TW201942102A - Actinic-light-sensitive or radiation-sensitive resin composition, resist film, pattern formation method, method of manufacturing electronic device - Google Patents

Abstract

Provided is an actinic-light-sensitive or radiation-sensitive resin composition capable of forming a pattern having a high aspect ratio and a narrow pitch. Provided are a resist film, a pattern formation method, and a method of manufacturing an electronic device. The actinic-light-sensitive or radiation-sensitive resin composition comprises an ether compound, a resin including a repeating unit having a phenolic polar group and a repeating unit having an acid-degradable group, a photoacid generator, an acid diffusion control agent that is a compound different from the ether compound, and a solvent. The mass ratio of the ether compound content to the acid diffusion control agent content is 0.2 or more, the mass ratio of the ether compound content to the resin B content is 0.1 or less, and the solid content concentration is more than 20% by mass.

Description

Photosensitized or radiation-sensitive resin composition, resist film, pattern forming method, and manufacturing method of electronic component

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

In order to compensate for the decrease in sensitivity caused by light absorption after the resist for KrF excimer laser (248 nm), an image forming method such as chemical amplification is used as an image forming method for the resist. For example, as a positive-type chemically-amplified image forming method, there can be mentioned an image forming method in which a photoacid generator in an exposed portion is decomposed and generated by exposure to an excimer laser, an electron beam, and extreme ultraviolet light, etc. Acid, and use it to generate acid as a reaction catalyst in baking after exposure (PEB: Post Exposure Bake) to change the alkali-insoluble group into alkali-soluble group, and the exposed portion is removed by the alkali developing solution.

For example, Patent Document 1 discloses a pattern forming method having a step of forming a film having a thickness T on a substrate using a predetermined photosensitized or radiation-sensitive resin composition. As the thickness T, for example, suppose Above 800 nm.
[Prior technical literature]
[Patent Literature]

[Patent Document 1] International Publication No. WO2017 / 057226

So far, ion implantation has been performed in semiconductors in manufacturing steps and the like of image sensors. In recent years, in consideration of the requirements for high resolution of the ion implantation, the high aspect ratio of the obtained pattern (the height of the formed line with respect to the amplitude is promoted even by making the resist film a thick film). When the ratio is large, it is also required that the pattern can have a narrow pitch (interval).
The present inventors have studied the photosensitized radioactive or radiation-sensitive resin composition described in Patent Document 1, and found that there is room for improvement in the pitch of the patterns when the high aspect ratio of the patterns is promoted.

Therefore, an object of the present invention is to provide a photosensitized radioactive 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 a method for manufacturing an electronic component.

As a result of intensive research in order to achieve the above-mentioned problems, the present inventors have found that the above-mentioned problems can be solved by a predetermined photosensitive radiation- or radiation-sensitive resin composition containing an ether compound, and the present invention has been completed.
That is, it was found that the above object can be achieved by the following configuration.

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

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

Hereinafter, the present invention will be described in detail.
The description of the constituent elements described below may be made based on a representative embodiment of the present invention, but the present invention is not limited to this embodiment.
In this specification, "actinic rays" or "radiation" means, for example, the bright line spectrum of a mercury lamp, extreme ultraviolet rays represented by excimer laser light, extreme ultraviolet rays (EUV light: Extreme Ultraviolet), X-rays, and electron beams ( EB: Electron Beam) and so on. The "light" in this specification means actinic rays or radiation.
Unless otherwise specified, "exposure" in this specification includes not only exposure using a bright line spectrum of a mercury lamp, extreme ultraviolet, extreme ultraviolet, X-ray, and EUV light represented by an excimer laser, but also the use of electrons. Beams and ion beams.
In this specification, "~" is used as the meaning which includes the numerical value before and after that as a lower limit value and an upper limit value.

In this specification, (meth) acrylate means an acrylate and a methacrylate. Moreover, (meth) acrylic acid means acrylic acid and methacrylic acid.
In this specification, the weight average molecular weight (Mw), number average molecular weight (Mn), and dispersion (also known as molecular weight distribution) (Mw / Mn) of a resin are defined by GPC (Gel Permeation Chromatography) )) GPC measurement (HLC-8120GPC manufactured by TOSOH CORPORATION) (solvent: tetrahydrofuran, flow rate (sample injection amount): 10 μL, column: TSK gel Multipore HXL-M manufactured by TOSOH CORPORATION, column temperature: 40 ° , Flow rate: 1.0 mL / min, Detector: Polystyrene conversion value of differential refractive index detector (Refractive Index Detector).

In the present specification, pKa (acid dissociation constant pKa) refers to the acid dissociation constant pKa in an aqueous solution, for example, as defined in Chemical Handbook (II) (4th edition revised, 1993, edited by the Japanese Chemical Society, Maruzen Company, Limited). The lower the value of the acid dissociation constant pKa, the higher the acid strength. Specifically, the acid dissociation constant pKa in the aqueous solution can be measured by measuring the acid dissociation constant at 25 ° C using an infinitely diluted aqueous solution. Alternatively, the value of a database based on Hammett's substituent constants and well-known literature values can also be calculated by calculation using the following software suite 1. All the values of pKa described in this specification represent values obtained by calculation using the software package.

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

In the description of the group (atomic group) label in this specification, the undescribed and unsubstituted labels include a group having no substituent and a group having a substituent. For example, "alkyl" means not only an alkyl group (unsubstituted alkyl group) without a substituent, but also an alkyl group (substituted alkyl group) with a substituent. The "organic group" in the present specification means a group containing at least one carbon atom.

In addition, in this specification, the kind of the substituent, the position of the substituent, and the number of the substituent are not particularly limited, such as when "may have a substituent". The number of substituents may be, for example, one, two, three or more. Examples of the substituent include a monovalent non-metallic atomic group other than a hydrogen atom. For example, it can be selected from the following substituent group group T.
(Substituent T)
Examples of the substituent T include 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 third butoxy group; phenoxy groups and p-toluene Aryloxy groups such as oxy; alkoxycarbonyl groups such as methoxycarbonyl, butoxycarbonyl, and phenoxycarbonyl; ethoxyl groups such as ethoxyl, propionyloxy, and benzyloxy; Fluorenyl groups such as fluorenyl, benzamyl, isobutylfluorenyl, acrylfluorenyl, methacrylfluorenyl, and methoxalyl; methyl sulfanyl and tertiary butylsulfanyl Alkyl sulfanyl; aryl sulfanyl such as phenyl sulfanyl and p-toluene sulfanyl; alkyl; cycloalkyl; aryl; heteroaryl Hydroxy; carboxyl; methylamido; sulfo; cyano; alkylaminocarbonyl; arylaminocarbonyl; sulfamidino; silyl; amine; monoalkylamino; dialkylamino; arylamine Base; and such combinations.

[Photosensitized radiation- or radiation-sensitive resin composition]
The actinic radiation- or radiation-sensitive resin composition of the present invention (hereinafter, also referred to as "resist composition") includes: an ether compound; a resin, including a repeating unit having a phenolic polar group and an acid-decomposable group A repeating unit; a photoacid generator; an acid diffusion control agent which is a compound different from the ether compound; and a solvent.
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, in the resist composition, the mass ratio of the content of the ether compound to the content of the resin is 0.1 or less.
The solid content concentration is more than 20% by mass.

Although the mechanism which can solve the subject of this invention by employing such a structure in a resist composition is not clear, the present inventors etc. thought that it is as follows.
It is considered that the following is helpful to solve the problem of the present invention, that is, the ether compound is present in the resist composition in a certain ratio, thereby improving the adhesion of the resist film to a substrate or the like, even when forming a high aspect ratio In the case of a pattern, it is also possible to suppress the collapse of the pattern, thereby improving the contrast of the pattern analyzed during exposure to development.
The resist composition of the present invention is considered to have a solid content concentration of more than 20% by mass, and the resin contains a repeating unit having a phenolic polar group, and is used to form a thick resist for obtaining a pattern having a high aspect ratio The suitability of the etching film is improved.
Moreover, the pattern obtained by using the resist composition of this invention is also excellent in the cross-sectional shape (rectangularity) of a pattern.

Hereinafter, the components contained in the resist composition of the present invention will be described in detail. In addition, the resist composition of the present invention may be a positive resist composition or a negative resist composition. Moreover, it may be a resist composition for alkali development or a resist composition for organic solvent development. Among them, a positive-type resist composition and a resist composition for alkali development are preferred.
The resist composition of the present invention is typically a chemically amplified resist composition.

<Ether compound>
The resist composition of the present invention contains an ether compound.
The molecular weight of the ether compound is preferably 100 to 2000, more preferably 150 to 1,000, and still more preferably 200 to 600.
The ether compound is a compound having an ether group (-O-).
The ether group is respectively bonded to a carbon atom at two bonding positions.
The ether group contained in the ether compound does not mean a group directly bonded to a carbonyl carbon (a carbon atom forming -C (= O)-) to form an ester group.

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

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

AL stands for alkylene. The above-mentioned alkylene group may be branched or linear. It may or may not have a cyclic structure.
The number of carbons of the alkylene group is preferably 1 to 10, more preferably 1 to 5 and even more preferably 2 to 3.
The substituent which the above-mentioned alkylene group may have is not particularly limited, and unsubstituted is preferred. In addition, the above-mentioned preferable carbon number is a number which does not include the number of carbon atoms contained in a substituent.
Among them, as the alkylene group, -CH ₂ -CH ₂ -or -CH ₂ -CH ₂ -CH ₂ -is preferred.
When there are plural ALs, the plural ALs may be the same or different.

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

The group bonded to the group represented by the general formula (O1) at * x is not particularly limited, and examples thereof include a hydrogen atom, an alkylene group, and an aromatic ring group (preferably having 6 to 15 carbon atoms). For example, a benzene ring group) or an alkyl group (preferably having 1 to 5 carbon atoms).
When a is 1, the atom bonded to the group represented by the general formula (O1) at * x is a carbon atom other than a carbonyl carbon. The carbon atoms other than the carbonyl carbon are, for example, carbon atoms constituting an aromatic ring group (preferably 6 to 15 carbon atoms. An aromatic hydrocarbon group is preferable, and a benzene ring group is more preferable). It is preferably a carbon atom having 1 to 5 carbon atoms or a carbon atom constituting an alkylene group.

The group bonded to the group represented by the general formula (O1) at * y is not particularly limited, and examples thereof include a hydrogen atom, a hydroxyl group, an ether group, and an aryloxy group (preferably having 6 to 15 carbon atoms) (For example, phenoxy) 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 be bonded to each other to form a ring. R _p or R _q may be a divalent linking group (for example, an alkylene group (preferably having 1 to 5 carbon atoms)) and a group represented by the general formula (O1) is bonded at * x to form a radical containing The ring of the group represented by formula (O1).
R _p , R _q, and a ring formed by bonding R _p and R _{q to} each other may each have a group represented by general formula (O1). In addition, R _p or R _q as the divalent linking group may have a group represented by the general formula (O1).

The group represented by the general formula (O1) satisfies at least one of a group bonded at * x is a group other than a hydrogen atom and a group bonded at * y is a group other than a hydroxyl group. The necessary conditions are better.

The number of the groups represented by the general formula (O1) in the ether compound is preferably 1 or more, 1 to 5 is more preferable, and 1 to 3 is further more preferable.
When plural groups represented by the general formula (O1) exist in the ether compound, these may be the same or different.
The number of groups represented by the general formula (O1) in the ether compound is a number obtained by counting as few as possible the number of groups represented by the general formula (O1) present in each compound. . For example, the ether compound represented by "phenyl-O-CH ₂ -CH ₂ -O-CH ₂ -CH ₂ -O-CH ₂ -CH ₂ -O-phenyl" has a general formula of a = 3 ( 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 in the ether compound as the nitrogen-containing compound is not limited, and for example, 1 to 5 is preferable.

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

In General Formula (X1), m represents an integer of 1-10. m is preferably from 1 to 6, and more preferably from 1 to 4.
When there are a plurality of m, that is, when n is an integer of 2 or more, the m of the plurality may be the same or different.

n represents an integer of 1 to 3.

AL stands for alkylene. The form that the AL in the general formula (X1) can take is the same as the form that the AL in the general formula (O1) can take.
When there are plural ALs, the plural ALs may be the same or different.

R ^q1 represents a hydrogen atom or a substituent. As the substituent of R ^q1 , for example, an organic group is preferred, an aromatic ring group (preferably 6 to 15 carbon atoms. An aryl group is preferred, a benzene ring group is more preferred) or an alkyl group (preferably carbon) Numbers 1 to 5) are more preferred.
Moreover, as a substituent which the aromatic ring group in R ^q1 has, for example, an alkoxy group (preferably having 1 to 5 carbon atoms) is preferred.
When plural R ^q1s exist, the plural R ^q1s may be the same or different.
^Among a plurality of R ^q1s , at least one R ^q1 is preferably a benzene ring group.

In addition, when one or more of plural m may be 1 and a group represented by [R ^q1 -(-O-AL-)] is present in the general formula (X1), R ^q1 is more preferably an organic group, an aromatic ring group (preferably 6 to 15 carbon atoms. An aryl group is preferred, a benzene ring group is more preferred) or an alkyl group (preferably carbon number 1 to 5) Is even better.
In this kind of [R ^q1 -(-O-AL-)], the atom directly bonded to (-O-AL-) in R ^q1 is an atom selected from the group consisting of a hydrogen atom and an carbonyl carbon atom as Preferably, carbon atoms other than carbonyl carbon are more preferred. As the carbon atoms other than the carbonyl carbon, for example, a carbon atom constituting an aromatic ring group (preferably 6 to 15 carbon atoms. An aromatic hydrocarbon ring group is preferable, and a benzene ring group is more preferable) or an alkyl group (more A carbon atom having 1 to 5 carbon atoms is more preferred.

R ^q2 represents a hydrogen atom or a substituent. The substituent of R ^q2 is not particularly limited. For example, an organic group having 1 to 20 carbon atoms is preferred, and an alkyl group having 1 to 17 carbon atoms is more preferred.
When there are plural R ^q2s , the plural R ^q2s may be the same or different.

When n is 1 or 2, R ^q1 and R ^q2 may be bonded to each other to form a ring.
The group formed by bonding R ^q1 and R ^{q2 to} each other is preferably an alkylene group (preferably having 1 to 5 carbon atoms).
Among them, when one or more of m is 1, it is preferable that R ^q1 and R ^q2 in [R ^q1 -(-O-AL-)] in the general formula (X1) are bonded to each other to form a ring. . In this case, among the groups formed by R ^q1 and R ^q2 mutually bonding, the atom directly bonded to (-O-AL-) is a carbon atom other than the carbonyl carbon (for example, a carbon constituting an alkylene group) Atomic) is preferred.

When there are a plurality of [R ^q1 -(-O-AL-) _m ] in the general formula (X1), the plurality of [R ^q1 -(-O-AL-) _m ] may be the same or different.
In the general formula (X1), at least one R ^q1 is preferably an aromatic ring group (preferably 6 to 15 carbons), an aryl group (preferably 6 to 15 carbons) is more preferable, and a phenyl group is more good.

The ether compound preferably does not have a fluorine atom.

In the resist composition, the mass ratio R1 (content of the ether compound / content of the acid diffusion control agent) of the content of the ether compound to the content of the acid diffusion control agent is 0.2 or more, preferably 0.2 to 100, 0.2 to 20 More preferably, 0.2 to 1 is more preferable.
In the resist composition, the mass ratio R2 (content of the ether compound / content of the resin) of the content of the ether compound to the content of the resin is 0.1 or less, preferably 0.0002 to 0.05, and more preferably 0.0002 to 0.01. 0.0003 to 0.005 is more preferable.
The acid diffusion control agent and resin will be described in detail in the following paragraphs.
The content of the ether compound in the resist composition is not particularly limited as long as it satisfies the above-mentioned requirements of R1 and R2. For example, it is preferably 0.006 to 8% by mass relative to the total solid content of the resist composition, and 0.01 -1 mass% is more preferable, and 0.02-0.5 mass% is more preferable.
The solid content means a component that forms a resist film, and does not include a solvent. Moreover, as long as it is a component which forms a resist film, even if the property is liquid, it is considered a solid component.
The ether compound may be used alone or in combination of two or more. When two or more kinds of ether compounds are used, the total content is preferably within the above range.

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

(Repeating unit with phenolic polar group)
Resin B contains a repeating unit having a phenolic polar group. The phenolic polar group refers to a group in which a polar group is bonded to an aromatic ring group.
The aromatic ring group may be an aromatic hydrocarbon ring group or an aromatic heterocyclic group. The aromatic ring group may be monocyclic or polycyclic. A non-aromatic ring may be fused to the aromatic ring group.
Examples of the aromatic ring group include an aromatic hydrocarbon ring group having 6 to 18 carbon atoms such as a benzene ring group, a naphthalene ring group and an anthracene ring group, or a thiophene ring group, a furan ring group, a pyrrole ring group, a benzothiophene ring group, Aromatic heterocyclic rings containing heterocyclic rings such as benzofuran ring, benzopyrrole ring, triple well ring, imidazole ring, benzimidazole ring, triazole ring, thiadiazole ring, and thiazole ring. Basis is better.
Among them, the aromatic ring group is preferably an aromatic hydrocarbon group, and the benzene ring group is more preferable.

As the polar group bonded to the aromatic ring group, an alkali-soluble group is preferred. Examples of the polar group include a hydroxyl group, a carboxyl group, a fluorinated alcohol group, a sulfonic acid group, a sulfonamido group, a sulfonamido group, and an (alkyl group). Sulfonyl) (alkylcarbonyl) methylene, (alkylsulfonyl) (alkylcarbonyl) fluorenimine, bis (alkylcarbonyl) methylene, bis (alkylcarbonyl) fluorenimine Acid groups such as bis (alkylsulfonyl) methylene, bis (alkylsulfonyl) fluorenimine, tris (alkylcarbonyl) methylene and tris (alkylsulfonyl) methylene .

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

[Chemical 1]

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 a hydrogen atom.

As the alkyl group of R ₄₁ , R ₄₂ and R ₄₃ , methyl, ethyl, propyl, isopropyl, n-butyl, second butyl, hexyl, 2-ethylhexyl, octyl and dodecyl An alkyl group having 20 or less carbon atoms is preferred, and an alkyl group having 8 or less carbon atoms is more preferred.

As the alkyl group contained in the alkoxycarbonyl group, the same groups as those described above for R ₄₁ , R ₄₂ and R ₄₃ are preferred.

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

As the halogen atom, a fluorine atom is preferred.

R ₄₂ may be bonded to a substituent of Ar ₄ described later or L ₄ to form a ring.

X ₄ represents a single bond, -COO- or -CONR _44- .
R ₄₄ represents a hydrogen atom or an alkyl group.
As the alkyl group, an alkyl group similar to the alkyl group of R ₄₁ to R ₄₃ is preferable.
As X ₄ , a single bond, -COO- or -CONH- is preferred, a single bond or -COO- is more preferred, and a single bond is further preferred.

L ₄ represents a single bond or a divalent linking group.
Examples of the divalent linking group include an ether group, a carbonyl group, an ester group, a thioether group, -SO _2- , -NR- (R represents a hydrogen atom or an alkyl group), and a divalent hydrocarbon group (for example, Alkyl, alkenyl (example: -CH = CH-), alkynyl (example: -C≡C-), and aryl) or a combination of these.
Among them, as the divalent linking group, an alkylene group is preferred, and as the alkylene group, methylene, ethylene, propyl, butyl, hexyl, and octyl have 1 to 8 carbon atoms. Is more preferred.
When L ₄ and R _{42 are} bonded to form a ring, L ₄ represents a trivalent linking group. In this case, in the group which is a divalent linking group of L ₄ and which can further have a substituent, the substituents and R ₄₂ are bonded to each other to form a single bond or a divalent link. The group (for example, the above-mentioned group) is preferably a single bond or an alkylene group (methylene, ethylene, propyl, butyl, hexyl, and octyl, etc.) Alkylene is more preferred).
It is preferred that the ring formed when R ₄₂ and L _{4 are} bonded is a 5- or 6-membered ring.
Among them, it is preferable that L ₄ is a single bond.

Ar ₄ represents a (n + 1) -valent aromatic ring group. Ar ₄ may have a substituent other than Y, and it is preferable that the substituent other than Y is not a polar group. When a substituent of Ar ₄ is bonded to R ₄₂ to form a ring, Ar ₄ represents a (n + 2) -valent aromatic ring group.
As the aromatic ring group of Ar ₄ , the aforementioned aromatic ring group is similarly exemplified.
Among them, Ar ₄ is preferably an aromatic hydrocarbon ring group having 6 to 18 carbon atoms, and benzene ring group is more preferable.
Regarding those formed by the bonding of a substituent of Ar ₄ and R ₄₂ , a single bond or a divalent linking group (for example, the above-mentioned group) is preferred, and a single bond or an alkylene group (methylene, 1 to 8 carbons such as ethyl, propyl, butyl, hexyl and octyl are preferred) are more preferred).

Y represents a polar group.
As the polar group, the aforementioned polar group is similarly exemplified. Among them, as the polar group, a hydroxyl group is preferred.
When Ar ₄ is an aromatic heterocyclic group having a benzene ring group portion, it is preferable that Y is bonded to a benzene ring group portion included in the aromatic heterocyclic group.

n represents an integer of 1 to 4.

Examples of the substituent which the above-mentioned alkyl group, cycloalkyl group, alkoxycarbonyl group, alkylene group, aromatic ring group, and aromatic hydrocarbon ring group can have include the above-mentioned substituent T. The number of carbon atoms described in the above-mentioned alkyl group, cycloalkyl group, alkoxycarbonyl group, alkylene group, aromatic ring group, and aromatic hydrocarbon ring group does not include the number of carbon atoms in the substituent.

The content of the repeating unit having a phenolic polar group is preferably 20 to 74 mol%, more preferably 30 to 64, and more preferably 45 to 64 mol% relative to all the repeating units of the resin B.
As the repeating unit having a phenolic polar group, only one kind may be used, or two or more kinds may be used. When two or more kinds are used, the total content of these is preferably within the above range.

(Repeating unit with acid-decomposable group)
Resin B contains a repeating unit having an acid-decomposable group.
An acid-decomposable group refers to a group having a structure in which a polar group is protected by a protecting group that is released by the action of an acid.
A protecting group refers to a group that is released by the action of an acid. The protective group is preferably substituted with a hydrogen atom of a polar group to form an acid-decomposable group.
Resin B is a kind of resin. Since resin B contains a repeating unit having such an acid-decomposable group, typically, resin B is an alkali-insoluble or poorly-soluble resin, and the protective group is released by the action of acid, thereby The solubility of alkali is increased. Also, similarly, the resin B is typically a resin that is soluble in an organic solvent, and the protective group is removed by the action of an acid, thereby reducing the solubility in the organic solvent.

As the polar group protected by a protecting group, an alkali-soluble group is preferred, and examples thereof include a carboxyl group, a phenolic hydroxyl group, a fluorinated alcohol group, a sulfonic acid group, a sulfonamido group, a sulfonamido group, and an (alkyl group) Sulfonyl) (alkylcarbonyl) methylene, (alkylsulfonyl) (alkylcarbonyl) fluorenimine, bis (alkylcarbonyl) methylene, bis (alkylcarbonyl) fluorenimine Acid groups such as bis (alkylsulfonyl) methylene, bis (alkylsulfonyl) fluorenimine, tris (alkylcarbonyl) methylene and tris (alkylsulfonyl) methylene And alcoholic hydroxyl groups.
Among them, as the polar group protected by a protecting group, a carboxyl group, a phenolic hydroxyl group, a fluorinated alcohol group (preferably a hexafluoroisopropanol group) or a sulfonic acid group is preferred, a carboxyl group or a phenolic hydroxyl group is more preferred, Is even better.

Examples of the protective group include groups represented by the formulae (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 each independently represent an alkyl group (linear or branched), a cycloalkyl group (monocyclic or polycyclic), an aryl group, an aralkyl group, or Alkenyl. When all of Rx ₁ to Rx ₃ are alkyl groups (straight-chain or branched), it is preferable that at least two of Rx ₁ to Rx ₃ are methyl groups.
Wherein, Rx ₁ ~ Rx ₃ each independently represents a linear or branched alkyl group is preferred, Rx ₁ ~ Rx ₃ each independently represent a linear alkyl group is more preferred.
Two of Rx ₁ to Rx ₃ may be bonded to form a monocyclic ring or a polycyclic ring.
As the alkyl group of Rx ₁ to Rx ₃ , an alkyl group having 1 to 4 carbon atoms such as methyl, ethyl, n-propyl, isopropyl, n-butyl, isobutyl, or third butyl is preferred.
As the cycloalkyl group of Rx ₁ to Rx _3, a monocyclic cycloalkyl group such as cyclopentyl group or cyclohexyl group, or a polycyclic group such as norbornyl group, tetracyclodecyl group, tetracyclododecyl group, or adamantyl group Is preferred.
The aryl group of Rx ₁ to Rx ₃ is preferably an aryl group having 6 to 10 carbon atoms, and examples thereof include a phenyl group, a naphthyl group, and an anthryl group.
The aralkyl group of Rx ₁ to Rx ₃ is preferably an aralkyl group having 7 to 12 carbon atoms, and examples thereof include benzyl, phenethyl, and naphthylmethyl.
The alkenyl group of Rx ₁ to Rx ₃ is preferably an alkenyl group having 2 to 8 carbon atoms, and examples thereof include vinyl, allyl, butenyl, and cyclohexenyl.
Cycloalkyl formed as two bonds between Rx ₁ to Rx ₃ , monocyclic cycloalkyl such as cyclopentyl or cyclohexyl, norbornyl, tetracyclodecyl, tetracyclododecyl Polycyclic cycloalkyl groups such as, or adamantyl are preferred, and monocyclic cycloalkyl groups having 5 to 6 carbon atoms are more preferred.
Regarding a cycloalkyl group formed by bonding two of Rx ₁ to Rx ₃ , for example, one of the methylene groups constituting the ring may be substituted with a hetero atom such as an oxygen atom or a group having a hetero atom such as a carbonyl group.
Regarding 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 are} bonded to form the aforementioned cycloalkyl group.

In the formula (Y3), R ₃₆ to R ₃₈ each independently represent a hydrogen atom or a monovalent organic group. R ₃₇ and R ₃₈ may be bonded to each other to form a ring. Examples of the monovalent organic group include a group represented by the formula (Y1) and an alkyl group other than the group represented by the formula (Y1) (which may be linear or branched, or It may have a cyclic structure. For example, carbon number is 1 to 10, methyl, ethyl, n-propyl, isopropyl, n-butyl, isobutyl, and 1-adamantyl, etc.), aryl, aralkyl And alkenyl. It is also preferable 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 .
In addition, 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 of the main chain in the repeating unit. When R _{38 is} bonded to other groups in the repeating unit, it is preferred that R ₃₈ and the other groups form a single bond or a divalent linking group (such as an alkylene group). When R _{38 is} bonded to another group in the repeating unit, the repeating unit forms a ring including a group represented by formula (Y3).

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

[Chemical 2]

Among them, 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 (for example, a group combining an alkyl group and an aryl group).
M represents a single bond or a divalent linking group.
Q represents an alkyl group which may have a hetero atom, a cycloalkyl group which may have a hetero atom, an aryl group which may have a hetero atom, an amine group, an ammonium group, a mercapto group, a cyano group, an aldehyde group, or a combination thereof (for example, , A group combining an alkyl group with a cycloalkyl group).
In the alkyl group and the cycloalkyl group, for example, one of the methylene groups may be substituted with a hetero atom such as an oxygen atom or a group having a hetero atom such as a carbonyl group.
In addition, one of L ₁ and L ₂ is a hydrogen atom, and the other is preferably an alkyl group, a cycloalkyl group, an aryl group, or a group in which an alkylene group and an aryl group are combined.
At least two of Q, M, and L ₁ may be bonded to form a ring (preferably, a 5-membered ring or a 6-membered ring).
From the viewpoint of miniaturization of the pattern, L ₂ is preferably a secondary or tertiary alkyl group, and tertiary alkyl group is more preferred. Examples of the secondary alkyl group include isopropyl, cyclohexyl, and norbornyl, and examples of the tertiary alkyl group include third butyl or adamantyl. In these aspects, Tg (glass transition temperature) and / or activation energy become high, so that the film strength can be secured, and blurring can be suppressed.

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

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

[Chemical 3]

In the general formula (A02),
Xa ₁ represents a hydrogen atom or an alkyl group which may have a substituent.
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). Among them, when all of Rx ₁ to Rx ₃ are alkyl groups (linear or branched), it is preferable that at least two of Rx ₁ to Rx ₃ are methyl groups.
Two of Rx ₁ to Rx ₃ may be bonded to form a cycloalkyl group (monocyclic or polycyclic).

Examples of the alkyl group which may have a substituent 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 thereof include an alkyl group having 5 or less carbon atoms and a fluorenyl group having 5 or less carbon atoms. Preferably, methyl 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 of 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, and -CH ₂ -group,-(CH ₂ ) ₂ -group, or-(CH ₂ ) ₃ -group is Better.

As the alkyl group of Rx ₁ to Rx ₃ , an alkyl group having 1 to 4 carbon atoms such as methyl, ethyl, n-propyl, isopropyl, n-butyl, isobutyl, or third butyl is preferred.
As the cycloalkyl group of Rx ₁ to Rx ₃ , monocyclic cycloalkyl group such as cyclopentyl group and cyclohexyl group, or polycyclic group such as norbornyl group, tetracyclodecyl group, tetracyclododecyl group and adamantyl group. Cycloalkyl is preferred.
As the cycloalkyl group formed by the two bonds of Rx ₁ to Rx ₃ , monocyclic cycloalkyl groups such as cyclopentyl group and cyclohexyl group are preferred. In addition, norbornyl group and tetracyclodecyl group Polycyclic cycloalkyl such as tetracyclododecyl and adamantyl are preferred. Among them, a monocyclic cycloalkyl group having 5 to 6 carbon atoms is preferred.
A cycloalkyl group formed by bonding two of Rx ₁ to Rx ₃ , for example, one of the methylene groups constituting the ring may be substituted with a hetero atom such as an oxygen atom or a group having a hetero atom such as a carbonyl group.
In the repeating unit represented by the general formula (AI), for example, it is preferable that Rx ₁ is a methyl group or an ethyl group, and Rx ₂ and Rx _{3 are} bonded to form the aforementioned cycloalkyl group.

When each of the above-mentioned groups has a substituent, examples of the substituent include an alkyl group (carbon number 1-4), a halogen atom, a hydroxyl group, an alkoxy group (carbon number 1-4), a carboxyl group, and an alkoxycarbonyl group. (Carbon number 2 to 6) and so on. 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%, and still more preferably 20 to 45 mol% relative to all the repeating units of the resin B.
The repeating unit having an acid-decomposable group may be used singly, or two or more kinds may be used. When two or more kinds are used, the total content of these is preferably within the above range.

(Repeating unit represented by general formula (VW))
It is also preferable that the resin B has a repeating unit represented by the general formula (VW).

[Chemical 4]

In the 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 a fluorenyl group.
Rv is preferably a hydrogen atom, a methyl group, a hydroxymethyl group, or a trifluoromethyl group, and more preferably a hydrogen atom or a methyl group.

Rw represents a hydrocarbon group having an alicyclic group. Regarding Rw, Rw may be an alicyclic group itself, and Rw may be a group containing an alicyclic group in part.
The above-mentioned hydrocarbon group may have a substituent, and as the substituent which may have, a group other than a polar group (a group exemplified as a polar group so far as a more specific example) is preferable.
The alicyclic group possessed by Rw may be a monocyclic (monocyclic hydrocarbon ring group) or a 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.
The polycyclic hydrocarbon ring group includes a ring collection hydrocarbon ring group and a crosslinked cyclic hydrocarbon ring group.
Examples of the ring group hydrocarbon ring group include a dicyclohexane ring group and a perhydronaphthalene ring group.
Examples of the cross-linked cyclic hydrocarbon ring group include a pinane ring group, a bornane ring group, a norbornane ring group, a norbornane ring group, and a bicyclooctane ring group (bicyclic [2.2. 2] Octane ring group, bicyclic [3.2.1] octane ring group, etc.) 2 cyclic hydrocarbon ring groups; homoblane ring group, adamantane ring group, tricyclic ring [5.2.1.0 ^{2, 6]} decane and tricyclo ring group [4.3.1.1 ^2,5] undecane ring group 3 cyclic hydrocarbon ring group; and tetracyclo [4.4.0.1 ^2,5 .1 ^7,10] dodecane ring And 4-ring hydrocarbon ring groups such as perhydro-1,4-methylene-5,8-methylene naphthalene ring groups. The crosslinked cyclic hydrocarbon ring group also includes a condensed cyclic hydrocarbon ring group (for example, a perhydronaphthalene (decahydronaphthalene) ring group, a perhydroanthracene ring group, a perhydrophenanthrene ring group, a perhydrofluorenyl ring group, Perhydrofluorenyl, perhydroindenyl and perhydrofluorinated rings are condensed condensed ring groups of 5 to 8-membered cycloalkane rings).

As the cross-linked cyclic hydrocarbon ring group, norbornane ring group, adamantane ring group, bicyclic octane ring group or tricyclic [5､2､1､0 ^2,6 ] decane ring group is more preferable, norbornene Alkane or adamantane is more preferred.

As the substituent which the alicyclic group may have, for example, a halogen atom or an alkyl group is preferred.

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

Hereinafter, the repeating unit represented by general formula (VW) is illustrated.
In the formula, Ra represents H, CH ₃ , CH ₂ OH, or CF ₃ .

[Chemical 5]

When the resin B has a repeating unit represented by the general formula (VW), its content is preferably 1 to 40 mol%, more preferably 3 to 25 mol%, and 5 to 15 with respect to all the repeating units of the resin B. Moire% is further preferred.
The repeating unit represented by the general formula (VW) may be used singly, or two or more kinds may be used. When two or more kinds are used, the total content of these is preferably within the above range.

The resin B may have a repeating unit other than the above-mentioned repeating unit. As such a repeating unit, for example, a repeating unit represented by general formula (P01), such as a repeating unit in which n is 0 (a repeating unit based on benzyl (meth) acrylate, etc.) is mentioned.

In all the repeating units of resin B, the content of repeating units having a benzene ring group is preferably 80 mol% or less, more preferably less than 65 mol%, and more preferably 60 mol% or less. The lower limit is not particularly limited, for example, 20 mol% or more is preferable, 30 mol% or more is more preferable, and 45 mol% or more is more preferable.
In addition, when the aromatic ring group having a repeating unit having a phenolic polar group in the resin B is a benzene ring group, the repeating unit having a phenolic polar group is equivalent to a repeating unit having a benzene ring group.

Resin B can be synthesized according to a conventional method (for example, using radical polymerization).
As a polystyrene conversion value based on the GPC method, the weight average molecular weight of the resin B is preferably 1,000 to 200,000, more preferably 3,000 to 25,000, and even more preferably 10,000 to 25,000. By setting the weight average molecular weight of the resin B to 1,000 to 200,000, deterioration in heat resistance and dry etching resistance can be prevented, and furthermore, deterioration in developability and deterioration in film-forming property due to increased viscosity can be prevented.
The degree of dispersion (molecular weight distribution) of the resin B is usually 1 to 5, 1 to 3 is preferable, 1.2 to 3.0 is more preferable, and 1.2 to 2.0 is more preferable. The smaller the dispersion, the better the resolution and the shape of the photoresist, and the smoother the sidewall of the photoresist pattern and the better the roughness.

The resist composition of the present invention is not limited as long as the content of the resin B satisfies the above-mentioned mass ratio R2. For example, it is preferably 70 to 99.9% by mass with respect to the total solid content, and 80 to 99.0% by mass. More preferably, 95 to 98.5% by mass is more preferable.
The resin B may be used alone or in combination of two or more. When two or more are used, the total content of these is preferably within the above range.

<Photo acid generator>
The resist composition of the present invention further contains a photoacid generator.
A photoacid generator is a compound which generates an acid by irradiation with actinic rays or radiation.
As the photoacid generator, a compound that generates an organic acid by irradiation with actinic rays or radiation is preferred. For example, a sulfonium salt compound, a sulfonium salt compound, a diazonium salt compound, a sulfonium salt compound, a fluorenimine sulfonate compound, an oxime sulfonate compound, a diazonium compound, a difluorene compound, and o-nitrobenzyl Sulfonate compound.

As the photoacid generator, a known compound that generates an acid by irradiation with actinic rays or radiation can be used alone, or a mixture of these can be appropriately selected and used. For example, paragraphs <0125> to <0319> of US Patent Application Publication No. 2016 / 0070167A1, paragraphs <0086> to <0094> of US Patent Application Publication No. 2015 / 0004544A1, and US Patent Application Publication No. 2016 / 0237190A1 can be made. The known compounds disclosed in paragraphs <0323> to <0402> of the specification are preferably used as the photoacid generator (C).

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

[Chemical 6]

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

As the organic groups of R ₂₀₁ , R ₂₀₂ and R ₂₀₃ , an aryl group (carbon number 6 to 15 is preferred), a linear or branched alkyl group (carbon number 1 to 10 are each independently) (Preferably) and cycloalkyl (preferably 3 to 15 carbons) and the like.
In addition, the preferred carbon numbers of the aryl, alkyl, and cycloalkyl groups do not include the number of carbon atoms contained in the substituents of the groups.

In addition, two of R ₂₀₁ to R ₂₀₃ may be bonded to form a ring structure, and the ring may have an oxygen atom, a sulfur atom, an ester group, an amido group, or a carbonyl group. Examples of the group formed by the two bonds among R ₂₀₁ to R ₂₀₃ include an alkylene group (for example, butylene and pentayl) and -CH ₂ -CH ₂ -O-CH ₂ -CH ₂ -Wait.
Z ^- represents an anion (non-nucleophilic anion is preferred.).

Preferred embodiments of the cation in the general formula (ZI) include correspondence among the compound (ZI-1), compound (ZI-2), compound (ZI-3), and compound (ZI-4) described later. Of groups.
The photoacid generator may be a compound having a structure represented by a plurality of general formulas (ZI). For example, R having the general formula (ZI) of the compound represented by ₂₀₁ ~ R ₂₀₃ and at least one R another compound of formula (ZI) represented in the ₂₀₁ ~ R ₂₀₃ by at least one A compound having a single bond or a linking structure.

First, the compound (ZI-1) will be described.
The compound (ZI-1) is an arylfluorene compound in which at least one of R ₂₀₁ to R ₂₀₃ in the general formula (ZI) is an aryl group, that is, a compound in which arylfluorene is a cation.
Regarding the arylfluorene compound, all of R ₂₀₁ to R ₂₀₃ may be an aryl group, or a part of R ₂₀₁ to R ₂₀₃ may be an aryl group, and the remaining portion may be an alkyl group or a cycloalkyl group.
Examples of the arylfluorene compound include a triarylfluorene compound, a diarylalkylfluorene compound, an aryldialkylfluorene compound, a diarylcycloalkylfluorene compound, and an arylbicycloalkylfluorene compound.

As the aryl group contained in the arylfluorene compound, a phenyl group or a naphthyl group is preferable, and a phenyl group is more preferable. The aryl group may be an aryl group including a heterocyclic structure having an oxygen atom, a nitrogen atom, a sulfur atom, or the like. Examples of the heterocyclic structure include a pyrrole residue, a furan residue, a thiophene residue, an indole residue, a benzofuran residue, and a benzothiophene residue. When the arylfluorene compound has two or more aryl groups, the two or more aryl groups may be the same or different.
The arylfluorene compound may have 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. Examples include methyl, ethyl, propyl, n-butyl, second butyl, third butyl, cyclopropyl, cyclobutyl, and cyclohexyl.

The aryl, alkyl, and cycloalkyl groups of R ₂₀₁ to R ₂₀₃ may each independently have an alkyl group (for example, a carbon number of 1 to 15), a cycloalkyl group (for example, a carbon number of 3 to 15), and an aryl group (for example, The carbon number is 6 to 14), an alkoxy group (for example, 1 to 15 carbon numbers), a halogen atom, a hydroxyl group, or a phenylthio group as a substituent.

Next, the compound (ZI-2) will be described.
In the compound (ZI-2), R ₂₀₁ to R ₂₀₃ in the formula (ZI) are each independently a compound representing an organic group having no aromatic ring. The aromatic ring also includes an aromatic ring including a hetero atom.
As the organic group having no aromatic ring in R ₂₀₁ to R ₂₀₃ , a carbon number of 1 to 30 is preferable, and a carbon number of 1 to 20 is more preferable.
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, a 2-oxocycloalkyl group, or an alkane group is preferred. Oxocarbonylmethyl is more preferred, and linear or branched 2-oxoalkyl is more preferred.

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

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

[Chemical 7]

In the 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 above-mentioned ring structure may have an oxygen atom, a sulfur atom, an ester group, an amido group, or a carbon-carbon double bond.
R ₂ and R ₃ 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 be bonded to each other to form a ring. R ₁ and R ₂ may be bonded to each other to form a ring, and the formed ring preferably has a carbon-carbon double bond. R _x and R _y may be bonded to each other to form a ring, and the formed ring preferably has an oxygen atom, a sulfur atom, an ester group, an amido group, or a carbon-carbon double bond.
Z ^- represents an anion.

In the general formula (ZI-3), the alkyl group and cycloalkyl group represented by R ₁ are a linear alkyl group having 1 to 15 carbon atoms (preferably 1 to 10 carbon atoms), and 3 to 15 carbon atoms ( It is preferably a branched alkyl group having 3 to 10 carbon atoms or a cycloalkyl group having 3 to 15 carbon atoms (preferably 1 to 10 carbon atoms). Specific examples include methyl and ethyl groups. Group, propyl, n-butyl, second butyl, third butyl, cyclopropyl, cyclobutyl, cyclohexyl and norbornyl.
As the aryl group represented by R ₁ , a phenyl group or a naphthyl group is preferable, and a phenyl group is more preferable. The aryl group may be an aryl group containing a heterocyclic structure having an oxygen atom, a sulfur atom, or the like. Examples of the heterocyclic structure include a furan ring, a thiophene ring, a benzofuran ring, a benzothiophene ring, and the like.

It is also preferred that R ₁ further has a substituent (for example, a substituent group group T).
In addition, when R ₁ has a ring structure, the above-mentioned ring structure may have an oxygen atom, a sulfur atom, an ester group, an amido group, or a carbon-carbon double bond.

Examples of the alkyl group, cycloalkyl group, and aryl group represented by R ₂ and R ₃ are the same as those of R ₁ described above, and preferred embodiments thereof are also the same. R ₂ and R ₃ may be bonded to form a ring.
Examples of the halogen atom represented by R ₂ and R ₃ include a fluorine atom, a chlorine atom, a bromine atom, and an iodine atom.

_Examples of the alkyl group and cycloalkyl group represented by R _x and R _y are the same as those of 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), and specifically, 2-oxopropyl groups And 2-oxobutyl.
Examples of the alkoxycarbonylalkyl group represented by R _x and R _y include those having 1 to 15 carbon atoms (preferably having 1 to 10 carbon atoms). R _x and R _y may be bonded to form a ring.
R _x and R _y may be bonded to each other to form a ring, and a ring formed by R _x and R _y being bonded to each other may have an oxygen atom, a sulfur atom, an ester group, an amido group, or a carbon-carbon double bond.
In addition, the formed ring has an oxygen atom and the like means that, for example, two groups capable of bonding to each other (for example, R _x and R _y ) are bonded to each other to form an alkylene group. A form in which a methylene group is substituted with an oxygen atom or the like.
As a ring formed by bonding R _x and R _{y to} each other, a 3 to 10 member ring is more preferred, a 4 to 8 member ring is more preferred, and a 5 or 6 member ring is further preferred.

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

As for the compound (ZI-3), the compound (ZI-3A) is preferred.
The compound (ZI-3A) is a compound represented by the following general formula (ZI-3A) and is a compound having a benzamidine methylsulfonium salt structure.

[Chemical 8]

In the 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, Hydroxyl, nitro, alkylthio or arylthio.
R _6c and R _7c have the same meanings as R ₂ and R ₃ in the general formula (ZI-3), and their preferred aspects are also the same.
As R _x and R _y, the same as in the general formula R _x and R _y wherein the meaning (ZI-3) in which the preferred aspects are also the same.

Any two or more of R _1c to R _5c , R _x and R _y may be bonded to each other to form a ring, and the ring may independently have an oxygen atom, a sulfur atom, an ester group, an amido group, or a carbon-carbon double bond . R _5c and R _6c , R _5c and R _x may be bonded to each other to form a ring, and it is preferable that the ring independently has a carbon-carbon double bond. R _6c and R _7c may be bonded to each other to form a ring.
In addition, the formed ring has an oxygen atom and the like means that, for example, two groups capable of bonding (for example, R _x and R _y ) are bonded to each other to form an alkylene group. A form in which a methyl group is substituted with an oxygen atom or the like.
Examples of the ring include an aromatic or non-aromatic hydrocarbon ring, an aromatic or non-aromatic hetero ring, and a polycyclic condensed ring obtained by combining two or more of these rings. As the ring, a 3 to 10 member ring is more preferable, a 4 to 8 member ring is more preferable, and a 5 or 6 member ring is more preferable.

_Examples of two or more of R _1c to R _5c which are formed by bonding R _6c and R _7c and R _x and R _y include butyl, pentyl, and -CH ₂ -CH ₂ -O-CH ₂ -CH ₂ -etc.
As the group formed by bonding R _5c and R _6c and R _5c and R _x , a single bond or an alkylene group is preferred. Examples of the alkylene group include a methylene group and an ethylene group.
Zc ^- represents an anion.

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

[Chemical 9]

In the general formula (ZI-4),
l represents an integer from 0 to 2.
r represents an integer from 0 to 8.
R ₁₃ represents a hydrogen atom, a fluorine atom, a hydroxyl group, an alkyl group, an alkoxy group, an alkoxycarbonyl group, or a group having a cycloalkyl group (which may be a cycloalkyl group itself, or a group containing a cycloalkyl group in part) The cycloalkyl moiety may be monocyclic or polycyclic). These groups may have a substituent.
R ₁₄ represents 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 (which may be a cycloalkyl group itself, or may include a ring in a part thereof) Alkyl group. The cycloalkyl moiety may be monocyclic or polycyclic. For example, cycloalkylsulfonyl, or cycloalkoxy, etc.). These groups may have a substituent. When a plurality of R ₁₄ are present, the R ₁₄ may be the same or different.
R ₁₅ each independently represents an alkyl group, a cycloalkyl group or a naphthyl group. These groups may have a substituent. Two R ₁₅ may be bonded to each other to form a ring. When two R ₁₅ are bonded to each other to form a ring, a hetero atom such as an oxygen atom or a nitrogen atom may be contained in the ring skeleton. In one aspect, it is preferable that two R ₁₅ are an alkylene group and are bonded to each other to form a ring structure.

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

Next, general formulae (ZII) and (ZIII) will be described.
In the general formulae (ZII) and (ZIII), R ₂₀₄ to R ₂₀₇ each independently represent an aryl group, an alkyl group, or a cycloalkyl group.
As the aryl group of R ₂₀₄ to R ₂₀₇ , a phenyl group or a naphthyl group is preferable, and a phenyl group is more preferable. The aryl group of R ₂₀₄ to R ₂₀₇ may be an aryl group including a heterocyclic structure having an oxygen atom, a nitrogen atom, a sulfur atom, or the like. Examples of the skeleton of the aryl group having a heterocyclic structure include pyrrole, furan, thiophene, indole, benzofuran, and benzothiophene.
As the alkyl group and cycloalkyl group of R ₂₀₄ to R ₂₀₇ , a linear alkyl group having 1 to 10 carbon atoms or a branched alkyl group having 3 to 10 carbon atoms (for example, methyl, ethyl, propyl, butane Group and pentyl group) or a cycloalkyl group having 3 to 10 carbon atoms (for example, 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 the substituent which the aryl group, alkyl group, and cycloalkyl group of R ₂₀₄ to R ₂₀₇ may have include an alkyl group (for example, a carbon number of 1 to 15) and a cycloalkyl group (for example, a carbon number of 3 to 3). 15), aryl (for example, 6 to 15 carbons), alkoxy (for example, 1 to 15 carbons), halogen atom, hydroxyl group, phenylthio group, and the like.
Z ^- represents an anion.

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

[Chemical 10]

In the general formula (3),
o represents an integer from 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 carbon number of the alkyl group is preferably 1 to 10, and more preferably 1 to 4. As the alkyl group substituted with at least one fluorine atom, a perfluoroalkyl group is preferred.
Xf is preferably a fluorine atom or a perfluoroalkyl group having 1 to 4 carbon atoms, and more preferably a fluorine atom or CF ₃ . In particular, it is more preferable that Xf of both is a fluorine atom.

R ₄ and R ₅ each independently represent a hydrogen atom, a fluorine atom, an alkyl group, or an alkyl group substituted with at least one fluorine atom. When a plurality of R ₄ and R ₅ exist, R ₄ and R ₅ may be the same or different, respectively.
The alkyl group represented by R ₄ and R ₅ may have a substituent, and the number of carbon atoms is preferably 1 to 4. R ₄ and R _{5 are} preferably a hydrogen atom.
Specific examples and preferable aspects of the alkyl group substituted with at least one fluorine atom are the same as specific examples and preferable aspects of Xf in the general formula (3).

L represents a divalent linking group. When there is a plurality of L, L may be the same or different.
Examples of the divalent linking group include -COO-(-C (= O) -O-), -OCO-, -CONH-, -NHCO-, -CO-, -O-, -S- , -SO-, -SO _2- , alkylene (preferably 1 to 6 carbons), cycloalkyl (preferably 3 to 15 carbons), alkenyl (preferably 2 to carbons) 6) and a bivalent linking base formed by combining a plurality of these. Among these, -COO-, -OCO-, -CONH-, -NHCO-, -CO-, -O-, -SO _2- , -COO-alkylene-, -OCO-alkylene-, -CONH-alkylene- or -NHCO-alkylene- is preferred, -COO-, -OCO-, -CONH-, -SO _2- , -COO-alkylene- or -OCO-alkylene -For better.

W represents an organic group containing a cyclic structure. Among these, a cyclic organic group is preferred.
Examples of the cyclic organic group include an alicyclic group, an aryl group, and a heterocyclic group.
The alicyclic group may be a monocyclic alicyclic group or a polycyclic alicyclic group. Examples of the monocyclic alicyclic group include monocyclic cycloalkyl groups such as cyclopentyl, cyclohexyl, and cyclooctyl. Examples of the polycyclic alicyclic group include polycyclic cycloalkyl groups such as norbornyl, tricyclodecyl, tetracyclodecyl, tetracyclododecyl, and adamantyl. Among them, alicyclic groups having a large volume structure of 7 or more, such as norbornyl, tricyclodecyl, tetracyclodecyl, tetracyclododecyl, and adamantyl, are preferred.

The aryl group may be a monocyclic aryl group or a polycyclic aryl group. Examples of the aryl group include a phenyl group, a naphthyl group, a phenanthryl group, and an anthryl group.
The heterocyclic group may be monocyclic or polycyclic. Polycyclics can more inhibit the diffusion of acids. The heterocyclic group may be aromatic or non-aromatic. Examples of the aromatic heterocyclic ring include a furan ring, a thiophene ring, a benzofuran ring, a benzothiophene ring, a dibenzofuran ring, a dibenzothiophene ring, and a pyridine ring. Examples of the heterocyclic ring having no aromaticity include a tetrahydropyran ring, a lactone ring, a sultone ring, and a decahydroisoquinoline ring. As the hetero ring in the heterocyclic group, a furan ring, a thiophene ring, a pyridine ring, or a decahydroisoquinoline ring is particularly preferred.

The cyclic organic group may have a substituent. Examples of the substituent include an alkyl group (which may be linear or branched, and preferably having 1 to 12 carbon atoms), a cycloalkyl group (which may be monocyclic or polycyclic (including Spiro), any of 3 to 20 carbons is preferred), aryl (6 to 14 carbons is preferred), hydroxyl, alkoxy, ester, amido, polyurethane, urea, Thioether group, sulfonamide group and sulfonate group. In addition, the carbon constituting the cyclic organic group (the carbon that contributes to the formation of the ring) may be a carbonyl carbon.

As the anion represented by the general formula (3), SO ₃ ^-- CF ₂ -CH ₂ -OCO- (L) q'-W, SO ₃ ^-- CF ₂ -CHF-CH ₂ -OCO- (L) q ' -W, SO ₃ ^-- CF ₂ -COO- (L) q'-W, SO ₃ ^-- CF ₂ -CF ₂ -CH ₂ -CH _2- (L) qW, SO ₃ ^-- CF ₂ -CH ( CF ₃ ) -OCO- (L) q'-W is more preferred. Among them, L, q, and W are the same as those in the general formula (3). q 'represents an integer from 0 to 10.

In one aspect, the general formula (ZI) in the Z ^-, of the general formula (ZII) of Z ^-, of the general formula (ZI-3) in Zc ^- and the general formula (ZI-4) in the Z ^- Also, a fluoroalkylsulfonic acid anion (more preferably a perfluoroalkylsulfonic acid anion) is also preferred. The carbon number of the fluoroalkylsulfonic acid anion (including the perfluoroalkylsulfonic acid anion) is 2 to 10, preferably 3 to 5, and more preferably.

Hereinafter, anions and cations of the photoacid generator are exemplified.

[Chemical 11]

[Chemical 12]

[Chemical 13]

These cations and anions can be used in any combination to serve as a photoacid generator.

The photoacid generator may be in the form of a low-molecular-weight compound, or it may be in the form of a part incorporated in a polymer. Further, the form of the low-molecular compound and the form incorporated in a part of the polymer may be used in combination.
The photoacid generator is preferably in the form of a low-molecular compound.
When the photoacid generator is in the form of a low-molecular compound, its molecular weight is preferably 3,000 or less, more preferably 2,000 or less, and 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 relative to the total solid content of the composition, more preferably 0.5 to 20% by mass, and further 1 to 10% by mass. Preferably, 1 to 5 mass% is particularly preferred.
The resin B may be used alone or in combination of two or more. When two or more are used, the total content of these is preferably within the above range.

＜ Acid diffusion control agent ＞
The resist composition of the present invention further contains an acid diffusion controlling agent as a compound different from the ether compound.
The acid diffusion controlling agent preferably captures an acid generated from a photoacid generator or the like at the time of exposure and functions as a quencher that suppresses the reaction of the resin B in the unexposed portion due to the excess acid generation.
For example, basic compounds (DA), basic compounds (DB) capable of reducing or disappearing basicity by irradiation with actinic rays or radiation (having proton-accepting functional groups, and actinic rays or radiation) Decomposed by irradiation to decompose proton acceptors, disappear, or change from proton acceptors to acidic compounds), onium salts (DCs) that are relatively weak acids with respect to photoacid generators, have nitrogen atoms, and have Low-molecular compounds (DD) which are separated by the action of an acid, or onium salt compounds (DE) having a nitrogen atom in the cation part are used as acid diffusion control agents.
Among them, the acid diffusion control agent is preferably a basic compound (DA) and a low-molecular compound (DD) having a nitrogen atom and having a group detached by the action of an acid.

(Basic Compound (DA))
As the basic compound (DA), a compound having a structure represented by the following formulae (A) to (E) is preferable.

[Chemical 14]

In the general formulae (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 with a carbon number of 1 to 20), a cycloalkyl group (preferably with a carbon number of 3 to 20), or an aromatic group. Base (carbon number 6 to 20). R ²⁰¹ and R ²⁰² may be bonded to each other to form a ring.
R ²⁰³ , R ²⁰⁴ , R ²⁰⁵ and R ²⁰⁶ may be the same or different, and each independently represents an alkyl group having 1 to 20 carbon atoms.

The alkyl group in the general formulae (A) and (E) may have a substituent or may be unsubstituted.
As the alkyl group, as the alkyl group having a substituent, an amino alkyl group having 1 to 20 carbon atoms, a hydroxyalkyl group having 1 to 20 carbon atoms, or a cyanoalkyl group having 1 to 20 carbon atoms is preferable.
It is more preferred that the alkyl groups in the general formulae (A) and (E) are unsubstituted.

As the basic compound (DA), guanidine, aminopyrrolidine, pyrazole, pyrazoline, pipeguchi, amino terminal morpholine, aminoalkyl terminal morpholine, or piperidine are preferred, and imidazole is provided. Structure, diazabicyclic structure, onium hydroxide structure, onium carboxylic acid structure, trialkylamine structure, aniline structure, or pyridine structure compound, alkylamine derivative having hydroxyl group, or aniline derivative having hydroxyl group, etc. For the better.

(Low-molecular compound (DD) having a nitrogen atom and a group which is released by the action of an acid)
Moreover, it is also preferable that the acid diffusion control agent is a low-molecular compound (DD) (hereinafter, also referred to as a "compound (DD)") having a nitrogen atom and a group detached by the action of an acid. It is preferable that the compound (DD) is an amine derivative having a group detached by the action of an acid on a nitrogen atom.
As the group to be released by the action of an acid, an acetal group, a carbonate group, a urethane group, a tertiary ester group, a tertiary hydroxyl group or a hemiacetal amine ether is preferable, and the urethane group or Hemiacetal ethers are more preferred.
The molecular weight of the compound (DD) is preferably from 100 to 1,000, more preferably from 100 to 700, and even more preferably from 100 to 500.
The compound (DD) may have a urethane group having a protective group on a nitrogen atom. The protective group constituting the urethane group is represented by the following general formula (d-1).

[Chemical 15]

In the general formula (d-1),
Rb each independently represents a hydrogen atom, an alkyl group (preferably a carbon number of 1 to 10), a cycloalkyl group (preferably a carbon number of 3 to 30), an aryl group (preferably a carbon number of 3 to 30), an arane Group (preferably having 1 to 10 carbons) or alkoxyalkyl (preferably having 1 to 10 carbons). Rb may be bonded to each other to form a ring.
The substituents which the alkyl group, cycloalkyl group, aryl group, aralkyl group, and alkoxyalkyl group represented by Rb may have are each independently a hydroxyl group, a cyano group, an amino group, a pyrrolidinyl group, or a piperidinyl group. Functional groups such as, terminal phenolinyl, bridging oxy, alkoxy, or halogen atom are preferred.

As Rb, a linear or branched alkyl group, a cycloalkyl group, or an aryl group is preferred, and a linear or branched alkyl group or a cycloalkyl group is more preferred.
Examples of the ring formed by bonding two Rb to each other include an alicyclic hydrocarbon ring, an aromatic hydrocarbon ring, a heterocyclic hydrocarbon ring, and a derivative thereof.
The specific structure of the group represented by the general formula (d-1) includes, but is not limited to, the structure disclosed in paragraph <0466> of the specification of US 2012/0135348 A1.

It is preferable that the compound (DD) has a structure represented by the following general formula (6).

[Chemical 16]

In the general formula (6),
l represents an integer from 0 to 2, m represents an integer from 1 to 3, and satisfies l + m = 3.
Ra represents a hydrogen atom, an alkyl group, a cycloalkyl group, an aryl group, or an aralkyl group. When l is 2, the two Ras may be the same or different, and the two Ras may be bonded to each other to form a heterocyclic ring with the nitrogen atom in the formula. The heterocyclic ring may have a hetero atom other than the nitrogen atom in the formula. Moreover, as a substituent of this heterocyclic ring, a hydroxyl group is preferable.
Rb has the same meaning as Rb in the general formula (d-1), and preferred examples are also the same.
In the general formula (6), the alkyl group, cycloalkyl group, aryl group, and aralkyl group as Ra each independently have a substituent that the alkyl group, cycloalkyl group, aryl group, and aralkyl group may have as Rb, and Exemplary substituents are also preferred.

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

Hereinafter, preferable examples of the acid diffusion controlling agent are shown.

[Chemical 17]

[Chemical 18]

In the resist composition of the present invention, there is no limitation as long as the content of the acid diffusion control agent satisfies the aforementioned mass ratio R1, but it is preferably 0.006 to 8% by mass relative to the total solid content, and 0.01 to 1% by mass is more preferred, and 0.02 to 0.1% by mass is even more preferred.

<Solvent>
The resist composition of the present invention contains a solvent.
In the resist composition of the present invention, a known resist solvent can be appropriately used. For example, paragraphs <0665> to <0670> of US Patent Application Publication No. 2016 / 0070167A1, paragraphs <0210> to <0235> of US Patent Application Publication No. 2015 / 0004544A1 can be preferably used, and US Patent Application Publication 2016 Known solvents disclosed in paragraphs <0424> to <0426> of the specification No. 0237190A1 and paragraphs <0357> to <0366> of the specification of US Patent Application Publication No. 2016 / 0274458A1.
Examples of the solvent that can be used in the preparation of the composition include alkylene glycol monoalkyl ether carboxylic acid esters, alkylene glycol monoalkyl ether carboxylic acid esters, alkyl lactate esters, and alkoxypropanoic acid alkyl esters. Esters, cyclic lactones (preferably 4 to 10 carbons), monoketone compounds that may have rings (preferably 4 to 10 carbons), alkylene carbonates, alkyl alkoxyacetates, and Organic solvents such as alkyl pyruvate.

As the organic solvent, a mixed solvent in which a solvent having a hydroxyl group and a solvent having no hydroxyl group in a structure are mixed can be used.
As the solvent having a hydroxyl group and the solvent not having a hydroxyl group, the foregoing exemplary compounds can be appropriately selected. As the solvent containing a hydroxyl group, alkylene glycol monoalkyl ether or lactic acid alkyl group is preferable. Propylene glycol monomethyl ether (PGME ), Propylene glycol monoethyl ether (PGEE), methyl 2-hydroxyisobutyrate or ethyl lactate are more preferred.
In addition, as the solvent having no hydroxyl group, alkylene glycol monoalkyl ether acetate, alkyl alkoxy propionate, monoketone compound which may have a ring, cyclic lactone or alkyl acetate, etc. are Preferably, among these, propylene glycol monomethyl ether acetate (PGMEA), ethyl ethoxy propionate, 2-heptanone, γ-butyrolactone, cyclohexanone, cyclopentanone, or butyl acetate More preferably, propylene glycol monomethyl ether acetate, γ-butyrolactone, ethyl ethoxypropionate, cyclohexanone, cyclopentanone, or 2-heptanone are further preferred. As a solvent having no hydroxyl group, propylene carbonate is also preferable.
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, 10/90 to 90/10 is more preferable, and 20/80 to 60/40 is more preferable. From the viewpoint of coating uniformity, a mixed solvent containing 50% by mass or more of a solvent having no hydroxyl group is preferred.
The solvent preferably contains propylene glycol monomethyl ether acetate, and may be a propylene glycol monomethyl ether acetate alone solvent or a mixed solvent of two or more solvents including propylene glycol monomethyl ether acetate.

＜ Surface active agent ＞
The resist composition of the present invention may further include a surfactant. As the surfactant, a fluorine-based and / or silicon-based surfactant (specifically, a fluorine-based surfactant, a silicon-based surfactant, or a surfactant having both a fluorine atom and a silicon atom) is preferred.

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

The surfactant may be used singly or in combination of two or more kinds.
When the resist composition of the present invention contains a surfactant, the content of the surfactant relative to the total solid content of the composition is preferably 0.0001 to 2% by mass, and more preferably 0.0005 to 1% by mass.
The surfactant may be used singly or in combination of two or more kinds. 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, for example, it may contain a member selected from the group consisting of a hydrophobic resin, an acid multiplying agent, a dye, a plasticizer, a photosensitizer, a light absorber, an alkali-soluble resin, and a dissolution inhibitor. And one or more components in a group such as a dissolution accelerator and the like.

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

The resist composition of the present invention is used by dissolving the above-mentioned components in a predetermined organic solvent, preferably in the above-mentioned mixed solvent, filtering it with a filter, and then applying the On a specified support (substrate). The pore size of the filter used in the filtration is preferably 0.1 μm or less, more preferably 0.05 μm or less, and 0.03 μm or less. When the solid content concentration of the composition is high (for example, 25% by mass or more), the pore size of the filter used in the filter filtration is preferably 3 μm or less, more preferably 0.5 μm or less, and 0.3 μm or less. Is even better. The filter is preferably made of polytetrafluoroethylene, polyethylene or nylon. In the filter filtration, for example, as disclosed in the specification of Japanese Patent Application Laid-Open No. 2002-062667 (Japanese Patent Application Laid-Open No. 2002-062667), circulating filtering may be performed, or a plurality of filters may be connected in series or in parallel to perform filtering . The composition can be filtered multiple times. Furthermore, the composition may be subjected to a degassing treatment and the like before and after the filtration by the filter.

The viscosity of the resist composition of the present invention is preferably 20 to 500 mPa ･ s. From the viewpoint of more excellent coatability, the viscosity of the resist composition of the present invention is more preferably 20 to 300 mPa ･ s.
In addition, at room temperature (23 ° C), viscosity can be measured using an E-type viscometer.

＜ Applications ＞
The resist composition of the present invention relates to a photosensitized radioactive or radiation-sensitive resin composition whose properties are changed by reaction with actinic radiation or radiation. In more detail, the resist composition of the present invention relates to a mold structure for use in semiconductor manufacturing steps such as IC (Integrated Circuit), circuit board manufacturing such as liquid crystal or thermal head, and imprint. Photosensitive radioactive or radiation-sensitive resin composition in production, other photolithography process steps, lithographic printing plates, or production of acid-curable compositions. The pattern formed in the present invention can be used in an etching step, an ion implantation step, a bump electrode forming step, a rewiring forming step, a MEMS (Micro Electro Mechanical Systems), and the like.

[Resist film, pattern formation method]
The present invention also relates to a pattern forming method using the above-mentioned photosensitive radiation- or radiation-sensitive resin composition. The pattern forming method of the present invention will be described below. The resist film (photosensitized radiation or radiation-sensitive film) of the present invention will be described together with the description of the pattern forming method.

The pattern forming method of the present invention has:
(I) A step of forming a resist film (photosensitive radioactive or radiation-sensitive film) on a support using the above-mentioned resist composition (photosensitive radioactive or radiation-sensitive resin composition) (resist film Forming step);
(Ii) a step of exposing the above-mentioned resist film (irradiating actinic rays or radiation) (exposure step); and (iii) a step of developing the above-mentioned exposed resist film using a developing solution (developing step) .

The pattern forming method of the present invention is not particularly limited as long as it includes the 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.
In the pattern forming method of the present invention, it is preferable to include (iv) a pre-bake (PB) step before the (ii) exposure step.
In the pattern forming method of the present invention, it is preferable to include (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 a plurality of (ii) exposure steps.
The pattern forming method of the present invention may include a plurality of (iv) pre-heating steps.
The pattern forming method of the present invention may include a plurality of (v) post-exposure heating steps.

In the pattern forming method of the present invention, the above-mentioned (i) film forming step, (ii) exposure step, and (iii) development step can be performed by a conventionally known method.

(I) The thickness of the resist film formed in the resist film forming step is preferably 500 to 11000 nm, more preferably 1000 to 9000 nm, and more preferably 3000 to 7000 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-based or inorganic-based material can be appropriately used.
A protective film (top coat) may be formed on the resist film. As a protective film, a well-known material can be used suitably. For example, US Patent Application Publication No. 2007/0178407, US Patent Application Publication No. 2008/0085466, US Patent Application Publication No. 2007/0275326, and US Patent Application Publication No. 2016/0299432 can be preferably used. The composition for forming a protective film disclosed in US Patent Application Publication No. 2013/0244438 and International Patent Application Publication No. 2016 / 157988A. As a composition for forming a protective film, it is preferable to include the said acid diffusion control agent.
A protective film may be formed on the upper layer of the resist film containing the above-mentioned hydrophobic resin.

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

Regarding the heating temperature, in any of the (iv) pre-heating step and (v) post-exposure heating step, 70-160 ° C is preferred, 70-155 ° C is more preferred, and 80-150 ° C is further Better.
Regarding the heating time, in any of (iv) the pre-heating step and (v) the post-exposure heating step, 30 to 300 seconds is preferable, 30 to 180 seconds is more preferable, and 30 to 90 seconds Is even better.
The heating may be performed by a mechanism provided in the exposure device and the developing device, or may be performed using a heating plate or the like.

The wavelength of the light source used in the exposure step is not particularly limited, and examples thereof include infrared light, visible light, ultraviolet light, extreme 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, it is KrF excimer laser (248 nm), ArF excimer laser (193 nm), F ₂ excimer laser (157 nm), X-ray, EUV light (13 nm), electron beam, etc. KrF excimer laser, ArF excimer laser, EUV light or electron beam are preferred, and KrF excimer laser is more preferred.

(Iii) The developing solution used in the developing step may be an alkaline developing solution or a developing solution containing an organic solvent (hereinafter, also referred to as an organic developing solution).

As the alkali developing solution, a quaternary ammonium salt typified by tetramethylammonium hydroxide is generally used. In addition, alkali aqueous solutions such as inorganic bases, primary to tertiary amines, alcohol amines, and cyclic amines can also be used.
Furthermore, the alkali developing solution may contain an appropriate amount of an alcohol and / or a surfactant. The alkali concentration of the alkali developer is usually 0.1 to 20% by mass. The pH of the alkaline developer is usually 10-15.
The development time using 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 preferably a developer containing at least one organic solvent selected from the group consisting of a ketone solvent, an ester solvent, an alcohol solvent, a amine solvent, an ether solvent, and a hydrocarbon solvent.

Examples of the ketone-based solvent include 1-octanone, 2-octanone, 1-nonanone, 2-nonanone, acetone, 2-heptanone (methylpentyl ketone), 4-heptanone, 1 -Hexanone, 2-hexanone, diisobutanone, cyclohexanone, methylcyclohexanone, phenylacetone, methylethylketone, methylisobutylketone, acetoacetone, acetoneacetone, violet Ketones, diacetone alcohol, acetomethanol, acetophenone, methylnaphthyl ketone, isophorone, and propylene carbonate.

Examples of the ester-based solvent include methyl acetate, butyl acetate, ethyl acetate, isopropyl acetate, pentyl acetate, isoamyl acetate, pentyl acetate, propylene glycol monomethyl ether acetate, and ethylene glycol. Alcohol monoethyl ether acetate, diethylene glycol monobutyl ether acetate, 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, butyl butyrate, Methyl 2-hydroxyisobutyrate, isoamyl acetate, isobutyl isobutyrate and butyl propionate.

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

The above-mentioned solvents may be mixed in a plurality of types, or may be mixed with a solvent or water other than the above-mentioned solvents. The moisture content of the entire developing solution is preferably less than 50% by mass, more preferably less than 20% by mass, even more preferably less than 10% by mass, and it is particularly preferred that it is substantially free of moisture.
The content of the organic solvent with respect to the organic developer is preferably 50 to 100% by mass, more preferably 80 to 100% by mass, even more preferably 90 to 100% by mass, and 95 to 100%. The mass% is particularly good.

The organic developer may contain a known surfactant in an appropriate amount as necessary.

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

The organic developer may contain the acid diffusion control agent.

Examples of the developing method include a method of immersing a substrate in a tank filled with a developing solution for a certain period of time (immersion method); a method of raising the developing solution on the surface of the substrate by surface tension and leaving it to stand for a predetermined period of time (immersion) Method); a method of spraying a developer solution on the surface of the substrate (jet method); and a method of continuously ejecting the developer solution while scanning the developer ejection nozzle at a constant speed on a substrate rotating at a certain speed (dynamic distribution method) and the like.

The step of developing using an aqueous alkaline solution (alkali developing step) and the step of developing using a developing solution containing an organic solvent (organic solvent developing step) may be combined. Thereby, a pattern can be formed only by dissolving a region with an intermediate level of exposure intensity, and thus a finer pattern can be formed.

After (iii) the developing step, it is preferable to include a step of washing with a washing solution (rinsing step).

As the rinsing solution used in the rinsing step subsequent to the developing step using the alkali developing solution, for example, pure water can be used. Pure water may contain a suitable amount of a surfactant. In this case, after the developing step or the rinsing step, a treatment for removing the developing solution or the rinsing solution attached to the pattern by a supercritical fluid may be added. Further, in order to remove the moisture remaining in the pattern, a heat treatment may be performed after a rinsing treatment or a treatment with a supercritical fluid.

The developing solution used in the developing step subsequent to the developing step using a developing solution containing an organic solvent is not particularly limited as long as it does not dissolve the pattern, and a solution containing a common organic solvent can be used. As the washing liquid, a washing liquid containing at least one organic solvent selected from the group consisting of a hydrocarbon-based solvent, a ketone-based solvent, an ester-based solvent, an alcohol-based solvent, an amidine-based solvent, and an ether-based solvent is used. good.
Specific examples of the hydrocarbon-based solvent, the ketone-based solvent, the ester-based solvent, the alcohol-based solvent, the amidine-based solvent, and the ether-based solvent are the same as those described in the developer containing an organic solvent.
As the rinsing liquid used in the rinsing step at this time, a rinsing liquid containing a monohydric alcohol is more preferable.

Examples of the monohydric alcohol used in the washing step include a linear, branched, or cyclic monohydric alcohol. Specific examples include 1-butanol, 2-butanol, 3-methyl-1-butanol, tertiary butanol, 1-pentanol, 2-pentanol, 1-hexanol, and 4-methyl alcohol. 2-Pentanol, 1-heptanol, 1-octanol, 2-hexanol, cyclopentanol, 2-heptanol, 2-octanol, 3-hexanol, 3-heptanol, 3-octanol , 4-octanol and methyl isobutyl methanol. Examples of the monovalent alcohol having 5 or more carbon atoms include 1-hexanol, 2-hexanol, 4-methyl-2-pentanol, 1-pentanol, 3-methyl-1-butanol, and methyl Isobutyl methanol and so on.

A plurality of components may be mixed, and they may be used in combination with an organic solvent other than the above.
The water content in the washing 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 characteristics can be obtained.

The rinse solution may contain a suitable amount of a surfactant.
In the rinsing step, the developing substrate is cleaned using a rinsing liquid. The method of cleaning treatment is not particularly limited, and examples thereof include a method of continuously spraying a rinsing liquid on a substrate rotating at a constant speed (spin coating method), and a method of immersing a substrate in a tank filled with the rinsing liquid for a predetermined time (Dipping method), or a method of spraying a developing solution on the substrate surface (jet method). Among them, it is preferable to perform a cleaning process by a spin coating method, and after the substrate is rotated, the substrate is rotated at a rotation speed of 2,000 to 4,000 rpm (revolution per minute) to remove the rinse liquid from the substrate. It is also preferable to include a heating step (Post Bake) after the rinsing step. The heating step removes the developer and rinse liquid 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, and more preferably 70 to 115 ° C. The heating time is usually 10 seconds to 3 minutes, and preferably 30 seconds to 90 seconds.

The film thickness (pattern height) of the pattern obtained in the pattern forming method of the present invention is preferably 500 to 11000 nm, more preferably 1000 to 9000 nm, and even more preferably 3000 to 7000 nm.
When the formed pattern 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 even more preferably 1 to 10.
When the formed pattern is a groove (groove) pattern or a contact hole pattern, the aspect ratio obtained by dividing the pattern height by the value of the groove width or aperture is preferably 0.3 to 20, and 0.5 to 15 More preferably, 1 to 10 is more preferable.

Various materials used in the resist composition of the present invention and the pattern forming method of the present invention (for example, a resist solvent, a developing solution, a developing solution, a composition for forming an antireflection film, or a composition for forming a top coat layer It is preferable that impurities such as metal components, isomers, and residual monomers are not included. The content of the impurities contained in the above-mentioned various materials is preferably 1 ppm or less, more preferably 100 ppt or less, even more preferably 10 ppt or less, and substantially not included (below the detection limit of the measurement device) is Extraordinary.

Examples of a method for removing impurities such as metals from the above-mentioned various materials include filtration using a filter. As the pore diameter of the filter, a pore size of 10 nm or less is preferable, 5 nm or less is more preferable, and 3 nm or less is more preferable. The material of the filter is preferably a filter made of polytetrafluoroethylene, polyethylene, or nylon. As the filter, an organic solvent may be used for cleaning. In the filter filtering step, a plurality of filters can be used in series or in parallel. When using multiple filters, filters with different pore sizes and / or materials can be used in combination. In addition, various materials may be filtered multiple times, and the step of filtering multiple times may be a cyclic filtering step. As the filter, it is preferable to reduce the amount of dissolved matter as disclosed in the specification of Japanese Patent Application Laid-Open No. 2016-201426 (Japanese Patent Application Laid-Open No. 2016-201426).
In addition to filter filtration, it is possible to remove impurities based on adsorbent materials, and it is also possible to use a combination of filter filtration and adsorbent materials. As the adsorbent, a known adsorbent can be used. For example, an inorganic adsorbent such as silica gel or zeolite, or an organic adsorbent such as activated carbon can be used. Examples of the metal adsorbent include those disclosed in Japanese Patent Application Publication No. 2016-206500 (Japanese Patent Application Laid-Open No. 2016-206500).
In addition, as a method for reducing impurities such as metals contained in the above-mentioned various materials, a raw material having a small metal content can be selected as a raw material constituting the various materials, and the raw material constituting the various materials can be filtered by filtering, or Teflon (register (Trademark) The method of lining the inside of the device and performing distillation and the like under conditions that minimize contamination. The preferable conditions in the filtration of the raw materials constituting the various materials are the same as those described above.
In order to reduce the content of metal impurities in the resist composition (for example, mass ppt level), in the manufacturing steps (synthetic raw material steps, etc.) of the material (resin, photoacid generator, etc.) of the resist composition It is also preferable to perform partial or whole glasslining in the device of the device used. This method is described in, for example, the Chemical Industry Daily on December 21, 2017.

In order to prevent contamination of impurities, the above-mentioned various materials are stored in containers described in US Patent Application Publication No. 2015/0227049, Japanese Patent Application Publication No. 2015-123351 (Japanese Patent Application Laid-Open No. 2015-123351), and the like. good.

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

[Manufacturing method of electronic component]
The present invention also relates to a method for manufacturing an electronic device including the pattern forming method. The electronic component manufactured by the method for manufacturing an electronic component of the present invention is preferably mounted on electrical and electronic equipment (for example, home appliances, OA (Office Automation: Office Automation) related equipment, media-related equipment, optical equipment, and communication equipment).
[Example]

Hereinafter, the present invention will be described in more detail based on examples. The materials, usage amounts, proportions, processing contents, processing steps, and the like shown in the following examples can be appropriately changed as long as they do not depart from the gist of the present invention. Therefore, the scope of the present invention is not limitedly interpreted by the examples shown below.

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

<Ether compound>
As the ether compound, the following compounds were used.

[Chemical 19]

＜ Resin ＞
As the resin, resins shown below were used.

[Chemical 20]

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

[Table 1]

<Photo acid generator>
As a photoacid generator, the photoacid generator shown below was used.

[Chemical 21]

＜ Acid diffusion control agent ＞
As the acid diffusion controlling agent, the following compounds were used.

[Chemical 22]

＜ Surface active agent ＞
As the surfactant, the following compounds were used.

G1: Compound shown below
G2: MEGAFACE-R4 (fluorine-based surfactant, manufactured by DIC Corporation)

[Chemical 23]

<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 a 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 mixing of the solid components described in the following table, and the solution is prepared into the solid described in the table. Ingredient concentration. The obtained solution was precisely filtered using a membrane filter having a diameter of 0.3 μm to obtain a resist composition.
The compounding of the resist composition used by each Example or a comparative example is shown to the following table.
The content mark in the table indicates the content (% by mass) of each component with respect to the total solid content.

[Table 2]

[Evaluation]
<Formation of the pattern>
An 8-inch Si substrate (manufactured by Advanced Materials Technology, Inc.) (hereinafter also referred to as a "substrate") having been subjected to hexamethyldisilazane treatment using a spin coater "ACT-8" manufactured by Tokyo Electron Limited. )), The resist composition was spin-coated.
The substrate was heated (PB: PreBake) at 140 ° C. for 60 seconds and dried to form a resist film having a thickness of 4.2 μm. Then, a KrF excimer laser scanner (manufactured by ASML, PAS5500 / 850C with a wavelength of 248 nm) was used, and exposure was performed at various exposures through a mask with a line width of 500 nm and a space width of 300 nm.
The exposed resist film was further heated at 115 ° C for 60 seconds, and then a 2.38% by mass tetramethylammonium hydroxide (TMAH) aqueous solution was immersed for 60 seconds and developed to obtain a wire and Space pattern.
The obtained pattern was washed with pure water for 30 seconds, and then heated at 110 ° C. for 60 seconds.

<Evaluation of Pitch (Measurement of Space)>
The pattern produced was observed using a side length SEM S-9380 manufactured by Hitachi, Ltd. The minimum exposure amount capable of confirming that the exposed portion of the resist film is completely developed (removed) so that the surface of the substrate is exposed is taken as the optimal exposure amount Eopt. The amplitude (space (nm)) between adjacent lines when the pattern was formed with this Eopt was measured. It can be evaluated that as the value is smaller, a pattern having excellent resolution and a narrower pitch can be formed.
In addition, the above-mentioned "amplitude between adjacent lines" refers to the distance between the positions where the height of d / 2 in the lines adjacent to each other is connected when the thickness of the pattern is d.

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

A: The shape of the line is rectangular.
B: The shape of the line is tapered.
C: The shape of the line is tapered, and a part of the non-exposed portion is removed during development to make the film thinner.
-: Pattern collapse occurred without being able to form a pattern.
In addition, when the width of the upper side of the trench (the area where the resist is removed by exposure) is 1.5 times greater than the width of the bottom side, the shape of the line is evaluated as a cone.

[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” shows the mass ratio of the content of the ether compound to the content of the acid diffusion control agent (content of the ether compound / content of the acid diffusion control agent) in the resist composition.
The column of “R2” indicates the mass ratio of the content of the ether compound to the content of the resin B (content of the ether compound / content of the resin B) in the resist composition.
The “nitrogen-containing” column indicates whether the ether compound in the resist composition is a nitrogen-containing compound. When this requirement is satisfied, it is A, and when it is not, it is B.
The column of “Formula (X1)” indicates whether the ether compound in the resist composition is a compound represented by General Formula (X1). When this requirement is satisfied, it is A, and when it is not, it is B.
The column of “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 a compound represented by formula (X1). When this requirement is satisfied, it is A, and when it is not, it is B.
The column of “phenolic polar unit” indicates whether the resin in the resist composition contains a repeating unit having a phenolic polar group. When this requirement is satisfied, it is A, and when it is not, it is B.
The column of “benzene unit content” shows the content (mass%) of the repeating unit having a benzene ring group in the resin in the resist composition with respect to the total mass of the resin.
The column of “Formula (Z1-3)” indicates whether the photoacid generator in the resist composition is a compound represented by General Formula (Z1-3). When this requirement is satisfied, it is A, and when it is not, it is B.

[table 3]

As shown in the above table, 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. The cross-sectional shape of the formed pattern is also better than the cross-sectional shape of the pattern obtained by using the resist composition of the comparative example.
On the other hand, a desired pattern cannot be obtained with the resist composition of the comparative example. Further, in Comparative Example 4, cracks occurred in the resist film after PB, and a pattern could not be formed.
In addition, as a result of a test using a resist composition having a solid content concentration of 10% by mass, a resist film having a film thickness (4.2 μm) as an evaluation standard could not be formed.

From the results shown in the table, it was confirmed that when the ether compound is a nitrogen-containing compound, a pattern with a narrower pitch can be formed (comparison of Examples 1 to 4).
It was confirmed that 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 obtained pattern is also more excellent. (Comparison of Examples 1 to 3).
It was confirmed that when the content of the repeating unit having a benzene ring group is less than 65 mol% relative to the total mass of the resin, a pattern with a narrower pitch can be formed, and the cross-sectional shape of the obtained pattern is also more excellent (Example 1 , 5 and 6).
It was confirmed that when the photoacid generator is a compound represented by the formula (ZI-3), a pattern with a narrower pitch can be formed (comparison of Examples 1, 7, and 10).

Claims (10)

A photosensitive radiation- or radiation-sensitive resin composition, comprising: Ether compound Resin, including a repeating unit having a phenolic polar group and a repeating unit having an acid-decomposable group; Photoacid generator An acid diffusion control agent, which is a compound different from the ether compound; and Solvents, In the photosensitive radiation-sensitive or radiation-sensitive resin 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, The mass ratio of the content of the ether compound to the content of the resin is 0.1 or less, The solid content concentration is more than 20% by mass. The actinic radiation- or radiation-sensitive resin composition according to item 1 of the scope of patent application, wherein the ether compound contains a nitrogen atom. The photosensitive radiation- or radiation-sensitive resin composition according to item 1 or item 2 of the scope of the patent application, wherein the ether compound is a compound represented by the general formula (X1), [R ^q1 -(-O-AL -) _m ] _n -NR ^q2 _3-n (X1) In the general formula (X1), m represents an integer of 1 to 10, n represents an integer of 1 to 3, AL represents an alkylene group, and R ^q1 and R ^q2 are independent of each other. Ground represents a hydrogen atom or a substituent. When n is 1 or 2, R ^q1 and R ^q2 may be bonded to each other to form a ring. When there is a plurality of m, m may be the same or different. When plural AL exists, the plural AL may be the same or different. When plural R ^q1 exists, the plural R ^q1 may be the same or different. When plural plural R ^q2 exists, The plural R ^q2s may be the same or different. The photosensitive radiation- or radiation-sensitive resin composition according to item 3 of the scope of the patent application, wherein at least one R ^q1 is a benzene ring group. The photosensitive radiation- or radiation-sensitive resin composition according to item 1 or item 2 of the patent application scope, wherein The content of the repeating unit having a benzene ring group in all the repeating units of the resin is less than 65 mol%. The photosensitive radiation- or radiation-sensitive resin composition according to item 1 or item 2 of the scope of the patent application, wherein the resin further has a repeating unit represented by the general formula (VW), In the 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 a fluorenyl group, and Rw represents a hydrocarbon group having an alicyclic group, wherein the general formula (VW) The repeating unit shown does not have an acid-decomposable group. The actinic radiation- or radiation-sensitive resin composition according to item 1 or item 2 of the scope of patent application, wherein the photoacid generator is selected from the group consisting of a compound represented by the general formula (ZI-3) and a general formula One or more compounds in the group of compounds represented by (ZI-4), In the 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, and an amino group. Or carbon-carbon double bond, R ₂ and R ₃ each independently represent a hydrogen atom, an alkyl group, a cycloalkyl group, a halogen atom, a cyano group, or an aryl group, and R _x and R _y each independently represent an alkyl group or a cycloalkyl group. , 2-oxoalkyl, alkoxycarbonylalkyl, allyl or vinyl, R ₂ and R ₃ may be bonded to each other to form a ring, R ₁ and R ₂ may be bonded to each other to form a ring, and R _x and R _y may be bonded to each other to form a ring. Z ^- represents an anion. In the general formula (ZI-4), l represents an integer of 0 to 2, r represents an integer of 0 to 8, and R ₁₃ represents a hydrogen atom, a fluorine atom, and a hydroxyl group. , Alkyl, alkoxy, alkoxycarbonyl, or a group having a cycloalkyl group, R ₁₄ represents 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 the group, when the presence of a plurality of R _14, there are a plurality of R ₁₄ may be the same, may be also different, R ₁₅ each independently represent an alkyl group, a cycloalkyl group or a naphthyl group, two R ₁₅ may be with When two R ₁₅ are bonded to each other to form a ring, and the two R ₁₅ are bonded to each other to form a ring, the ring skeleton may include a hetero atom such as an oxygen atom or a nitrogen atom. A resist film formed using the photosensitized radioactive or radiation-sensitive resin composition according to any one of claims 1 to 7 of the scope of patent application. A pattern forming method includes: A step of using a resist film formed by using a photosensitized radioactive or radiation-sensitive resin composition as described in any one of claims 1 to 7 of the scope of patent application; A step of exposing the resist film; and A step of developing the exposed resist film using a developing solution. A method for manufacturing an electronic component includes the pattern forming method described in item 9 of the scope of patent application.