid diffusion control agent) is 0.2 or more. ~100 is preferred, 0.2 to 20 is more preferred, and 0.2 to 1 is even more preferred.
In the resist composition, the mass ratio R2 of the content of the ether compound to the content of the resin (content of the ether compound/content of the resin) is 0.1 or less, and 0.0002 to 0.05. is preferred, 0.0002 to 0.01 is more preferred, and 0.0003 to 0.005 is even more preferred.
The acid diffusion control agent and resin will be detailed later.
The content of the ether compound in the resist composition is not particularly limited as long as it satisfies the above-mentioned R1 and R2 specifications, and for example, it is preferably 0.006 to 8% by mass based on the total solid content of the resist composition. 0.01 to 1% by mass is more preferable, and 0.02 to 0.5% by mass is even more preferable.
In addition, solid content intends the component which forms a resist film, and does not include a solvent. In addition, as long as it is a component that forms a resist film, it is regarded as a solid content even if its property is liquid.
An ether compound may be used individually by 1 type, and may be used 2 or more types. When two or more ether compounds are used, the total content is preferably within the above range.

<Resin>
The resist composition of the present invention contains a resin having a repeating unit having a phenolic polar group and a repeating unit having an acid-decomposable group (simply referred to as "resin B" or "resin").

(Repeating unit having phenolic polar group)
Resin B has repeating units with phenolic polar groups. By phenolic polar group is intended a group in which a polar group is attached to an aromatic ring group.
The aromatic ring group may be an aromatic hydrocarbon ring group or an aromatic heterocyclic group. Also, the aromatic ring group may be monocyclic or polycyclic. In addition, the aromatic ring group may be condensed with a non-aromatic ring.
The aromatic ring group includes a benzene ring group, a naphthalene ring group, and an aromatic hydrocarbon ring group having 6 to 18 carbon atoms such as an anthracene ring group, or, for example, a thiophene ring group, a furan ring group, a pyrrole ring group, benzothiophene ring group, benzofuran ring group, benzopyrrole ring group, triazine ring group, imidazole ring group, benzimidazole ring group, triazole ring group, thiadiazole ring group, thiazole ring group, and other heterocyclic aromatic heterocyclic groups is preferred.
Among them, the aromatic ring group is preferably an aromatic hydrocarbon group, more preferably a benzene ring group.

The polar group that binds to the aromatic ring group is preferably an alkali-soluble group, such as hydroxyl group, carboxyl 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) Acid groups such as a methylene group and a tris(alkylsulfonyl)methylene group are included.

・General formula (P01)
The repeating unit having a phenolic polar group is preferably a repeating unit represented by general formula (P01).

R ₄₁ , R ₄₂ and R ₄₃ each independently represent a hydrogen atom, an alkyl group, a cycloalkyl group, a halogen atom, a cyano group or an alkoxycarbonyl group.
Among them, R ₄₁ , R ₄₂ and R ₄₃ are preferably hydrogen atoms.

The alkyl groups for R ₄₁ , R ₄₂ and R ₄₃ include methyl group, ethyl group, propyl group, isopropyl group, n-butyl group, sec-butyl group, hexyl group, 2-ethylhexyl group, octyl group and An alkyl group having 20 or less carbon atoms such as , dodecyl group is preferable, and an alkyl group having 8 or less carbon atoms is more preferable.

As the alkyl group contained in the alkoxycarbonyl group, the same groups as the alkyl groups for R ₄₁ , R ₄₂ and R ₄₃ are preferable.

The cycloalkyl group may be monocyclic or polycyclic, and monocyclic cycloalkyl groups having 3 to 8 carbon atoms such as cyclopropyl, cyclopentyl and cyclohexyl are preferred.

A fluorine atom is preferable as the halogen atom.

R ₄₂ may combine with a substituent of Ar ₄ described below or with L ₄ to form a ring.

X ₄ represents a single bond, -COO- or -CONR ₄₄ -.
_R44 represents a hydrogen atom or an alkyl group.
As the alkyl group, the same alkyl groups as those of R ₄₁ to R ₄₃ are preferable.
X ₄ is preferably a single bond, -COO- or -CONH-, more preferably a single bond or -COO-, still more preferably a single bond.

L4 represents a single bond or a _divalent linking group.
Examples of divalent linking groups include ether groups, carbonyl groups, ester groups, thioether groups, —SO ₂ —, —NR— (R represents a hydrogen atom or an alkyl group), divalent hydrocarbon groups ( Examples thereof include an alkylene group, an alkenylene group (eg -CH=CH-), an alkynylene group (eg -C≡C-), and an arylene group), or a combination thereof.
Among them, the divalent linking group is preferably an alkylene group, and the alkylene group is more preferably an alkylene group having 1 to 8 carbon atoms such as a methylene group, an ethylene group, a propylene group, a butylene group, a hexylene group, and an octylene group. preferable.
Also, when L ₄ and R ₄₂ combine to form a ring, L ₄ represents a trivalent linking group. In this case, among the groups described above as the divalent linking group for L ₄ , the group that can further have a substituent, the substituent and R ₄₂ are bonded to each other to form a single bond or a divalent link It is preferable to form a group (for example, the groups described above), and a single bond or an alkylene group (methylene group, ethylene group, propylene group, butylene group, hexylene group, octylene group, etc.) is preferably an alkylene group having 1 to 8 carbon atoms. ) is more preferred.
The ring formed when _R42 and L4 are bonded is preferably a 5- or ₆ -membered ring.
Among them, _L4 is preferably a single bond.

Ar ₄ represents an (n+1)-valent aromatic ring group. Ar ₄ may have a substituent other than Y, and the substituent other than Y is preferably not a polar group. When the substituent of Ar ₄ and R ₄₂ combine to form a ring, Ar ₄ represents an (n+2)-valent aromatic ring group.
As the aromatic ring group for Ar ₄ , the same aromatic ring groups as described above are exemplified.
Among them, Ar ₄ is preferably an aromatic hydrocarbon ring group having 6 to 18 carbon atoms, more preferably a benzene ring group.
The substituent of Ar ₄ and R ₄₂ are preferably bonded to form a single bond or a divalent linking group (e.g., the group described above), and a single bond or an alkylene group (methylene group, ethylene preferably an alkylene group having 1 to 8 carbon atoms such as a propylene group, a butylene group, a hexylene group, and an octylene group).

Y represents a polar group.
The polar groups are similarly exemplified by the polar groups described above. Among them, a hydroxyl group is preferable as the polar group.
Moreover, when Ar ₄ is an aromatic heterocyclic group having a benzene ring group portion, Y is preferably bonded to the benzene ring group portion contained in the aromatic heterocyclic group.

n represents an integer of 1-4.

Examples of substituents that the above-described alkyl group, cycloalkyl group, alkoxycarbonyl group, alkylene group, aromatic ring group, aromatic hydrocarbon ring group, and the like may have include the substituent T described above. In addition, the number of carbon atoms described for the alkyl group, cycloalkyl group, alkoxycarbonyl group, alkylene group, aromatic ring group, aromatic hydrocarbon ring group, etc. described above does not include the number of carbon atoms possessed by the substituent. .

The content of repeating units having a phenolic polar group is preferably 20 to 74 mol %, more preferably 30 to 64 mol %, still more preferably 45 to 64 mol %, based on the total repeating units of Resin B.
Repeating units having a phenolic polar group may be used alone or in combination of two or more. When two or more are used, the total content thereof is preferably within the above range.

(Repeating unit having an acid-decomposable group)
Resin B has a repeating unit having an acid-decomposable group.
An acid-decomposable group is a group having a structure in which a polar group is protected with a protective group that is released by the action of an acid.
A protecting group is a group that is eliminated by the action of an acid. The protecting group preferably forms an acid-decomposable group by substituting a hydrogen atom of the polar group.
Since the resin B has a repeating unit having such an acid-decomposable group, the resin B is typically an alkali-insoluble or poorly soluble resin, and the protecting group is eliminated by the action of an acid. By doing so, it is a resin whose solubility in alkali increases. Similarly, typically, the resin B is a resin soluble in an organic solvent, and is a resin whose solubility in an organic solvent decreases due to elimination of protective groups by the action of an acid.

As the polar group to be protected with a protecting group, an alkali-soluble group is preferable, and examples thereof include a carboxyl group, a phenolic hydroxyl group, a fluorinated alcohol group, a sulfonic acid group, a sulfonamide group, a 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(alkyl carbonyl)methylene group, acidic groups such as tris(alkylsulfonyl)methylene group, and alcoholic hydroxyl group.
Among them, the polar group to be protected by a protecting group is preferably a carboxyl group, a phenolic hydroxyl group, a fluorinated alcohol group (preferably a hexafluoroisopropanol group), or a sulfonic acid group, and a carboxyl group or a phenolic hydroxyl group is preferable. A carboxyl group is more preferred, and a carboxyl group is even more preferred.

Examples of the protecting group include groups represented by formulas (Y1) to (Y4).
Formula (Y1): -C(Rx ₁ )(Rx ₂ )(Rx ₃ )
Formula (Y2): -C(=O)OC(Rx ₁ )(Rx ₂ )(Rx ₃ )
Formula (Y3): —C(R ₃₆ )(R ₃₇ )(OR ₃₈ )
Formula (Y4): -C(Rn)(H)(Ar)

In formula (Y1) and formula (Y2), Rx ₁ to Rx ₃ are each independently an alkyl group (linear or branched), a cycloalkyl group (monocyclic or polycyclic), an aryl group, an aralkyl group , or represents an alkenyl group. When all of Rx ₁ to Rx ₃ are alkyl groups (linear or branched), at least two of Rx ₁ to Rx ₃ are preferably methyl groups.
Among them, Rx ₁ to Rx ₃ preferably each independently represent a linear or branched alkyl group, and Rx ₁ to Rx ₃ each independently represent a linear alkyl group. more preferred.
Two of Rx ₁ to Rx ₃ may combine to form a monocyclic or polycyclic ring.
The alkyl groups of Rx ₁ to Rx ₃ are alkyl groups having 1 to 4 carbon atoms such as methyl group, ethyl group, n-propyl group, isopropyl group, n-butyl group, isobutyl group and t-butyl group. preferable.
Cycloalkyl groups for Rx ₁ to Rx ₃ include monocyclic cycloalkyl groups such as cyclopentyl group or cyclohexyl group, norbornyl group, tetracyclodecanyl group, tetracyclododecanyl group, adamantyl group, and the like. is preferred.
The aryl group represented by Rx ₁ to Rx ₃ is preferably an aryl group having 6 to 10 carbon atoms, such as phenyl group, naphthyl group and anthryl group.
The aralkyl groups represented by Rx ₁ to Rx ₃ are preferably aralkyl groups having 7 to 12 carbon atoms, such as benzyl, phenethyl and naphthylmethyl groups.
The alkenyl groups represented by Rx ₁ to Rx ₃ are preferably alkenyl groups having 2 to 8 carbon atoms, such as vinyl, allyl, butenyl and cyclohexenyl groups.
The cycloalkyl group formed by combining two of Rx ₁ to Rx ₃ includes a monocyclic cycloalkyl group such as a cyclopentyl group or a cyclohexyl group, a norbornyl group, a tetracyclodecanyl group, and a tetracyclododeca. A polycyclic cycloalkyl group such as a nyl group or an adamantyl group is preferable, and a monocyclic cycloalkyl group having 5 to 6 carbon atoms is more preferable.
A cycloalkyl group formed by combining two of Rx ₁ to Rx ₃ is, for example, a group in which one of the methylene groups constituting the ring has a heteroatom such as an oxygen atom or a heteroatom such as a carbonyl group. may be replaced.
In the group represented by formula (Y1) or formula (Y2), for example, Rx ₁ is a methyl group or an ethyl group, and Rx ₂ and Rx ₃ combine to form the above-described cycloalkyl group. is also preferred.

In formula (Y3), R ₃₆ to R ₃₈ each independently represent a hydrogen atom or a monovalent organic group. R ₃₇ and R ₃₈ may combine with each other to form a ring. The monovalent organic group includes a group represented by the above formula (Y1) and an alkyl group other than the group represented by the formula (Y1) (either linear or branched, or having a cyclic structure). For example, having 1 to 10 carbon atoms, methyl group, ethyl group, n-propyl group, isopropyl group, n-butyl group, isobutyl group, 1-adamantyl group, etc.), aryl group, aralkyl group, and Alkenyl group etc. are mentioned. It is also preferred that R ₃₆ is a hydrogen atom.
Examples of the aryl group, aralkyl group, and alkenyl group include the same groups as the aryl group, aralkyl group, and alkenyl group in Rx ₁ to Rx ₃ described above.
Also, R ₃₈ may be bonded to a group other than the group represented by formula (Y3) in the repeating unit. For example, R ₃₈ may be bonded to a group possessed by the main chain in the repeating unit. When R ₃₈ is bonded to another group in the repeating unit, R ₃₈ and the other group preferably form a single bond or a divalent linking group (such as an alkylene group). Also, when R ₃₈ is bonded to another group in the repeating unit, the repeating unit forms a ring containing the group represented by formula (Y3).

As the formula (Y3), a group represented by the following formula (Y3-1) is also preferable.

Here, L ₁ and L ₂ each independently represent a hydrogen atom, an alkyl group, a cycloalkyl group, an aryl group, or a group combining these (e.g., a group combining an alkyl group and an aryl group). .
M represents a single bond or a divalent linking group.
Q is an alkyl group optionally having a heteroatom, a cycloalkyl group optionally having a heteroatom, an aryl group optionally having a heteroatom, an amino group, an ammonium group, a mercapto group, a cyano group, an aldehyde group, or a group combining these (for example, a group combining an alkyl group and a cycloalkyl group).
In alkyl groups and cycloalkyl groups, for example, one of the methylene groups may be replaced by a heteroatom such as an oxygen atom or a group containing a heteroatom such as a carbonyl group.
One of L ₁ and L ₂ is preferably a hydrogen atom, and the other is preferably an alkyl group, a cycloalkyl group, an aryl group, or a combination of an alkylene group and an aryl group.
At least two of Q, M and L ₁ may combine to form a ring (preferably a 5- or 6-membered ring).
From the viewpoint of pattern refinement, L2 is preferably a _secondary or tertiary alkyl group, more preferably a tertiary alkyl group. Secondary alkyl groups include isopropyl, cyclohexyl and norbornyl groups, and tertiary alkyl groups include tert-butyl and adamantane groups. In these embodiments, the Tg (glass transition temperature) and/or the activation energy are increased, so that the film strength can be ensured and fogging can be suppressed.

In formula (Y4), Ar represents an aromatic ring group. Rn represents an alkyl group, a cycloalkyl group or an aryl group. Rn and Ar may combine with each other to form a non-aromatic ring. Ar is more preferably an aryl group.
Examples of the alkyl group, cycloalkyl group, and aryl group include the same groups as the alkyl group, cycloalkyl group, and aryl group in Rx ₁ to Rx ₃ described above.

・General formula (A02)
The repeating unit having an acid-decomposable group may be a repeating unit represented by general formula (A02).

In the general formula (A02),
Xa ₁ represents a hydrogen atom or an optionally substituted alkyl group.
T represents a single bond or a divalent linking group.
Rx ₁ to Rx ₃ each independently represent an alkyl group (linear or branched) or a cycloalkyl group (monocyclic or polycyclic). However, when all of Rx ₁ to Rx ₃ are alkyl groups (linear or branched), at least two of Rx ₁ to Rx ₃ are preferably methyl groups.
Two of Rx ₁ to Rx ₃ may combine to form a cycloalkyl group (monocyclic or polycyclic).

Examples of the optionally substituted alkyl group represented by Xa ₁ include a methyl group and a group represented by -CH ₂ -R ₁₁ . R ₁₁ represents a halogen atom (such as a fluorine atom), a hydroxyl group or a monovalent organic group, examples of which include alkyl groups having 5 or less carbon atoms, acyl groups having 5 or less carbon atoms, and An alkyl group is preferred, and a methyl group is more preferred. Xa ₁ is preferably a hydrogen atom, a methyl group, a trifluoromethyl group, or a hydroxymethyl group.

Examples of the divalent linking group for T include an alkylene group, an aromatic ring group, a --COO--Rt-- group, and an --O--Rt-- group. In the formula, Rt represents an alkylene group or a cycloalkylene group.
T is preferably a single bond or a -COO-Rt- group. When T represents a -COO-Rt- group, Rt is preferably an alkylene group having 1 to 5 carbon atoms, a -CH ₂ - group, a -(CH ₂ ) ₂ - group, or a -(CH ₂ ) ₃ - groups are more preferred.

The alkyl groups of Rx ₁ to Rx ₃ are alkyl groups having 1 to 4 carbon atoms such as methyl group, ethyl group, n-propyl group, isopropyl group, n-butyl group, isobutyl group and t-butyl group. preferable.
Cycloalkyl groups of Rx ₁ to Rx ₃ include monocyclic cycloalkyl groups such as cyclopentyl group and cyclohexyl group, norbornyl group, tetracyclodecanyl group, tetracyclododecanyl group, and adamantyl group. is preferred.
The cycloalkyl group formed by combining two of Rx ₁ to Rx ₃ is preferably a monocyclic cycloalkyl group such as a cyclopentyl group and a cyclohexyl group, and also a norbornyl group and a tetracyclodecanyl group. , a tetracyclododecanyl group, and a polycyclic cycloalkyl group such as an adamantyl group. Among them, monocyclic cycloalkyl groups having 5 to 6 carbon atoms are preferred.
A cycloalkyl group formed by combining two of Rx ₁ to Rx ₃ is, for example, a group in which one of the methylene groups constituting the ring has a heteroatom such as an oxygen atom or a heteroatom such as a carbonyl group. may be replaced.
In the repeating unit represented by formula (AI), for example, Rx ₁ is a methyl group or an ethyl group, and Rx ₂ and Rx ₃ are preferably combined to form the above-mentioned cycloalkyl group.

When each of the above groups has a substituent, examples of the substituent include an alkyl group (1 to 4 carbon atoms), a halogen atom, a hydroxyl group, an alkoxy group (1 to 4 carbon atoms), a carboxyl group, and an alkoxycarbonyl group. (2 to 6 carbon atoms) and the like. The number of carbon atoms in the substituent is preferably 8 or less.

The content of the repeating unit having an acid-decomposable group is preferably 10 to 80 mol%, more preferably 15 to 60 mol%, more preferably 20 to 45 mol%, based on the total repeating units of Resin B. % is more preferred.
The repeating units having an acid-decomposable group may be used alone or in combination of two or more. When two or more are used, the total content thereof is preferably within the above range.

(Repeating unit represented by general formula (VW))
Resin B also preferably has a repeating unit represented by general formula (VW).

In general formula (VW), Rv represents a hydrogen atom, an alkyl group, or —CH ₂ —O—Rv2. Rv2 represents a hydrogen atom, an alkyl group, or an acyl group.
Rv is preferably a hydrogen atom, a methyl group, a hydroxymethyl group, or a trifluoromethyl group, more preferably a hydrogen atom or a methyl group.

Rw represents a hydrocarbon group having an alicyclic group. Rw may be an alicyclic group itself, or may be a group partially containing an alicyclic group.
The hydrocarbon group may have a substituent, and the substituent that may have is a polar group (as a more specific example, a group exemplified as a polar group so far) other than groups are preferred.
The alicyclic group of Rw may be monocyclic (monocyclic hydrocarbon ring group) or polycyclic (polycyclic hydrocarbon ring group).

As the monocyclic hydrocarbon ring group, a monocyclic alicyclic group is preferable, and a cyclopentane ring group or a cyclohexane ring group is more preferable.
Polycyclic hydrocarbon ring groups include ring-assembled hydrocarbon ring groups and bridged ring hydrocarbon ring groups.
Examples of the ring-assembled hydrocarbon ring group include a bicyclohexane ring group and a perhydronaphthalene ring group.
Examples of the bridged cyclic hydrocarbon ring group include a pinane ring group, a bornane ring group, a norpinane ring group, a norbornane ring group, and a bicyclooctane ring group (bicyclo[2.2.2]octane ring group, bicyclo[3 .2.1] octane ring group, etc.); homobredan ring group, adamantane ring group, tricyclo[5.2.1.0 ^2,6 ]decane ring group, and tricyclo[4 ^{.3.1.1 2,5} ] tricyclic hydrocarbon ring groups such as undecane ring groups; 1 ^7,10 ]dodecane ring group and tetracyclic hydrocarbon ring groups such as perhydro-1,4-methano-5,8-methanonaphthalene ring group. The bridged cyclic hydrocarbon ring group includes condensed cyclic hydrocarbon ring groups (e.g., perhydronaphthalene (decalin) ring group, perhydroanthracene ring group, perhydrophenanthrene ring group, perhydroacenaphthene ring group, A condensed ring group in which a plurality of 5- to 8-membered cycloalkane ring groups such as a perhydrofluorene ring group, a perhydroindene ring group, and a perhydrophenalene ring group are condensed.

The bridged cyclic hydrocarbon ring group is preferably norbornane ring group, adamantane ring group, bicyclooctane ring group, or tricyclo[5,2,1,0 ^2,6 ]decane ring group, norbonane ring group or adamantane ring groups are more preferred.

As a substituent which these alicyclic groups may have, for example, a halogen atom or an alkyl group is preferable.

The repeating unit represented by formula (VW) does not have an acid-decomposable group. That is, for example, Rw does not represent a protecting group (eg, a group represented by formula (Y1)) that is released by the action of an acid as described above.

The repeating unit represented by formula (VW) is exemplified below.
In the formula, Ra represents H, _CH3 , _CH2OH , or _CF3 .

When the resin B has a repeating unit represented by the general formula (VW), the content thereof is preferably 1 to 40 mol%, more preferably 3 to 25, and 5 based on the total repeating units of the resin B. ~15 mol% is more preferred.
The repeating unit represented by the general formula (VW) may be used alone or in combination of two or more. preferable.

Resin B may have repeating units other than the repeating units described above. Examples of such repeating units include repeating units represented by the general formula (P01) in which n is 0 (such as repeating units based on benzyl (meth)acrylate).

The content of repeating units having a benzene ring group in all repeating units of Resin B is preferably 80 mol% or less, more preferably less than 65 mol%, and even more preferably 60 mol% or less. Although the lower limit is not particularly limited, it is preferably 20 mol % or more, more preferably 30 mol % or more, and even more preferably 45 mol % or more.
When the aromatic ring group of the repeating unit having the phenolic polar group of Resin B is a benzene ring group, the repeating unit having the phenolic polar group corresponds to the repeating unit having the benzene ring group.

Resin B can be synthesized according to a conventional method (for example, by radical polymerization).
The weight average molecular weight of Resin B is preferably from 1,000 to 200,000, more preferably from 3,000 to 25,000, and still more preferably from 10,000 to 25,000 as a polystyrene equivalent by GPC method. By setting the weight average molecular weight of Resin B to 1,000 to 200,000, it is possible to prevent deterioration of heat resistance and dry etching resistance, and further deteriorate developability and increase viscosity, resulting in film formation. You can prevent deterioration.
The degree of dispersion (molecular weight distribution) of Resin B is generally 1 to 5, preferably 1 to 3, more preferably 1.2 to 3.0, and even more preferably 1.2 to 2.0. The smaller the degree of dispersion, the better the resolution and resist shape, the smoother the side walls of the resist pattern, and the better the roughness.

In the resist composition of the present invention, the content of resin B is not limited as long as it satisfies the above definition of the mass ratio R2. 99.0% by mass is more preferable, and 95 to 98.5% by mass is even more preferable.
Also, the resin B may be used alone or in combination of two or more. When two or more are used, the total content thereof is preferably within the above range.

<Photoacid generator>
The resist composition of the present invention further contains a photoacid generator.
A photoacid generator is a compound that generates an acid upon exposure to actinic rays or radiation.
As the photoacid generator, a compound that generates an organic acid upon exposure to actinic rays or radiation is preferred. Examples include sulfonium salt compounds, iodonium salt compounds, diazonium salt compounds, phosphonium salt compounds, imidosulfonate compounds, oximesulfonate compounds, diazodisulfone compounds, disulfone compounds, and o-nitrobenzylsulfonate compounds.

As the photoacid generator, a known compound that generates an acid upon exposure to actinic rays or radiation can be appropriately selected and used either singly or as a mixture thereof. For example, paragraphs <0125>-<0319> of US Patent Application Publication No. 2016/0070167A1, paragraphs <0086>-<0094> of US Patent Application Publication No. 2015/0004544A1, and US Patent Application Publication No. 2016/ The known compounds disclosed in paragraphs <0323> to <0402> of 0237190A1 can be suitably used as the photoacid generator (C).

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

In the above general formula (ZI),
R ₂₀₁ , R ₂₀₂ and R ₂₀₃ each independently represent an organic group.
The number of carbon atoms in the organic group as R ₂₀₁ , R ₂₀₂ and R ₂₀₃ is preferably 1-30, more preferably 1-20.

The organic groups of R ₂₀₁ , R ₂₀₂ and R ₂₀₃ are each independently an aryl group (preferably having 6 to 15 carbon atoms) or a linear or branched alkyl group (preferably having 1 to 10 carbon atoms). ), and a cycloalkyl group (preferably having 3 to 15 carbon atoms).
In addition, the number of carbon atoms contained in the substituents of these groups is not included in the preferable number of carbon atoms of these aryl groups, alkyl groups, and cycloalkyl groups.

Also, two of R ₂₀₁ to R ₂₀₃ may combine to form a ring structure, and the ring may have an oxygen atom, a sulfur atom, an ester group, an amide group, or a carbonyl group. Groups formed by combining two of R ₂₀₁ to R ₂₀₃ include an alkylene group (e.g., butylene group, pentylene group) and —CH ₂ —CH ₂ —O—CH ₂ —CH ₂ —. .
Z ⁻ represents an anion (preferably a non-nucleophilic anion).

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

First, compound (ZI-1) will be described.
Compound (ZI-1) is an arylsulfonium compound in which at least one of R ₂₀₁ to R ₂₀₃ in general formula (ZI) is an aryl group, that is, a compound having an arylsulfonium cation.
In the arylsulfonium compound, all of R ₂₀₁ to R ₂₀₃ may be aryl groups, or part of R ₂₀₁ to R ₂₀₃ may be aryl groups and the rest may be alkyl groups or cycloalkyl groups.
Arylsulfonium compounds include, for example, triarylsulfonium compounds, diarylalkylsulfonium compounds, aryldialkylsulfonium compounds, diarylcycloalkylsulfonium compounds, and aryldicycloalkylsulfonium compounds.

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

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

Next, compound (ZI-2) will be described.
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 heteroatom.
The organic group having no aromatic ring as R ₂₀₁ to R ₂₀₃ preferably has 1 to 30 carbon atoms, more preferably 1 to 20 carbon atoms.
R ₂₀₁ to R ₂₀₃ are each independently preferably an alkyl group, a cycloalkyl group, an allyl group, or a vinyl group, and a linear or branched 2-oxoalkyl group, 2-oxocycloalkyl group, or , an alkoxycarbonylmethyl group is more preferred, and a linear or branched 2-oxoalkyl group is even more preferred.

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

Next, compound (ZI-3) will be described. Compound (ZI-3) is a compound represented by general formula (ZI-3).

In general formula (ZI-3), R ₁ represents an alkyl group, a cycloalkyl group, an aryl group, or a benzyl group. When R ₁ has a ring structure, the ring structure may have an oxygen atom, a sulfur atom, an ester group, an amide group, or a carbon-carbon double bond.
_R2 and R3 _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, an alkoxycarbonylalkyl group, an allyl group, or a vinyl group.
In addition, R ₂ and R ₃ may combine with each other to form a ring. Also, R ₁ and R ₂ may combine to form a ring, and the ring formed preferably has a carbon-carbon double bond. In addition, R _x and R _y may combine with each other to form a ring, and the formed ring has an oxygen atom, a sulfur atom, an ester group, an amide group, or a carbon-carbon double bond. It is also preferable to have
Z ⁻ represents an anion.

In general formula (ZI-3), the alkyl group and cycloalkyl group represented by R ₁ include a linear alkyl group having 1 to 15 carbon atoms (preferably 1 to 10 carbon atoms) and 3 to 15 carbon atoms. A branched alkyl group (preferably having 3 to 10 carbon atoms) or a cycloalkyl group having 3 to 15 carbon atoms (preferably 1 to 10 carbon atoms) is preferred, specifically, a methyl group, an ethyl group, Examples include propyl group, n-butyl group, sec-butyl group, t-butyl group, cyclopropyl group, cyclobutyl group, cyclohexyl group and norbornyl group.
The aryl group represented by R ₁ 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 sulfur atom, or the like. Heterocyclic structures include a furan ring, a thiophene ring, a benzofuran ring, a benzothiophene ring, and the like.

It is also preferable that the above R ₁ further has a substituent (for example, substituent group T).
When R ₁ has a ring structure, the ring structure may have an oxygen atom, a sulfur atom, an ester group, an amide group, or a carbon-carbon double bond.

Examples of the alkyl group, cycloalkyl group, and aryl group represented by R ₂ and R ₃ include the same groups as those for R ₁ described above, and preferred embodiments thereof are also the same. Also, R ₂ and R ₃ may combine to form a ring.
Halogen atoms represented by R ₂ and R ₃ include, for example, fluorine, chlorine, bromine and iodine atoms.

Examples of the alkyl group and cycloalkyl group represented by R _x and R _y include the same groups as those for R ₁ described above, and preferred embodiments thereof are also the same.
Examples of the 2-oxoalkyl group represented by R _x and R _y include those having 1 to 15 carbon atoms (preferably 1 to 10 carbon atoms), specifically 2-oxopropyl group, and 2-oxobutyl group.
Alkoxycarbonylalkyl groups represented by R _x and R _y include, for example, those having 1 to 15 carbon atoms (preferably 1 to 10 carbon atoms). Also, R _x and R _y may combine to form a ring.
In addition, R _x and R _y may be bonded to each other to form a ring, and the ring formed by bonding R _x and R _y to each other includes an oxygen atom, a sulfur atom, an ester group, an amide group, Alternatively, it may have a carbon-carbon double bond.
The ring to be formed having an oxygen atom or the like means, for example, two groups that can be bonded to each other (for example, R _x and R _y ) are linked to each other to form an alkylene group, and Examples include a form in which a methylene group is substituted with an oxygen atom or the like.
The ring formed by combining R _x and R _y is preferably a 3- to 10-membered ring, more preferably a 4- to 8-membered ring, and even more preferably a 5- or 6-membered ring.

In general formula (ZI-3), R ₁ and R ₂ may combine to form a ring structure, and the formed ring structure may have a carbon-carbon double bond.

Compound (ZI-3) above is preferably compound (ZI-3A).
Compound (ZI-3A) is a compound represented by the following general formula (ZI-3A) and having a phenacylsulfonium salt structure.

In general formula (ZI-3A),
R _1c to R _5c each independently represent a hydrogen atom, an alkyl group, a cycloalkyl group, an aryl group, an alkoxy group, an aryloxy group, an alkoxycarbonyl group, an alkylcarbonyloxy group, a cycloalkylcarbonyloxy group, a halogen atom, or a hydroxyl group , represents a nitro group, an alkylthio group, or an arylthio group.
R _6c and R _7c have the same definitions as R ₂ and R ₃ in general formula (ZI-3) described above, and preferred embodiments thereof are also the same.
R _x and R _y have the same meanings as R _x and R _y in general formula (ZI-3) described above, and preferred embodiments thereof are also the same.

Any two or more of R _1c to R _5c and R _x and R _y may each be combined to form a ring, and this ring is each independently an oxygen atom, a sulfur atom, an ester group, or an amide group. , or may have a carbon-carbon double bond. In addition, R _5c and R _6c , and R _5c and R _x may be combined to form a ring, and this ring preferably independently has a carbon-carbon double bond. Also, R _6c and R _7c may combine to form a ring.
The ring to be formed having an oxygen atom or the like means, for example, two groups that can be bonded (e.g., R _x and R _y ) are bonded to each other to form an alkylene group, and a methylene group in such an alkylene group is substituted with an oxygen atom or the like.
Examples of the ring include aromatic or non-aromatic hydrocarbon rings, aromatic or non-aromatic heterocyclic rings, and polycyclic condensed rings in which two or more of these rings are combined. The ring is preferably a 3- to 10-membered ring, more preferably a 4- to 8-membered ring, and still more preferably a 5- or 6-membered ring.

Groups formed by bonding two or more of R _1c to R _5c , R _6c and R _7c , and R _x and R _y include a butylene group, a pentylene group, and —CH ₂ —CH ₂ —. O—CH ₂ —CH ₂ — and the like are included.
The group formed by combining R _5c and R _6c and R _5c and R _x is preferably a single bond or an alkylene group. The alkylene group includes a methylene group, an ethylene group, and the like.
^Zc- represents an anion.

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

In general formula (ZI-4),
l represents an integer of 0 to 2;
r represents an integer of 0 to 8;
R ₁₃ is a hydrogen atom, a fluorine atom, a hydroxyl group, an alkyl group, an alkoxy group, an alkoxycarbonyl group, or a group having a cycloalkyl group (it may be a cycloalkyl group itself, or a group partially containing a cycloalkyl group The cycloalkyl group moiety may be monocyclic or polycyclic). These groups may have a substituent.
R ₁₄ is a hydroxyl group, an alkyl group, an alkoxy group, an alkoxycarbonyl group, an alkylcarbonyl group, an alkylsulfonyl group, or a group having a cycloalkyl group (it may be the cycloalkyl group itself, or a cycloalkyl group The cycloalkyl group moiety may be monocyclic or polycyclic, and represents, for example, a cycloalkylsulfonyl group or a cycloalkoxy group. These groups may have a substituent. When multiple R ₁₄ are present, the multiple R ₁₄ may be the same or different.
Each R ₁₅ independently represents an alkyl group, a cycloalkyl group, or a naphthyl group. These groups may have a substituent. Two R ₁₅ may be joined together to form a ring. When two R ₁₅ are combined to form a ring, the ring skeleton may contain a heteroatom such as an oxygen atom or a nitrogen atom. In one aspect, two R ₁₅ are alkylene groups, preferably joined together to form a ring structure.

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

Next, general formulas (ZII) and (ZIII) are described.
In general 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 for R ₂₀₄ to R ₂₀₇ is preferably a phenyl group or a naphthyl group, more preferably a phenyl group. The aryl group of R ₂₀₄ to R ₂₀₇ may be an aryl group having a heterocyclic structure containing an oxygen atom, a nitrogen atom, a sulfur atom, or the like. Skeletons of aryl groups having a heterocyclic structure include, for example, pyrrole, furan, thiophene, indole, benzofuran, and benzothiophene.
The alkyl group and cycloalkyl group represented by R ₂₀₄ to R ₂₀₇ include linear alkyl groups having 1 to 10 carbon atoms or branched alkyl groups having 3 to 10 carbon atoms (e.g., methyl, ethyl, propyl, butyl group and pentyl group) or a cycloalkyl group having 3 to 10 carbon atoms (eg, cyclopentyl group, cyclohexyl group and norbornyl group) are preferred.

The aryl group, alkyl group and cycloalkyl group of R ₂₀₄ to R ₂₀₇ may each independently have a substituent. Examples of substituents that the aryl group, alkyl group and cycloalkyl group of R ₂₀₄ to R ₂₀₇ may have include an alkyl group (eg, having 1 to 15 carbon atoms) and a cycloalkyl group (eg, having 3 carbon atoms). 15), aryl groups (eg, 6 to 15 carbon atoms), alkoxy groups (eg, 1 to 15 carbon atoms), halogen atoms, hydroxyl groups, and phenylthio groups.
Z ⁻ represents an anion.

Z - in general formula (ZI), Z ^- in general formula (ZII), Zc ^- in general formula (ZI-3), ^{and Z - in} general formula (ZI-4) are represented by the following general formula (3) The anions represented are preferred.

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

Xf represents a fluorine atom or an alkyl group substituted with at least one fluorine atom. The number of carbon atoms in this alkyl group is preferably 1-10, more preferably 1-4. A perfluoroalkyl group is preferable as the alkyl group substituted with at least one fluorine atom.
Xf is preferably a fluorine atom or a C 1-4 perfluoroalkyl group, more preferably a fluorine atom or CF ₃ . In particular, both Xf are more preferably fluorine atoms.

_R4 and R5 each independently represent a hydrogen atom, a fluorine atom, an alkyl group, or an alkyl group substituted with at _least one fluorine atom. When multiple R ₄ and R ₅ are present, each of R ₄ and R ₅ may be the same or different.
The alkyl groups represented by R ₄ and R ₅ may have substituents and preferably have 1 to 4 carbon atoms. R ₄ and R ₅ are preferably hydrogen atoms.
Specific examples and preferred aspects of the alkyl group substituted with at least one fluorine atom are the same as the specific examples and preferred aspects of Xf in general formula (3).

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

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

Aryl groups may be monocyclic or polycyclic. This aryl group includes, for example, a phenyl group, a naphthyl group, a phenanthryl group, and an anthryl group.
A heterocyclic group may be monocyclic or polycyclic. A polycyclic ring can further suppress acid diffusion. Moreover, the heterocyclic group may or may not have aromaticity. Heterocyclic rings having aromaticity include, for example, furan ring, thiophene ring, benzofuran ring, benzothiophene ring, dibenzofuran ring, dibenzothiophene ring, and pyridine ring. Non-aromatic heterocycles include, for example, a tetrahydropyran ring, a lactone ring, a sultone ring, and a decahydroisoquinoline ring. The heterocyclic ring in the heterocyclic group is particularly preferably a furan ring, a thiophene ring, a pyridine ring, or a decahydroisoquinoline ring.

The cyclic organic group may have a substituent. Examples of such substituents include alkyl groups (either linear or branched, preferably having 1 to 12 carbon atoms), cycloalkyl groups (monocyclic, polycyclic (including spirocyclic) preferably having 3 to 20 carbon atoms), aryl group (preferably having 6 to 14 carbon atoms), hydroxyl group, alkoxy group, ester group, amide group, urethane group, ureido group, thioether group, sulfone Amide groups and sulfonate groups are included. In addition, carbonyl carbon may be sufficient as carbon (carbon which contributes to ring formation) which comprises a cyclic|annular organic group.

Examples of anions represented by the general formula (3) include SO ₃ ⁻ —CF ₂ —CH ₂ —OCO-(L)q′-W, SO ₃ ^— —CF ₂ —CHF—CH ₂ —OCO-(L) q′-W, SO ₃ ⁻ —CF ₂ —COO-(L)q′-W, SO ₃ ⁻ —CF ₂ —CF ₂ —CH ₂ —CH ₂ —(L)qW, SO ₃ ^— —CF ₂ -CH(CF ₃ )-OCO-(L)q'-W is preferred. Here, L, q and W are the same as in general formula (3). q' represents an integer from 0 to 10;

In one embodiment, Z - in general formula (ZI), Z ^- in general formula (ZII), Zc ^- in general formula (ZI-3), ^{and Z - in} general formula (ZI-4) are fluoroalkylsulfones Acid anions (more preferably perfluoroalkylsulfonate anions) are also preferred. The fluoroalkylsulfonate anion (including perfluoroalkylsulfonate anion) preferably has 2 to 10 carbon atoms, more preferably 3 to 5 carbon atoms.

The anions and cations of the photoacid generator are exemplified below.

Any combination of the above cations and anions can be used as a photoacid generator.

The photoacid generator may be in the form of a low-molecular-weight compound, or may be in the form of being incorporated into a part of the polymer. Moreover, the form of a low-molecular-weight compound and the form incorporated into a part of a polymer may be used in combination.
The 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, even more preferably 1,000 or less.
In the resist composition of the present invention, the content of the photoacid generator is preferably 0.1 to 35% by mass, more preferably 0.5 to 20% by mass, more preferably 1 to 35% by mass, based on the total solid content of the composition. 10% by mass is more preferred, and 1 to 5% by mass is particularly preferred.
Also, the resin B may be used alone or in combination of two or more. When two or more are used, the total content thereof is preferably within the above range.

<Acid diffusion control agent>
The resist composition of the present invention further contains an acid diffusion control agent which is a compound different from the ether compounds described above.
The acid diffusion control agent preferably traps the acid generated from the photoacid generator or the like during exposure, and acts as a quencher that suppresses the reaction of the resin B in the unexposed area due to excess generated acid.
For example, a basic compound (DA), a basic compound (DB) whose basicity is reduced or lost by irradiation with actinic rays or radiation (having a proton acceptor functional group and decomposed by irradiation with actinic rays or radiation) a compound whose proton acceptor property is reduced, lost, or changes from proton acceptor property to acidic), an onium salt (DC) that is relatively weakly acidic with respect to the photoacid generator, and a nitrogen atom, A low-molecular-weight compound (DD) having a group that leaves under the action of an acid, an onium salt compound (DE) having a nitrogen atom in the cation portion, or the like can be used as an acid diffusion controller.
Among them, the acid diffusion controller is preferably a basic compound (DA) and a low-molecular-weight compound (DD) having a nitrogen atom-containing group that is released by the action of an acid.

(Basic compound (DA))
As the basic compound (DA), compounds having structures represented by the following formulas (A) to (E) are preferred.

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

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

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

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

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

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

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

In general formula (6),
l represents an integer of 0 to 2, m represents an integer of 1 to 3, and satisfies l+m=3.
Ra represents a hydrogen atom, an alkyl group, a cycloalkyl group, an aryl group, or an aralkyl group. When l is 2, the two Ra's may be the same or different, and the two Ra's may bond together to form a heterocyclic ring together with the nitrogen atom in the formula. This heterocyclic ring may have a heteroatom other than the nitrogen atom in the formula. Moreover, a hydroxyl group is preferable as a substituent of this heterocyclic ring.
Rb has the same definition as Rb in formula (d-1) above, and preferred examples are also the same.
In the general formula (6), the alkyl group, cycloalkyl group, aryl group, and aralkyl group as Ra are each independently represented by the alkyl group, cycloalkyl group, aryl group, and aralkyl group as Rb. It is also preferable to have a substituent exemplified as an optional substituent.

Specific examples of the alkyl group, cycloalkyl group, aryl group, and aralkyl group (these groups may be substituted with the above groups) for Ra include the same groups as those described above for Rb. .
Specific examples of particularly preferred compounds (DD) in the present invention include, but are not limited to, the compounds disclosed in paragraph <0475> of US Patent Application Publication No. 2012/0135348A1.

Preferred examples of acid diffusion control agents are shown below.

The content of the acid diffusion control agent in the resist composition of the present invention is not limited as long as it satisfies the above definition of the mass ratio R1. 0.01 to 1% by mass is more preferable, and 0.02 to 0.1% by mass is even more preferable.

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

As the organic solvent, a mixed solvent in which a solvent having a hydroxyl group in its structure and a solvent having no hydroxyl group are mixed may be used.
As the solvent having a hydroxyl group and the solvent not having a hydroxyl group, the above-described exemplary compounds can be appropriately selected. As the solvent containing a hydroxyl group, alkylene glycol monoalkyl ether, alkyl lactate, etc. ), propylene glycol monoethyl ether (PGEE), methyl 2-hydroxyisobutyrate, or ethyl lactate are more preferred.
As the solvent having no hydroxyl group, alkylene glycol monoalkyl ether acetate, alkylalkoxypropionate, monoketone compound which may have a ring, cyclic lactone, or alkyl acetate are preferable. Propylene glycol monomethyl ether acetate (PGMEA), ethyl ethoxypropionate, 2-heptanone, γ-butyrolactone, cyclohexanone, cyclopentanone, or butyl acetate are more preferable, and propylene glycol monomethyl ether acetate, γ-butyrolactone, ethyl ethoxypropionate Pionate, cyclohexanone, cyclopentanone or 2-heptanone are more preferred. Propylene carbonate is also preferred as the solvent having no hydroxyl group.
The mixing ratio (mass ratio) of the solvent having a hydroxyl group and the solvent having no hydroxyl group is 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.

<Surfactant>
The resist composition of the invention may further contain a surfactant. Surfactants include fluorine-based and/or silicon-based surfactants (specifically, fluorine-based surfactants, silicon-based surfactants, or surfactants having both fluorine atoms and silicon atoms). is preferred.

Fluorinated and/or silicon-based surfactants include surfactants described in paragraph <0276> of US Patent Application Publication No. 2008/0248425.
Also, other surfactants than the fluorine-based and/or silicon-based surfactants described in paragraph <0280> of US Patent Application Publication No. 2008/0248425 can be used.

Surfactants may be used singly or in combination of two or more.
When the resist composition of the present invention contains a surfactant, the content of the surfactant is preferably 0.0001 to 2% by mass, more preferably 0.0005 to 1% by mass, based on the total solid content of the composition. more preferred.
One type of surfactant may be used alone, or two or more types may be used. When two or more surfactants are used, the total content is preferably within the above range.

(Other additives)
The resist composition of the present invention may further contain different components such as hydrophobic resins, acid multipliers, dyes, plasticizers, photosensitizers, light absorbers, alkali-soluble resins, dissolution inhibitors. , and one or more components selected from the group consisting of dissolution accelerators and the like.

<Preparation method>
The solid content concentration of the resist composition of the present invention is more than 20% by mass, preferably 21 to 50% by mass, more preferably 22 to 40% by mass, and even more preferably 23 to 35% by mass.
The solid content concentration is the mass percentage of the total solid content (the total mass of other resist components excluding the solvent) with respect to the total mass of the composition.

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

The resist composition of the present invention preferably has a viscosity of 20 to 500 mPa·s. The viscosity of the resist composition of the present invention is more preferably 20 to 300 mPa·s from the viewpoint of superior coatability.
The viscosity can be measured with an E-type viscometer at room temperature (23°C).

<Application>
The resist composition of the present invention relates to an actinic ray- or radiation-sensitive resin composition that reacts with irradiation of actinic rays or radiation to change its properties. More specifically, the resist composition of the present invention can be used in semiconductor manufacturing processes such as ICs (Integrated Circuits), manufacturing of circuit boards such as liquid crystals or thermal heads, manufacturing of imprint mold structures, other photofabrication processes, Or it 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 process, an ion implantation process, a bump electrode forming process, a rewiring forming process, MEMS (Micro Electro Mechanical Systems), and the like.

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

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

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

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

(i) The film thickness of the resist film formed in the resist film forming step is preferably 500 to 11,000 nm, more preferably 1,000 to 9,000 nm, and still more preferably 3,000 to 7,000 nm.

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

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

The heating temperature is preferably 70 to 160°C, more preferably 70 to 155°C, and even more preferably 80 to 150°C in both (iv) the preheating step and (v) the post-exposure heating step.
The heating time is preferably 30 to 300 seconds, more preferably 30 to 180 seconds, and even more preferably 30 to 90 seconds in both (iv) the preheating step and (v) the post-exposure heating step.
Heating can be performed by means provided in the exposure device and the development device, and may be performed using a hot plate or the like.

The wavelength of the light source used in the exposure process is not limited, but examples include infrared light, visible light, ultraviolet light, far ultraviolet light, extreme ultraviolet light (EUV light), X-rays, and electron beams. Among these, far-ultraviolet light is preferred, and its wavelength is preferably 250 nm or less. Specifically, KrF excimer laser (248 nm), ArF excimer laser (193 nm), F2 excimer laser ₍ 157 nm), X-ray, EUV light (13 nm), electron beam, etc., KrF excimer laser, ArF excimer laser A laser, EUV light, or an electron beam is preferred, and a KrF excimer laser is more preferred.

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

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

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

Ketone solvents include, for example, 1-octanone, 2-octanone, 1-nonanone, 2-nonanone, acetone, 2-heptanone (methyl amyl ketone), 4-heptanone, 1-hexanone, 2-hexanone, diisobutyl ketone, Cyclohexanone, methylcyclohexanone, phenylacetone, methylethylketone, methylisobutylketone, acetylacetone, acetonylacetone, ionone, diacetonyl alcohol, acetylcarbinol, acetophenone, methylnaphthylketone, isophorone, and propylene carbonate.

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

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

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

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

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

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

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

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

(iii) It is preferable to include a step of washing with a rinse solution (rinse step) after the development step.

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

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

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

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

The rinse liquid may contain an appropriate amount of surfactant.
In the rinsing step, the developed substrate is washed with a rinsing liquid. The method of the cleaning treatment is not particularly limited, but for example, a method of continuously discharging the rinse solution onto the substrate rotating at a constant speed (rotation coating method), or a method of immersing the substrate in a bath filled with the rinse solution for a certain period of time. method (dip method), or a method of spraying a rinse liquid onto the substrate surface (spray method). Among them, it is preferable that the cleaning treatment is performed by a spin coating method, and after cleaning, the substrate is rotated at a rotation speed of 2,000 to 4,000 rpm (revolution per minute) to remove the rinsing liquid from the substrate. It is also preferable to include a heating step (Post Bake) after the rinsing step. This heating process removes the developer and rinse remaining between the patterns and inside the patterns. In the heating step after the rinsing step, the heating temperature is usually 40 to 160°C, preferably 70 to 120°C, more preferably 70 to 115°C. The heating time is usually 10 seconds to 3 minutes, preferably 30 seconds to 90 seconds.

The film thickness (pattern height) of the pattern obtained by the pattern forming method of the present invention is preferably 500 to 11,000 nm, more preferably 1,000 to 9,000 nm, and even more preferably 3,000 to 7,000 nm.
When the pattern to be formed is linear, the aspect ratio obtained by dividing the pattern height by the line width is preferably 0.3 to 20, more preferably 0.5 to 15, and more preferably 1 to 10. preferable.
When the pattern to be formed is a trench (groove) pattern or a contact hole pattern, the aspect ratio obtained by dividing the pattern height by the trench width or hole diameter is preferably 0.3 to 20, and 0.3 to 20. 5 to 15 are more preferred, and 1 to 10 are even more preferred.

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

As a method for removing impurities such as metals from the above various materials, for example, filtration using a filter can be mentioned. The pore size of the filter is preferably 10 nm or less, more preferably 5 nm or less, and even more preferably 3 nm or less. As the material of the filter, a filter made of polytetrafluoroethylene, polyethylene, or nylon is preferable. A filter that has been pre-washed with an organic solvent may be used. In the filter filtration step, multiple types of filters may be connected in series or in parallel for use. When multiple types of filters are used, filters with different pore sizes and/or materials may be used in combination. Further, various materials may be filtered multiple times, and the process of filtering multiple times may be a circulation filtration process. As the filter, those with reduced extractables as disclosed in Japanese Patent Application Publication No. 2016-201426 (JP 2016-201426) are preferable.
In addition to filter filtration, impurities may be removed using an adsorbent, or a combination of filter filtration and adsorbent may be used. As the adsorbent, a known adsorbent can be used, and for example, an inorganic adsorbent such as silica gel or zeolite, or an organic adsorbent such as activated carbon can be used. Examples of metal adsorbents include those disclosed in Japanese Patent Application Publication No. 2016-206500 (JP 2016-206500).
In addition, as a method for reducing impurities such as metals contained in the various materials, selecting raw materials with a low metal content as raw materials constituting various materials, performing filter filtration on raw materials constituting various materials, Alternatively, distillation may be performed under conditions in which contamination is suppressed as much as possible by, for example, lining the inside of the apparatus with Teflon (registered trademark). Preferred conditions for filtering the raw materials constituting various materials are the same as those described above.
Part or all of the inside of the apparatus used in the manufacturing process (process for synthesizing the raw material, etc.) of the materials of the resist composition (resin, photoacid generator, etc.) may also be glass-lined. It is preferable to keep the content of impurities to a small amount (for example, mass ppt order). Such a method is described, for example, in the December 21, 2017 Chemical Daily.

The above various materials are described in US Patent Application Publication No. 2015/0227049, Japanese Patent Application Publication No. 2015-123351 (JP 2015-123351), etc., in order to prevent contamination of impurities. preferably stored in an airtight container.

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

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

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

[Preparation of resist composition (actinic ray-sensitive or radiation-sensitive resin composition)]
A resist composition (actinic ray-sensitive or radiation-sensitive resin composition) was prepared using the components shown below.

<Ether compound>
The compounds shown below were used as ether compounds.

<Resin>
As resins, the following resins were used.

The following table shows the compositional ratio (molar ratio, corresponding from left to right), weight average molecular weight, and degree of dispersion (weight average molecular weight/number average molecular weight) of each repeating unit in each resin.

<Photoacid generator>
As the photoacid generator, the following photoacid generator was used.

＜酸拡散制御剤＞
酸拡散制御剤として、以下の化合物を使用した。

<Acid diffusion control agent>
The following compounds were used as acid diffusion control agents.

<Surfactant>
The following compounds were used as surfactants.

G1: Compound shown below G2: Megafac-R4 (fluorosurfactant, manufactured by DIC)

<Solvent>
As a solvent, a mixed solvent of PGMEA (propylene glycol monomethyl ether acetate) and PGME (propylene glycol monomethyl ether) (mixing ratio: PGMEA/PGME=80/20 (mass ratio)) was used.
<Preparation of resist composition>

An ether compound, a resin, a photoacid generator, an acid diffusion control agent, and a surfactant are dissolved in a solvent so as to satisfy the solid content composition shown in the table below, and the solid content concentration shown in the table is reached. A solution was prepared as follows. The obtained solution was subjected to microfiltration with a 0.3 μm caliber membrane filter to obtain a resist composition.
The formulation of the resist composition used in each example or comparative example is shown in the table below.
The notation of content in the table indicates the content (% by mass) of each component relative to the total solid content.

〔evaluation〕
<Formation of pattern>
Using Tokyo Electron's spin coater "ACT-8", a resist composition was applied onto a hexamethyldisilazane-treated 8-inch Si substrate (manufactured by Advanced Materials Technology (hereinafter also referred to as "substrate")). was spin-coated.
This substrate was heated at 140° C. for 60 seconds (PB: PreBake) and dried to form a resist film having a thickness of 4.2 μm. After that, using a KrF excimer laser scanner (manufactured by ASML, PAS5500/850C wavelength 248 nm), exposure was performed at various exposure doses through a mask having a line width of 500 nm and a space width of 300 nm.
Further, the resist film after exposure is heated at 115° C. for 60 seconds, then immersed in a 2.38 mass % tetramethylammonium hydroxide (TMAH) aqueous solution for 60 seconds for development to obtain a line-and-space pattern. rice field.
The obtained pattern was rinsed with pure water for 30 seconds and then heated at 110° C. for 60 seconds.

<Evaluation of pitch (measurement of space)>
The produced pattern was observed using a critical dimension SEM S-9380 manufactured by Hitachi. The minimum exposure dose at which it was confirmed that the exposed portions of the resist film were completely developed (removed) until the surface of the substrate was exposed was taken as the optimum exposure dose Eopt. The width (space (nm)) between adjacent lines was measured when a pattern was formed with this Eopt. It can be evaluated that the smaller this value is, the better the resolution is, and the narrower the pitch of the pattern can be formed.
Note that the above-mentioned "width between adjacent lines" is intended to be a distance connecting two adjacent lines with a height of d/2, where d is the thickness of the pattern.

<Evaluation of cross-sectional shape (rectangularity)>
The cross-section of the pattern formed at the optimum exposure dose Eopt was observed with a scanning electron microscope, and the cross-sectional shape (rectangularity) of the observed line shape was evaluated according to the following criteria.

A: The shape of the line is rectangular.
B: The shape of the line was tapered.
C: The shape of the line was tapered, and further, the non-exposed portion was partially removed during development, resulting in film reduction.
-: The pattern collapsed and the pattern could not be formed.
When the width of the top side of the trench (the area where the resist was removed by exposure) was 1.5 times or more larger than the width of the bottom side, the shape of the line was evaluated as being tapered.

〔result〕
The following table shows the evaluation results in each example or comparative example and the characteristics of the resist composition used in each example or comparative example.
In the table, the column "R1" indicates the mass ratio of the content of the ether compound to the content of the acid diffusion control agent in the resist composition (content of ether compound/content of acid diffusion control agent). .
The column "R2" indicates the mass ratio of the content of the ether compound to the content of the resin B in the resist composition (content of the ether compound/content of the resin B).
The "nitrogen-containing" column indicates whether the ether compound in the resist composition is a nitrogen-containing compound. If this requirement is met, it is rated as A, and if it is not met, it is rated as B.
The column of "formula (X1)" indicates whether the ether compound in the resist composition is a compound represented by general formula (X1). If this requirement is met, it is rated as A, and if it is not met, it is rated as B.
The column "R ^q1 : benzene ring group" indicates whether or not R ^q1 is a benzene ring group when the ether compound in the resist composition is the compound represented by formula (X1). If this requirement is met, it is rated as A, and if it is not met, it is rated as B.
The column of "phenolic polar unit" indicates whether or not the resin in the resist composition has a repeating unit having a phenolic polar group. If this requirement is met, it is rated as A, and if it is not met, it is rated as B.
The column "Benzene unit content" indicates the content (% by mass) of repeating units having a benzene ring group with respect to the total mass of the resin in the resist composition.
The column of "formula (Z1-3)" indicates whether the photoacid generator in the resist composition is a compound represented by general formula (Z1-3). If this requirement is met, it is rated as A, and if it is not met, it is rated as B.

As shown in the table above, it was confirmed that a pattern having a high aspect ratio and a narrow pitch can be formed by using the resist composition of the present invention. Moreover, the cross-sectional shape of the pattern formed was also better than the cross-sectional shape of the pattern obtained using the resist composition of the comparative example.
On the other hand, the desired pattern could not be obtained with the resist composition of the comparative example. In Comparative Example 4, cracks occurred in the resist film after PB, and the pattern could not be formed.
Further, when a test was conducted using a resist composition having a solid content concentration of 10% by mass, a resist film having a film thickness (4.2 μm), which was used as an evaluation criterion, could not be formed.

From the results shown in the table, it was confirmed that a pattern with a narrower pitch can be formed when the ether compound is a nitrogen-containing compound (comparison of Examples 1 to 4).
When the ether compound is a compound represented by the general formula (X1), and the group corresponding to R ^q1 is a benzene ring group, a pattern with a narrower pitch can be formed, and the cross-sectional shape of the resulting pattern can be improved. It was confirmed to be excellent (comparison of Examples 1 to 3).
When the content of the repeating unit having a benzene ring group is less than 65 mol% with respect to the total mass of the resin, it was confirmed that a pattern with a narrower pitch can be formed and the cross-sectional shape of the resulting pattern is also superior (implementation (compare Examples 1, 5 and 6).
It was confirmed that a pattern with a narrower pitch can be formed when the photoacid generator is the compound represented by formula (ZI-3) (comparison of Examples 1, 7, and 10).

Claims (11)

an ether compound;
a resin having a repeating unit having a phenolic polar group and a repeating unit having an acid-decomposable group;
a photoacid generator;
an acid diffusion controller that is a compound different from the ether compound;
An actinic ray-sensitive or radiation-sensitive resin composition containing a solvent,
The ether compound is a compound having a group represented by the following general formula (O1),
The mass ratio of the content of the ether compound to the content of the acid diffusion control agent is 0.2 or more,
The mass ratio of the content of the ether compound to the content of the resin is 0.1 or less,
An actinic ray-sensitive or radiation-sensitive resin composition having a solid content concentration of more than 20% by mass.
*x-(-O-AL-) _a- *y (O1)
In general formula (O1), AL represents an alkylene group having 2 to 3 carbon atoms.
a represents an integer of 1 or more.
*x represents an alkyl group having 1 carbon atom.
*y represents a bonding position with a group other than the group represented by general formula (O1). 2. The actinic ray-sensitive or radiation-sensitive resin composition according to claim 1, wherein said ether compound contains a nitrogen atom. The actinic ray-sensitive or radiation-sensitive resin composition according to claim 1 or 2, wherein the ether compound is a compound represented by formula (X1).
[R ^q1 -(-O-AL-) _m ] _n -N-R ^q2 _3-n (X1)
In general formula (X1), m represents an integer of 1-10.
n represents an integer of 1 to 3;
AL represents an alkylene group.
R ^q1 and R ^q2 each independently represent a hydrogen atom or a substituent.
When n is 1 or 2, R ^q1 and R ^q2 may combine with each other to form a ring.
When there are multiple m's, the multiple m's may be the same or different. When multiple ALs are present, the multiple ALs may be the same or different. When multiple R ^q1 are present, the multiple R ^q1 may be the same or different. When multiple R ^q2 are present, the multiple R ^q2 may be the same or different. 4. The actinic ray-sensitive or radiation-sensitive resin composition according to claim 3, wherein at least one R ^q1 is a benzene ring group. The actinic ray-sensitive or radiation-sensitive resin composition according to any one of claims 1 to 4, wherein the content of repeating units having a benzene ring group in all repeating units of the resin is less than 65 mol%. thing. The actinic ray-sensitive or radiation-sensitive resin composition according to any one of claims 1 to 5, wherein the resin further has a repeating unit represented by general formula (VW).

In general formula (VW), Rv represents a hydrogen atom, an alkyl group, or —CH ₂ —O—Rv2. Rv2 represents a hydrogen atom, an alkyl group, or an acyl group.
Rw represents a hydrocarbon group having an alicyclic group.
However, the repeating unit represented by general formula (VW) does not have an acid-decomposable group. wherein the photoacid generator is one or more compounds selected from the group consisting of compounds represented by general formula (ZI-3) and compounds represented by general formula (ZI-4); The actinic ray-sensitive or radiation-sensitive resin composition according to any one of items 1 to 6.

In general formula (ZI-3), R ₁ represents an alkyl group, a cycloalkyl group, an aryl group, or a benzyl group. When R ₁ has a ring structure, the ring structure may have an oxygen atom, a sulfur atom, an ester group, an amide group, or a carbon-carbon double bond.
_R2 and R3 _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, an alkoxycarbonylalkyl group, an allyl group, or a vinyl group.
R ₂ and R ₃ may combine with each other to form a ring. R ₁ and R ₂ may combine with each other to form a ring. R _x and R _y may combine with each other to form a ring.
Z ⁻ represents an anion.
In general formula (ZI-4),
l represents an integer of 0 to 2;
r represents an integer of 0 to 8;
_R13 represents a group having a hydrogen atom, a fluorine atom, a hydroxyl group, an alkyl group, an alkoxy group, an alkoxycarbonyl group, or a cycloalkyl group.
R ₁₄ represents a group having a hydroxyl group, an alkyl group, an alkoxy group, an alkoxycarbonyl group, an alkylcarbonyl group, an alkylsulfonyl group, or a cycloalkyl group. When multiple R ₁₄ are present, the multiple R ₁₄ may be the same or different.
Each R ₁₅ independently represents an alkyl group, a cycloalkyl group, or a naphthyl group. Two R ₁₅ may be joined together to form a ring. When two R ₁₅ are combined to form a ring, the ring skeleton may contain a heteroatom such as an oxygen atom or a nitrogen atom. The actinic ray-sensitive or radiation-sensitive resin composition according to any one of claims 1 to 7, wherein the ether compound has a molecular weight of 100 to 2,000. A resist film formed using the actinic ray-sensitive or radiation-sensitive resin composition according to any one of claims 1 to 8. A step of forming a resist film using the actinic ray-sensitive or radiation-sensitive resin composition according to any one of claims 1 to 8;
exposing the resist film;
and developing the exposed resist film using a developer. A method for manufacturing an electronic device, comprising the pattern forming method according to claim 10 .