WO2020137921A1

WO2020137921A1 - Actinic light sensitive or radiation sensitive resin composition, resist film, pattern forming method, and electronic device production method

Info

Publication number: WO2020137921A1
Application number: PCT/JP2019/050208
Authority: WO
Inventors: 直也畠山; 康智米久田; 英明椿; 敬充冨賀; 東　耕平; 康史大石
Original assignee: 富士フイルム株式会社
Priority date: 2018-12-28
Filing date: 2019-12-20
Publication date: 2020-07-02
Also published as: JP2023082000A; JPWO2020137921A1; CN113260604A; JP7295886B2; TW202036159A; CN113260604B; KR20210099049A; KR102603416B1

Abstract

The present invention provides an actinic light sensitive or radiation sensitive resin composition, a resist film, a pattern forming method, and an electronic device production method, wherein the actinic light sensitive or radiation sensitive resin composition comprises a compound (P), which is at least one of specific compounds represented by general formula (1) and specific compounds represented by general formula (2), the compound (P) content being between 1 ppm and 1,000 ppm inclusive relative to the total mass of the actinic light sensitive or radiation sensitive resin composition, and the molecular weight of the compound (P) being 500 or lower.

Description

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

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

Since the resist for KrF excimer laser (248 nm), a pattern forming method using chemical amplification has been used in order to compensate the sensitivity decrease due to light absorption. For example, in the positive-type chemical amplification method, first, the photo-acid generator contained in the exposed portion is decomposed by light irradiation to generate an acid. Then, in a post exposure bake (PEB: Post Exposure Bake) process or the like, the alkali-insoluble group contained in the photosensitive composition is changed into an alkali-soluble group by the catalytic action of the acid generated. After that, development is performed using, for example, an alkaline solution. As a result, the exposed portion is removed and a desired pattern is obtained.
In the above method, various alkaline developers have been proposed. For example, as this alkaline developer, an aqueous alkaline developer of 2.38 mass% TMAH (tetramethylammonium hydroxide aqueous solution) is generally used.

Due to the miniaturization of semiconductor elements, the wavelength of the exposure light source has been shortened and the numerical aperture (high NA) of the projection lens has been increased. At present, an exposure machine using an ArF excimer laser having a wavelength of 193 nm has been developed. ing. As a technique for further increasing the resolution, there is a method (that is, an immersion method) in which a liquid having a high refractive index (hereinafter, also referred to as “immersion liquid”) is filled between the projection lens and the sample.

Various conventional resist compositions are known, for example, the one described in Patent Document 1 is known.
Patent Document 1 describes a photoresist composition containing a polymer having a structural unit containing an acid-dissociable group that dissociates by the action of an acid, a radiation-sensitive acid generator, and a solvent.

Japanese Unexamined Patent Publication No. 2015-57638

In recent years, there has been a demand for a resist composition that achieves both excellent rectangular cross-sectional shape of a pattern and excellent temporal stability at a high level.

It is an object of the present invention to provide an actinic ray-sensitive or radiation-sensitive resin composition that achieves both excellent rectangularity of the obtained pattern cross-sectional shape and excellent stability over time in a high dimension.
A further object of the present invention is to provide a resist film, a pattern forming method and an electronic device manufacturing method using the above actinic ray-sensitive or radiation-sensitive resin composition.

-Means for solving the above problems include the following aspects.

[1]
An actinic ray-sensitive or radiation-sensitive resin composition containing a compound represented by the following general formula (1) and a compound (P) which is at least one of the compounds represented by the following general formula (2): ,
The content of the compound (P) is 1 ppm or more and 1000 ppm or less based on the total mass of the actinic ray-sensitive or radiation-sensitive resin composition,
An actinic ray-sensitive or radiation-sensitive resin composition, wherein the compound (P) has a molecular weight of 500 or less.

In the general formula (1),
R ₁ and R ₂ each independently represent a hydrogen atom or a substituent.
L represents a divalent linking group, and the group represented by L has 1 to 5 carbon atoms.
n represents an integer of 1 or more. However, when n represents 1, the carbon number of L is 1 or 2.
When n represents an integer of 2 or more, a plurality of Ls may be the same or different.
In the general formula (2),
R ₃ represents a hydrogen atom or a substituent. However, when R ₃ represents a substituent, the atom bonded to H—C(═O)— in R ₃ is a carbon atom.

[2]
The actinic ray-sensitive or radiation-sensitive resin composition according to [1], wherein the compound (P) is a compound represented by the following general formula (3) or the following general formula (4).

In the general formula (3),
R ₄ and R ₅ each independently represent a hydrogen atom or a substituent.
n represents an integer of 1 or more.
In the general formula (4),
R ₆ and R ₇ each independently represent a hydrogen atom or a substituent.
n1 represents an integer of 1 or more.
n2 represents an integer of 1 or more.

[3]
The actinic ray-sensitive property according to [1] or [2], wherein the content of the compound (P) is 1 ppm or more and 500 ppm or less based on the total mass of the actinic ray-sensitive or radiation-sensitive resin composition. Radiation-sensitive resin composition.
[4]
The content of the compound (P) is 1 ppm or more and 200 ppm or less with respect to the total mass of the actinic ray-sensitive or radiation-sensitive resin composition, according to any one of [1] to [3]. An actinic ray-sensitive or radiation-sensitive resin composition.

[5]
The content of the compound (P) is 1 ppm or more and 100 ppm or less with respect to the total mass of the actinic ray-sensitive or radiation-sensitive resin composition, according to any one of [1] to [4]. An actinic ray-sensitive or radiation-sensitive resin composition.
[6]
The actinic ray-sensitive or radiation-sensitive resin composition according to any one of [1] to [5], which further contains an acid diffusion controller.

[7]
A resist film formed from the actinic ray-sensitive or radiation-sensitive resin composition according to any one of [1] to [6].
[8]
A pattern forming method comprising: a step of exposing the resist film according to [7]; and a step of developing the exposed resist film with a developing solution.
[9]
An electronic device manufacturing method, including the pattern forming method according to [8].

According to the present invention, it is possible to provide an actinic ray-sensitive or radiation-sensitive resin composition that achieves both excellent rectangularity of the obtained pattern cross-sectional shape and excellent stability over time at a high level.
The present invention can further provide a resist film, a pattern forming method and an electronic device manufacturing method using the above actinic ray-sensitive or radiation-sensitive resin composition.

The details of the present invention will be described below.
The description of the constituents described below may be made based on a typical embodiment of the present invention, but the present invention is not limited to such an embodiment.
Regarding the notation of the group (atomic group) in the present specification, the notation that does not indicate substituted or unsubstituted includes not only those having no substituent but also those having a substituent. For example, the “alkyl group” includes not only an alkyl group having no substituent (unsubstituted alkyl group) but also an alkyl group having a substituent (substituted alkyl group). Moreover, the "organic group" in this specification means the group containing at least 1 carbon atom.

Further, in the present specification, the kind of the substituent, the position of the substituent, and the number of the substituents when the phrase “may have a substituent” are not particularly limited. The number of substituents may be, for example, 1, 2, 3, or more. Examples of the substituent include a monovalent non-metal atomic group excluding a hydrogen atom, and the substituent can be selected from the following substituents T, for example.

(Substituent T)
As the substituent T, a halogen atom such as a fluorine atom, a chlorine atom, a bromine atom and an iodine atom; an alkoxy group such as a methoxy group, an ethoxy group and a tert-butoxy group; an aryloxy group such as a phenoxy group and a p-tolyloxy group; Alkoxycarbonyl group such as methoxycarbonyl group, butoxycarbonyl group and phenoxycarbonyl group; Acyloxy group such as acetoxy group, propionyloxy group and benzoyloxy group; Acetyl group, benzoyl group, isobutyryl group, acryloyl group, methacryloyl group and methoxalyl group An acyl group; an alkylsulfanyl group such as a methylsulfanyl group and a tert-butylsulfanyl group; an arylsulfanyl group such as a phenylsulfanyl group and a p-tolylsulfanyl group; an alkyl group; a cycloalkyl group; an aryl group; a heteroaryl group; a hydroxyl group; Carboxyl group; formyl group; sulfo group; cyano group; alkylaminocarbonyl group; arylaminocarbonyl group; sulfonamide group; silyl group; amino group; monoalkylamino group; dialkylamino group; arylamino group, nitro group; formyl group As well as combinations thereof.

The term “actinic ray” or “radiation” used herein refers to, for example, a bright line spectrum of a mercury lamp, deep ultraviolet rays represented by excimer laser, extreme ultraviolet rays (EUV light: Extreme Ultraviolet), X-rays, and electron rays (EB). : Electron Beam) and the like. Unless otherwise specified, the “light” in the present specification means actinic rays or radiation.
Unless otherwise specified, the term "exposure" in the present specification means not only exposure with a bright line spectrum of a mercury lamp, deep ultraviolet rays represented by excimer laser, extreme ultraviolet rays, X-rays, EUV light, etc., but also electron beam, and It also includes exposure with a particle beam such as an ion beam.
In the present specification, “to” is used to mean that numerical values described before and after the “to” are included as a lower limit value and an upper limit value.

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

In the present specification, the amount of each component in the composition refers to the total amount of the corresponding substances present in the composition, unless there is a plurality of substances corresponding to each component in the composition, unless otherwise specified. means.
In the present specification, the term “step” is included in the term as long as the intended purpose of the step is achieved, not only when it is an independent step but also when it cannot be clearly distinguished from other steps.
In the present specification, the "total solid content" refers to the total mass of components excluding the solvent from the total composition. The “solid content” is a component excluding the solvent as described above, and may be a solid or a liquid at 25° C., for example.
In the present specification, “mass %” and “weight %” have the same meaning, and “mass part” and “weight part” have the same meaning.
Further, in the present specification, a combination of two or more preferable aspects is a more preferable aspect.

(Actinic ray-sensitive or radiation-sensitive resin composition)
The actinic ray-sensitive or radiation-sensitive resin composition (hereinafter, also simply referred to as “composition”) according to the present invention,
An actinic ray-sensitive or radiation-sensitive resin composition containing a compound represented by the general formula (1) described below and a compound (P) which is at least one of the compounds represented by the general formula (2) described below. hand,
The content of the compound (P) is 1 ppm or more and 1000 ppm or less based on the total mass of the actinic ray-sensitive or radiation-sensitive resin composition,
The molecular weight of the compound (P) is 500 or less.

By adopting the above configuration, the present inventor can achieve both excellent rectangularity of the obtained pattern cross-sectional shape and excellent stability over time at a high level.
The reason is not clear, but it is presumed to be as follows.
First, the present inventors have added to the actinic ray-sensitive or radiation-sensitive resin composition at least one of the compound represented by the general formula (1) and the compound represented by the general formula (2) as described above. By containing the compound (P), which is a compound, in a predetermined range of 1 ppm or more and 1000 ppm or less with respect to the total mass of the actinic ray-sensitive or radiation-sensitive resin composition, the rectangularity of the pattern cross-sectional shape is extremely excellent. I found that it would be a good thing. This is because the actinic ray-sensitive or radiation-sensitive resin composition contains the compound (P) in the above-mentioned trace amount range, but the exact reason is unclear, but the exposed portion of the resist film is It is presumed that this is due to the fact that the generated acid was suppressed from being excessively diffused in the unexposed area.
Further, the molecular weight of the compound (P) is set to 500 or less by adjusting the molecular weight of the compound (P), which is at least one of the compound represented by the general formula (1) and the compound represented by the general formula (2), to 500 or less. It is considered that the improvement in flexibility of the resist film is suppressed as compared with the case where the value is more than 500. As a result, the acid generated in the exposed portion of the resist film is suppressed from being excessively diffused in the unexposed portion, and from this viewpoint, it is assumed that the rectangularity of the pattern cross-sectional shape is extremely excellent. To be done.
In addition, the actinic ray-sensitive or radiation-sensitive resin composition contains the compound (P) having a molecular weight of 500 or less in the above-mentioned trace amount range, so that the actinic ray-sensitive or radiation-sensitive resin composition The fact that the temporal stability can be further improved is a finding that the present inventors have earnestly studied, but the reason is unknown.

The actinic ray-sensitive or radiation-sensitive resin composition according to the present invention is preferably a so-called resist composition, and may be a positive resist composition or a negative resist composition. Further, it may be a resist composition for alkali development or a resist composition for organic solvent development.
The composition of the present invention is typically preferably a chemically amplified resist composition.
Hereinafter, the details of each component contained in the actinic ray-sensitive or radiation-sensitive resin composition (also simply referred to as “composition”) according to the present invention will be described.

<Compound (P) which is at least one of the compound represented by the general formula (1) and the compound represented by the general formula (2)>
The composition of the present invention comprises a compound (P) which is at least one of the compound represented by the general formula (1) and the compound represented by the general formula (2) (hereinafter, also referred to as “compound (P)”). ) Is included.

The substituents as R ₁ and R ₂ are not particularly limited, and examples thereof include monovalent organic groups. Specific examples of the monovalent organic group include an alkyl group, an alkenyl group, a cycloalkyl group, an aryl group, a heterocyclic group, and an acyl group.

Examples of the alkyl group include an alkyl group having 1 to 20 carbon atoms, which may be linear or branched, preferably an alkyl group having 1 to 10 carbon atoms, and an alkyl group having 1 to 5 carbon atoms. More preferable.
Examples of the alkenyl group include alkenyl groups having 2 to 5 carbon atoms, which may be linear or branched and are preferably alkenyl groups having 2 to 3 carbon atoms.
Examples of the cycloalkyl group include a cycloalkyl group having 3 to 10 carbon atoms, and a cycloalkyl group having 3 to 6 carbon atoms is preferable.
The cycloalkyl group may have a hetero atom between carbon-carbon bonds. Examples of the hetero atom include an oxygen atom, a sulfur atom and a nitrogen atom.
Examples of the aryl group include an aryl group having 6 to 14 carbon atoms, and an aryl group having 6 to 10 carbon atoms is preferable.
The heterocyclic group may be monocyclic or polycyclic. The polycyclic type can suppress the diffusion of acid more. Further, the heterocyclic group may have aromaticity or may not have aromaticity. Examples of the heterocyclic ring having aromaticity include a furan ring, a thiophene ring, a benzofuran ring, a benzothiophene ring, a dibenzofuran ring, a dibenzothiophene ring, and a pyridine ring. Examples of the heterocycle having no aromaticity include a tetrahydropyran ring, a lactone ring, a sultone ring and a decahydroisoquinoline ring. Examples of the lactone ring and the sultone ring include the lactone structure and the sultone structure exemplified in the above resin. A furan ring, a thiophene ring, a pyridine ring, or a decahydroisoquinoline ring is particularly preferable as the heterocycle in the heterocyclic group.

Examples of the acyl group include an acyl group having 1 to 4 carbon atoms, and specifically, an acetyl group.

The above alkyl group, alkenyl group, cycloalkyl group, aryl group, heterocyclic group, or acyl group may further have a substituent. Examples of the substituent include the above substituent T.

R ₁ is preferably a hydrogen atom, an alkyl group, an aryl group or an acyl group, more preferably a hydrogen atom, an alkyl group or an aryl group.
R ₂ is preferably a hydrogen atom or an alkyl group.

L represents a divalent linking group, and the group represented by L has 1 to 5 carbon atoms.
The divalent linking group is not particularly limited, and examples thereof include an alkylene group having 1 to 5 carbon atoms, which may be linear or branched and is preferably an alkylene group having 1 to 3 carbon atoms. Preferably, it represents an alkylene group having 1 or 2 carbon atoms.
The divalent linking group may further have a substituent. Examples of the substituent include the above substituent T.
The group represented by L has 1 to 5 carbon atoms.

n represents an integer of 1 or more. However, when n represents 1, the carbon number of L is 1 or 2.
When n represents 1, the carbon number of L is 1 or 2. If this is not satisfied, it tends to be difficult to improve the temporal stability and the pattern rectangularity.
The upper limit of n is not particularly limited, but is 10 for example.
n is preferably 1 to 4, and more preferably 1 to 3.

The substituent as R ₃ is not particularly limited, but examples thereof include a monovalent organic group. Specific examples of the monovalent organic group include an alkyl group, an alkenyl group, a cycloalkyl group, an aryl group, a heterocyclic group, and an acyl group.

Examples of the alkyl group include an alkyl group having 1 to 20 carbon atoms, which may be linear or branched, preferably an alkyl group having 1 to 10 carbon atoms, and an alkyl group having 1 to 5 carbon atoms. More preferable.
Examples of the alkenyl group include alkenyl groups having 2 to 5 carbon atoms, which may be linear or branched and are preferably alkenyl groups having 2 to 3 carbon atoms.
Examples of the cycloalkyl group include a cycloalkyl group having 3 to 10 carbon atoms, and a cycloalkyl group having 3 to 6 carbon atoms is preferable.
The cycloalkyl group may have a hetero atom between carbon-carbon bonds. Examples of the hetero atom include an oxygen atom, a sulfur atom and a nitrogen atom.

Examples of the aryl group include an aryl group having 6 to 14 carbon atoms, and an aryl group having 6 to 10 carbon atoms is preferable.
The heterocyclic group may be monocyclic or polycyclic. The polycyclic type can suppress the diffusion of acid more. Further, the heterocyclic group may have aromaticity or may not have aromaticity. Examples of the heterocyclic ring having aromaticity include a furan ring, a thiophene ring, a benzofuran ring, a benzothiophene ring, a dibenzofuran ring, a dibenzothiophene ring, and a pyridine ring. Examples of the heterocycle having no aromaticity include a tetrahydropyran ring, a lactone ring, a sultone ring and a decahydroisoquinoline ring. Examples of the lactone ring and the sultone ring include the lactone structure and the sultone structure exemplified in the above resin. A furan ring, a thiophene ring, a pyridine ring, or a decahydroisoquinoline ring is particularly preferable as the heterocycle in the heterocyclic group.

The alkyl group, alkenyl group, cycloalkyl group, aryl group, heterocyclic group, heteroaryl group, and acyl group may further have a substituent.
The substituent is not particularly limited, and examples thereof include the above-mentioned substituent T, and examples thereof include an alkyl group, a halogen atom (for example, a fluorine atom, a chlorine atom, a bromine atom and an iodine atom), a nitro group and a formyl group.

When R ₃ represents a substituent, the atom bonded to H—C(═O)— in R ₃ is a carbon atom. If this is not satisfied, it tends to be difficult to improve the temporal stability and the pattern rectangularity.

The above compound (P) is preferably a compound represented by the following general formula (3) or the following general formula (4).

Specific examples of the substituent of R ₄ are the same as the specific examples of the substituent of R ₁ in the general formula (1), and the preferred ranges are also the same.
Specific examples of the substituent of R ₅ are the same as the specific examples of the substituent of R ₂ in the general formula (1), and the preferred range is also the same.
n represents an integer of 1 or more.
The upper limit of n is not particularly limited, but is 10 for example.
n is preferably 1 to 4, and more preferably 1 to 3.

Specific examples of the substituent of R ₆ are the same as the specific examples of the substituent of R ₁ in the above general formula (1), and the preferred range is also the same.
Specific examples of the substituent of R ₇ are the same as the specific examples of the substituent of R ₂ in the general formula (1), and the preferable range is also the same.
n1 represents an integer of 1 or more.
The upper limit of n1 is not particularly limited, but is 5, for example.
n1 is preferably 1 to 4, and preferably 1 or 2.

n2 represents an integer of 1 or more.
The upper limit of n2 is not particularly limited, but is 5, for example.
n2 is preferably 1 to 2, and more preferably 1.

In the general formula (4), C ₃ H ₆ may be linear or branched.

Specific examples of the compound (P) are shown below, but the present invention is not limited to these specific examples. C ₃ H ₆ may be linear or branched.

The content of the above compound (P) (when there are a plurality of compounds (P), the total thereof) is 1 ppm or more and 1000 ppm or less based on the total mass of the actinic ray-sensitive or radiation-sensitive resin composition.
If the content of the compound (P) (the total of the compounds (P) when there are a plurality of compounds) is less than 1 ppm, the effect of the present invention cannot be exhibited. If the content of the compound (P) (the total when plural compounds (P) are present) exceeds 1000 ppm, the rectangularity of the pattern shape and the temporal stability cannot both be achieved.
The content of the above compound (P) (when there are a plurality of compounds (P), the total thereof) is an actinic ray-sensitive or radiation-sensitive resin composition from the viewpoint of the rectangularity of the obtained pattern shape and the stability over time. It is preferably 1 ppm or more and 500 ppm or less, more preferably 1 ppm or more and 200 ppm or less, and further preferably 1 ppm or more and 100 ppm or less, based on the total mass of the product.

The molecular weight of the compound (P) is 500 or less. When multiple compounds (P) are present, the molecular weight of each compound (P) is 500 or less.
When the molecular weight of the compound (P) exceeds 500, the plasticity of the compound is developed to promote the diffusion of the acid generated in the exposed portion of the resist film, and the rectangularity of the obtained pattern is deteriorated.
The lower limit of the molecular weight of the compound (P) is not particularly limited, but is 30 for example.
The molecular weight of the compound (P) is preferably 30 to 400, more preferably 30 to 300, from the viewpoint of suppressing plasticization.

The composition of the present invention contains the compound (P) described above, but may contain the compound represented by the general formula (1), and the compound represented by the general formula (2). May be contained, and the compound represented by the above general formula (1) and the compound represented by the above general formula (2) may be contained.
When the composition of the present invention contains the compound represented by the general formula (1), the compound represented by the general formula (1) may be used alone or in combination of two or more. You may use together.
When the composition of the present invention contains the compound represented by the general formula (2), the compound represented by the general formula (2) may be used alone or in combination of two or more. You may use together.

The content of the above compound (P) in the actinic ray-sensitive or radiation-sensitive resin composition of the present invention can be measured, for example, by the following method.

(Compound represented by the general formula (1))
A resist solution containing the compound represented by the general formula (1) was prepared, and a FID detector (Agilent-6890A, Agilent) using a WAX-based column (DB-HeaveWAX (#123-7162), manufactured by Agilent Technologies) was used. -Analysis was carried out with a GC (gas chromatograph) device (Agilent-6890A, manufactured by Agilent Technologies) manufactured by Technology. The content of the compound represented by the general formula (1) was quantified by the absolute calibration curve method using the standard reagent of each compound.
The standard reagent is a mixture of a compound represented by the general formula (1) to be quantified with a known concentration and acetonitrile with a known concentration. A commercial item can be used as said acetonitrile.

(Compound represented by the general formula (2))
A resist solution containing the compound represented by the general formula (2) was prepared, and ultrasonic waves were irradiated for 3 minutes using an ultrasonic device (tabletop ultrasonic cleaner (#5510), manufactured by Bransonic Corp.). The obtained solution was used as a liquid chromatograph apparatus (Agilent 1100 HPLC G1315B, manufactured by Agilent Technologies) using a UV detector (Agilent 1100 HPLC G1315B manufactured by Agilent Technologies) using a reversed-phase column (Shim-pack CLC-ODS (M), manufactured by Shimadzu GLC). 1100 HPLC G1311A, manufactured by Agilent Technologies). The content of the compound represented by the general formula (2) was quantified by the absolute calibration curve method using the standard reagent of each compound.
The standard reagent is a mixture of the compound represented by the general formula (2) whose concentration is known and the DNPH whose concentration is known.

<Resin whose polarity increases due to the action of acid>
The actinic ray-sensitive or radiation-sensitive resin composition according to the present invention is typically a resin whose polarity is increased by the action of an acid to change its solubility in a developing solution (hereinafter, also referred to as “resin (A)”). It is preferable to contain).

The resin (resin (A)) whose polarity increases due to the action of the acid is preferably a resin obtained by polymerizing at least an ethylenically unsaturated compound.
The ethylenically unsaturated compound preferably has 1 to 4 ethylenically unsaturated bonds, and more preferably one. Further, the ethylenically unsaturated compound is preferably a monomer.
The molecular weight of the ethylenically unsaturated compound is preferably 28 to 1,000, more preferably 50 to 800, particularly preferably 100 to 600.

The resin whose polarity increases by the action of an acid preferably has an acid-decomposable group, and more preferably a resin having a structural unit having an acid-decomposable group.
In this case, in the pattern forming method according to the present invention to be described later, when an alkali developing solution is used as the developing solution, a positive pattern is preferably formed, and when an organic developing solution is used as the developing solution, A negative pattern is preferably formed.

[Structural unit having an acid-decomposable group]
The resin (A) preferably has a structural unit having an acid-decomposable group (also referred to as “repeating unit”).

As the resin (A), a known resin can be appropriately used. For example, paragraphs 0055 to 0191 of US Patent Application Publication No. 2016/0274458, paragraphs 0035 to 0085 of US Patent Application Publication No. 2015/0004544, and paragraphs 0045 of US Patent Application Publication No. 2016/0147150. Known resins disclosed in Nos. 0090 to 9090 can be preferably used as the resin (A).

The acid-decomposable group preferably has a structure in which a polar group is protected by a group capable of decomposing and leaving by the action of an acid (leaving group).
As the polar group, carboxy group, phenolic hydroxyl group, sulfonic acid group, sulfonamide group, sulfonylimide group, (alkylsulfonyl)(alkylcarbonyl)methylene group, (alkylsulfonyl)(alkylcarbonyl)imide group, bis(alkylcarbonyl) ) Methylene group, bis(alkylcarbonyl)imide group, bis(alkylsulfonyl)methylene group, bis(alkylsulfonyl)imide group, tris(alkylcarbonyl)methylene group, tris(alkylsulfonyl)methylene group and other acidic groups (2 Group which dissociates in an aqueous solution of tetramethylammonium hydroxide of 0.38% by mass), alcoholic hydroxyl group and the like.

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

Favorable polar groups include a carboxy group, a phenolic hydroxyl group, and a sulfonic acid group.

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

The alkyl group of R ³⁶ to R ³⁹ , R ⁰¹ and R ⁰² is preferably an alkyl group having 1 to 8 carbon atoms, and examples thereof include a methyl group, an ethyl group, a propyl group, an n-butyl group, a sec-butyl group and hexyl. Group, octyl group and the like.
The cycloalkyl group of R ³⁶ to R ³⁹ , R ⁰¹ and R ⁰² may be monocyclic or polycyclic. The monocyclic type is preferably a cycloalkyl group having a carbon number of 3 to 8, and examples thereof include a cyclopropyl group, a cyclobutyl group, a cyclopentyl group, a cyclohexyl group, and a cyclooctyl group. As the polycyclic type, a cycloalkyl group having 6 to 20 carbon atoms is preferable, and examples thereof include an adamantyl group, a norbornyl group, an isobornyl group, a camphanyl group, a dicyclopentyl group, an α-pinel group, a tricyclodecanyl group, and a tetracyclododecyl group. Group, and androstanyl group and the like. At least one carbon atom in the cycloalkyl group may be substituted with a hetero atom such as an oxygen atom.
The aryl group of R ³⁶ to R ³⁹ , R ⁰¹ and R ⁰² is preferably an aryl group having a carbon number of 6 to 10, and examples thereof include a phenyl group, a naphthyl group and an anthryl group.
The aralkyl group of R ³⁶ to R ³⁹ , R ⁰¹ and R ⁰² is preferably an aralkyl group having a carbon number of 7 to 12, and examples thereof include a benzyl group, a phenethyl group and a naphthylmethyl group.
The alkenyl group of R ³⁶ to R ³⁹ , R ⁰¹ and R ⁰² is preferably an alkenyl group having a carbon number of 2 to 8, and examples thereof include a vinyl group, an allyl group, a butenyl group, and a cyclohexenyl group.
The ring formed by combining R ³⁶ and R ³⁷ with each other is preferably a cycloalkyl group (monocyclic or polycyclic). As the cycloalkyl group, a cyclopentyl group, and a monocyclic cycloalkyl group such as a cyclohexyl group, or a polycyclic cycloalkyl group such as a norbornyl group, a tetracyclodecanyl group, a tetracyclododecanyl group, and an adamantyl group Is preferred.

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

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

In formula AI, Xa ¹ represents a hydrogen atom, a halogen atom other than a fluorine atom, or a monovalent organic group, T represents a single bond or a divalent linking group, and Rx ¹ to Rx ³ are each independently. Represents an alkyl group or a cycloalkyl group, and any two of Rx ¹ to Rx ³ may or may not form a ring structure.

Examples of the divalent linking group of T include an alkylene group, an arylene group, —COO—Rt—, and —O—Rt—. In the formula, Rt represents an alkylene group, a cycloalkylene group or an arylene group,
T is preferably a single bond or -COO-Rt-. Rt is preferably a chain alkylene group having 1 to 5 carbon atoms, more preferably —CH ₂ —, —(CH ₂ ) ₂ —, or —(CH ₂ ) ₃ —. More preferably, T is a single bond.

Xa ¹ is preferably a hydrogen atom or an alkyl group.
The alkyl group of Xa ¹ may have a substituent, and examples of the substituent include a hydroxyl group and a halogen atom other than a fluorine atom.
The alkyl group of Xa ¹ preferably has 1 to 4 carbon atoms, and examples thereof include a methyl group, an ethyl group, a propyl group, and a hydroxymethyl group. The alkyl group of Xa ¹ is preferably a methyl group.

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

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

Specific examples of the monomer corresponding to the structural unit represented by the formula AI will be shown below, but the present invention is not limited to these specific examples. The following specific examples correspond to the case where Xa ¹ in formula AI is a methyl group, but Xa ¹ can be optionally substituted with a hydrogen atom, a halogen atom other than a fluorine atom, or a monovalent organic group. ..

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

Further, the resin (A) is decomposed by the action of an acid described in US Patent Application Publication No. 2016/0070167, paragraphs 0363 to 0364, to generate an alcoholic hydroxyl group as a structural unit having an acid decomposable group. You may have the structural unit containing a group.

Further, the resin (A) has a repeating unit having an acid-decomposable group and a structure (acid-decomposable group) protected by a leaving group in which a phenolic hydroxyl group is decomposed and released by the action of an acid. It is preferable to have In addition, in this specification, a phenolic hydroxyl group is a group formed by substituting a hydrogen atom of an aromatic hydrocarbon group with a hydroxyl group. The aromatic ring of the aromatic hydrocarbon group is a monocyclic or polycyclic aromatic ring, and examples thereof include a benzene ring and a naphthalene ring.

Examples of the leaving group that is decomposed and released by the action of an acid include groups represented by formulas (Y1) to (Y4).
Formula (Y1): -C(Rx ₁ )(Rx ₂ )(Rx ₃ )
Formula (Y2): -C(=O)OC(Rx ₁ )(Rx ₂ )(Rx ₃ )
Formula (Y3): -C(R ₃₆ )(R ₃₇ )(OR ₃₈ ).
Formula (Y4): -C(Rn)(H)(Ar)

In formulas (Y1) and (Y2), Rx ₁ to Rx ₃ each independently represent an alkyl group (linear or branched) or a cycloalkyl group (monocyclic or polycyclic). However, when all of Rx ₁ to Rx ₃ are alkyl groups (linear or branched), at least two of Rx ₁ to Rx ₃ are preferably methyl groups.
Among _them, Rx 1 ~ Rx ₃ are each independently, more preferably a repeating unit represents a linear or branched alkyl _group, Rx 1 ~ Rx ₃ each independently represents a linear It is more preferable that the repeating unit is an alkyl group.
Two of Rx ₁ to Rx ₃ may combine to form a monocyclic or polycyclic ring.
The alkyl group of Rx ₁ to Rx ₃ is preferably an alkyl group having 1 to 4 carbon atoms such as methyl group, ethyl group, n-propyl group, isopropyl group, n-butyl group, isobutyl group, and t-butyl group. ..
The cycloalkyl group of Rx ₁ to Rx ₃ is a monocyclic cycloalkyl group such as a cyclopentyl group or a cyclohexyl group, or a polycyclic ring such as a norbornyl group, a tetracyclodecanyl group, a tetracyclododecanyl group or an adamantyl group. The cycloalkyl group of is preferred.
The cycloalkyl group formed by combining two members of Rx ₁ to Rx ₃ is a monocyclic cycloalkyl group such as a cyclopentyl group and a cyclohexyl group, or a norbornyl group, a tetracyclodecanyl group, a tetracyclododecanyl group. Groups and polycyclic cycloalkyl groups such as adamantyl groups are preferred. Of these, a monocyclic cycloalkyl group having 5 to 6 carbon atoms is more preferable.
The cycloalkyl group formed by combining two members of Rx ₁ to Rx ₃ is, for example, a group in which one of the methylene groups constituting the ring has a hetero atom such as an oxygen atom or a hetero atom such as a carbonyl group. It may be replaced.
In the groups represented by the formulas (Y1) and (Y2), for example, Rx ₁ is a methyl group or an ethyl group, and Rx ₂ and Rx ₃ are bonded to each other to form the above cycloalkyl group. preferable.

In formula (Y3), R ₃₆ to R ₃₈ each independently represent a hydrogen atom or a monovalent organic group. R ₃₇ and R ₃₈ may combine with each other to form a ring. Examples of the monovalent organic group include an alkyl group, a cycloalkyl group, an aryl group, an aralkyl group, and an alkenyl group. R ₃₆ is preferably a hydrogen atom.

In the formula (Y4), Ar represents an aromatic hydrocarbon group. Rn represents an alkyl group, a cycloalkyl group, or an aryl group. Rn and Ar may combine with each other to form a non-aromatic ring. Ar is more preferably an aryl group.

As the repeating unit having a structure protected by a leaving group (acid-decomposable group) in which the phenolic hydroxyl group is decomposed and released by the action of an acid, a hydrogen atom in the phenolic hydroxyl group is represented by formulas (Y1) to (Y4) Those having a structure protected by a group represented by are preferred.

A repeating unit represented by the following general formula (AII) is preferable as the repeating unit having a structure protected by a leaving group (acid-decomposable group) in which a phenolic hydroxyl group is decomposed and released by the action of an acid.

In general formula (AII),
R ₆₁ , R _62, and R ₆₃ each independently represent a hydrogen atom, an alkyl group, a cycloalkyl group, a halogen atom, a cyano group, or an alkoxycarbonyl group. However, R ₆₂ may combine with Ar ₆ to form a ring, in which case R ₆₂ represents a single bond or an alkylene group.
X ₆ represents a single bond, —COO—, or —CONR ₆₄ —. R ₆₄ represents a hydrogen atom or an alkyl group.
L ₆ represents a single bond or an alkylene group.
Ar ₆ represents a (n+1)-valent aromatic hydrocarbon group, and represents a (n+2)-valent aromatic hydrocarbon group when it forms a ring by bonding with R ₆₂ .
Y ₂ each independently represents a hydrogen atom or a group capable of leaving by the action of an acid when n≧2. However, at least one of Y ₂ represents a group capable of leaving by the action of an acid. The groups capable of leaving by the action of an acid as Y ₂ are preferably of the formulas (Y1) to (Y4).
n represents an integer of 1 to 4.

Each of the above groups may have a substituent, and examples of the substituent include an alkyl group (having 1 to 4 carbon atoms), a halogen atom, a hydroxyl group, an alkoxy group (having 1 to 4 carbon atoms), a carboxyl group, and Examples thereof include alkoxycarbonyl groups (having 2 to 6 carbon atoms), and those having 8 or less carbon atoms are preferable.

The resin (A) may include one type of structural unit having an acid-decomposable group, or may include two or more types.

The content of the constitutional unit having an acid-decomposable group contained in the resin (A) (when there are a plurality of constitutional units having an acid-decomposable group, the total thereof) is, with respect to all the constitutional units of the resin (A), 5 mol% to 90 mol% is preferable, 10 mol% to 80 mol% is more preferable, and 15 mol% to 70 mol% is further preferable.
In the present invention, when the content of the “constituent unit” is defined by a molar ratio, the “constituent unit” is synonymous with the “monomer unit”. Further, in the present invention, the “monomer unit” may be modified after polymerization by a polymer reaction or the like. The same applies to the following.

[Structural unit having at least one selected from the group consisting of lactone structure, sultone structure, and carbonate structure]
The resin (A) preferably has a structural unit having at least one selected from the group consisting of a lactone structure, a sultone structure, and a carbonate structure.

Any lactone structure or sultone structure may be used as long as it has a lactone structure or a sultone structure, but is preferably a 5- to 7-membered lactone structure or a 5 to 7-membered sultone structure, A bicyclic structure in a membered lactone structure, or another ring structure condensed to form a spiro structure, or another ring structure in which a bicyclo structure or a spiro structure is formed in a 5- to 7-membered sultone structure Is more preferably a condensed ring. It is more preferable to have a structural unit having a lactone structure represented by any of the following formulas LC1-1 to LC1-21 or a sultone structure represented by any of the following formulas SL1-1 to SL1-3. Further, the lactone structure or the sultone structure may be directly bonded to the main chain. Preferred structures are LC1-1, LC1-4, LC1-5, LC1-8, LC1-16, LC1-21, SL1-1.

The lactone structure portion or the sultone structure portion may or may not have a substituent (Rb ² ). Preferred substituents (Rb ² ) are alkyl groups having 1 to 8 carbon atoms, cycloalkyl groups having 4 to 7 carbon atoms, alkoxy groups having 1 to 8 carbon atoms, alkoxycarbonyl groups having 2 to 8 carbon atoms, and carboxyl groups. , A halogen atom other than a fluorine atom, a hydroxyl group, a cyano group, and an acid-decomposable group. More preferably, they are an alkyl group having 1 to 4 carbon atoms, a cyano group, and an acid-decomposable group. n2 represents an integer of 0 to 4. When n2 is 2 or more, the plural substituents (Rb ² ) may be the same or different. Further, a plurality of substituents (Rb ² ) may be bonded to each other to form a ring.

The constitutional unit having a lactone structure or a sultone structure is preferably a constitutional unit represented by the following formula III.
Further, the resin having a structural unit having an acid-decomposable group preferably contains a structural unit represented by the following formula III.

In the above formula III,
A represents an ester bond (group represented by —COO—) or an amide bond (group represented by —CONH—).
n is the repeating number of the structure represented by -R ⁰ -Z-, represents an integer of 0 to 5, is preferably 0 or 1, and is more preferably 0. When n is 0, -R ⁰ -Z- is absent and A and R ⁸ are bonded by a single bond.
R ⁰ represents an alkylene group, a cycloalkylene group, or a combination thereof. When there are a plurality of R ^0's , each independently represents an alkylene group, a cycloalkylene group, or a combination thereof.
Z represents a single bond, an ether bond, an ester bond, an amide bond, a urethane bond or a urea bond. When a plurality of Z's are present, each independently represents a single bond, an ether bond, an ester bond, an amide bond, a urethane bond or a urea bond.
R ⁸ represents a monovalent organic group having a lactone structure or a sultone structure.
R ⁷ represents a hydrogen atom, a halogen atom other than a fluorine atom, or a monovalent organic group (preferably a methyl group).

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

Specific examples of the monomer corresponding to the constitutional unit represented by the formula III and specific examples of the monomer corresponding to the constitutional unit represented by the formula A-1 described later are shown below, but the present invention is not limited to these specific examples. Not limited to. The following specific examples correspond to the case where R ⁷ in formula III and R _A ¹ in formula A-1 described later are methyl groups, and R ⁷ and R _A ¹ are a hydrogen atom or a halogen atom other than a fluorine atom. , Or a monovalent organic group can be optionally substituted.

In addition to the above monomers, the following monomers are also suitably used as a raw material for the resin (A).

The resin (A) may have a structural unit having a carbonate structure. The carbonate structure is preferably a cyclic carbonic acid ester structure.
The structural unit having a cyclic carbonic acid ester structure is preferably a structural unit represented by the following formula A-1.

In formula A-1, R _A ¹ represents a hydrogen atom, a halogen atom other than a fluorine atom, or a monovalent organic group (preferably a methyl group), n represents an integer of 0 or more, and R _A ² represents a substituent. Represents a group. R _A ² each independently represents a substituent when n is 2 or more, A represents a single bond or a divalent linking group, and Z represents —O—C(═O) in the formula. ) Represents an atomic group forming a monocyclic structure or a polycyclic structure with a group represented by —O—.

The resin (A) is described in paragraphs 0370 to 0414 of US Patent Application Publication No. 2016/0070167 as a structural unit having at least one selected from the group consisting of a lactone structure, a sultone structure, and a carbonate structure. It is also preferable to have a structural unit.

The resin (A) preferably has at least two structural units (a) having a lactone structure (hereinafter, also referred to as “structural unit (a)”).
The at least two lactone structures may be, for example, a structure in which at least two lactone structures are condensed, or may be a structure in which at least two lactone structures are linked by a single bond or a linking group. Good.
The lactone structure contained in the structural unit (a) is not particularly limited, but a 5- to 7-membered ring lactone structure is preferable, and a bicyclo structure or a spiro structure is formed in the 5- to 7-membered ring lactone structure to reduce other ring structures. A ring is preferable.
The lactone structure is preferably, for example, the lactone structure represented by any of LC1-1 to LC1-21 described above.

The structural unit having at least two lactone structures (hereinafter, also referred to as “structural unit (a)”) is preferably a structural unit represented by the following formula L-1.

In Formula L-1, Ra represents a hydrogen atom or an alkyl group, and Rb represents a partial structure having two or more lactone structures.

The Ra alkyl group is preferably an alkyl group having 1 to 4 carbon atoms, more preferably a methyl group or an ethyl group, and particularly preferably a methyl group. The alkyl group of Ra may be substituted. Examples of the substituent include a halogen atom such as a fluorine atom, a chlorine atom and a bromine atom, a mercapto group, a hydroxy group, a methoxy group, an ethoxy group, an isopropoxy group, an alkoxy group such as a t-butoxy group and a benzyloxy group, an acetyl group. And acetoxy groups such as propionyl group. Ra is preferably a hydrogen atom, a methyl group, a trifluoromethyl group, or a hydroxymethyl group.

Examples of the lactone structure contained in the Rb partial structure include the lactone structure described above.
The partial structure of Rb having two or more lactone structures is preferably, for example, a structure in which at least two lactone structures are linked by a single bond or a linking group, and a structure in which at least two lactone structures are condensed. ..
A structural unit (a1) having a structure in which at least two lactone structures are condensed and a structural unit (a2) having a structure in which at least two lactone structures are linked by a single bond or a linking group are described below. Each will be explained.

-Structural unit (a1) having a structure in which at least two lactone structures are condensed ring-
The structure in which at least two lactone structures are condensed is preferably a structure in which two or three lactone structures are condensed, and is a structure in which two lactone structures are condensed. Is more preferable.
Examples of the structural unit having a structure in which at least two lactone structures are condensed (hereinafter also referred to as “structural unit (a1)”) include structural units represented by the following formula L-2.

In formula L-2, Ra has the same meaning as Ra in formula L-1, Re ₁ to Re ₈ each independently represent a hydrogen atom or an alkyl group, and Me ₁ represents a single bond or a divalent linking group. And Me ₂ and Me ₃ each independently represent a divalent linking group.

The alkyl group of Re ₁ to Re ₈ preferably has, for example, 5 or less carbon atoms, and more preferably has 1 carbon atom.
Examples of the alkyl group of Re ₁ to Re ₈ having 5 or less carbon atoms include, for example, methyl group, ethyl group, n-propyl group, isopropyl group, n-butyl group, isobutyl group, t-butyl group, n-pentyl group and isopentyl. Group, s-pentyl group, t-pentyl group and the like.
Among them, Re ₁ to Re ₈ are preferably hydrogen atoms.

Examples of the divalent linking group of Me ₁ include an alkylene group, a cycloalkylene group, —O—, —CO—, —COO—, —OCO—, and a group in which two or more of these groups are combined. To be
The alkylene group of Me ₁ preferably has, for example, 1 to 10 carbon atoms. Moreover, it is more preferable that it has 1 or 2 carbon atoms, and the alkylene group having 1 or 2 carbon atoms is, for example, preferably a methylene group or an ethylene group.
The alkylene group of Me ₁ may be linear or branched, and examples thereof include methylene group, ethane-1,1-diyl group, ethane-1,2-diyl group, propane-1,1-diyl group, propane. Examples thereof include a 1,3-diyl group, a propane-2,2-diyl group, a pentane-1,5-diyl group and a hexane-1,6-diyl group.
The cycloalkylene group of Me ₁ has, for example, preferably 5 to 10 carbon atoms, and more preferably 5 or 6 carbon atoms.
Examples of the cycloalkylene group of Me ₁ include a cyclopentylene group, a cyclohexylene group, a cycloheptylene group, a cyclooctylene group, and a cyclodecylene group.
As the divalent linking group of Me ₁ , a group in which two or more groups are combined is, for example, a group in which an alkylene group and —COO— are combined or a group in which —OCO— and an alkylene group are combined. preferable. Further, the group in which two or more groups are combined is more preferably a group in which a methylene group and a —COO— group are combined and a group in which a —COO— group and a methylene group are combined.

Examples of the divalent linking group of Me ₂ and Me ₃ include an alkylene group and —O—. The divalent linking group of Me ₂ and Me ₃ is preferably a methylene group, an ethylene group or —O—, more preferably —O—.

The monomer corresponding to the structural unit (a1) can be synthesized, for example, by the method described in JP-A-2005-160836.

Specific examples of the structural unit (a1) are shown below, but the present invention is not limited thereto. In each of the following formulas, R ₉ represents a hydrogen atom, a methyl group, a trifluoromethyl group or a hydroxymethyl group, and * represents a bonding position with another structural unit.

-Structural unit (a2) having a structure in which at least two lactone structures are linked by a single bond or a linking group-
The structure in which at least two lactone structures are linked by a single bond or a linking group is preferably a structure in which 2 to 4 lactone structures are linked by a single bond or a linking group, and the two lactone structures are It is more preferable that the structure is a single bond or a connecting group.
Examples of the linking group include the same groups as those mentioned as the linking group of M ₂ in formula L-3 described later.
The structural unit having a structure in which two or more lactone structures are linked by a single bond or a linking group (hereinafter, also referred to as “structural unit (a2)”) has, for example, a structure represented by the following formula L-3. The unit is mentioned.

In formula L-3, Ra has the same meaning as Ra in formula L-1, M ₁ and M ₂ each independently represent a single bond or a linking group, and Lc ₁ and Lc ₂ each independently represent a lactone. It represents a group having a structure.

Examples of the linking group of M ₁ include an alkylene group, a cycloalkylene group, —O—, —CO—, —COO—, —OCO—, and groups in which two or more of these groups are combined.
The alkylene group of M ₁ preferably has, for example, 1 to 10 carbon atoms.
The alkylene group for M ₁ may be linear or branched, and examples thereof include methylene group, ethane-1,1-diyl group, ethane-1,2-diyl group, propane-1,1-diyl group, propane. Examples thereof include a 1,3-diyl group, a propane-2,2-diyl group, a pentane-1,5-diyl group and a hexane-1,6-diyl group.
The cycloalkylene group of M ₁ preferably has, for example, 5 to 10 carbon atoms.
Examples of the cycloalkylene group of M ₁ include a cyclopentylene group, a cyclohexylene group, a cycloheptylene group, a cyclooctylene group, a cyclodecylene group and the like.
The group in which two or more groups are combined as the linking group for M ₁ is preferably, for example, a group in which an alkylene group and —COO— are combined, or a group in which —OCO— and an alkylene group are combined. Further, the group in which two or more groups are combined is more preferably a group in which a methylene group and a —COO— group are combined and a group in which a —COO— group and a methylene group are combined.
Examples of the linking group for M ₂ include the same groups as those mentioned for the linking group for M ₁ .

The lactone structure of Lc ₁ is, for example, preferably a 5- to 7-membered ring lactone structure, in which a 5- to 7-membered lactone structure is condensed with another ring structure to form a bicyclo structure or a spiro structure. preferable. The lactone structure is more preferably a lactone structure represented by any of LC1-1 to LC1-21. More preferable lactone structures include LC1-1, LC1-4, LC1-5, LC1-6, LC1-13, LC1-14 and LC1-17.
The lactone structure of Lc ₁ may contain a substituent. Examples of the substituent that the lactone structure of Lc1 may include include the same substituents as the above-described substituent (Rb2) of the lactone structure.
The lactone structure of Lc ₂ includes, for example, the same lactone structure as the lactone structure of Lc ₁ .

The structural unit (a2) is preferably a structural unit represented by the following formula L-4 as the structural unit represented by the above formula L-3.

In formula L-4, Ra has the same meaning as Ra in formula L-1, Mf ₁ and Mf ₂ each independently represent a single bond or a linking group, and Rf ₁ , Rf ₂ and Rf ₃ are independent of each other. Represents a hydrogen atom or an alkyl group, and Mf ₁ and Rf ₁ may be bonded to each other to form a ring, and Mf ₂ and Rf ₂ or Rf ₃ are bonded to each other to form a ring. It may be formed.

The linking group for Mf _{1 has} the same meaning as the linking group for M _{1 in} formula L-3 above.
The linking group for Mf _{2 has} the same meaning as the linking group for M _{2 in} formula L-3 above.
Examples of the alkyl group of Rf ₁ include an alkyl group having 1 to 4 carbon atoms. The alkyl group having 1 to 4 carbon atoms of Rf ₁ is preferably a methyl group or an ethyl group, more preferably a methyl group. The alkyl group of Rf ₁ may have a substituent. Examples of the substituent that the alkyl group of Rf ₁ may have include a hydroxy group, an alkoxy group such as a methoxy group and an ethoxy group, a cyano group, and a halogen atom such as a fluorine atom.
The alkyl group of Rf ₂ and Rf ₃ has the same meaning as the alkyl group of Rf ₁ .

Mf ₁ and Rf ₁ may combine with each other to form a ring. Examples of the structure in which Mf1 and Rf1 are bonded to each other to form a ring include the lactone structure represented by LC1-13, LC1-14, or LC1-17 described above in the lactone structure described above.
Mf ₂ and Rf ₂ or Rf ₃ may be bonded to each other to form a ring.
Examples of the structure in which Mf2 and Rf2 are bonded to each other to form a ring include the lactone structure represented by LC1-7, LC1-8 or LC1-15 described above in the lactone structure described above.
Examples of the structure in which Mf ₂ and Rf ₃ are bonded to each other to form a ring include the lactone structure represented by any of the above-mentioned LC1-3 to LC1-6 in the above-mentioned lactone structure.
Specific examples of the structural unit (a2) are shown below, but the invention is not limited thereto. * Represents a bonding position with another structural unit.

The constituent unit having at least two lactone structures usually has optical isomers, but any optical isomer may be used. Moreover, one optical isomer may be used alone, or a plurality of optical isomers may be mixed and used. When one type of optical isomer is mainly used, the optical purity (ee) thereof is preferably 90% or more, more preferably 95% or more.

The content of the structural unit having at least two lactone structures is preferably 10 mol% to 60 mol%, more preferably 20 mol% to 50 mol%, and even more preferably the content of all structural units in the resin (A). It is 30 to 50 mol %.
In order to enhance the effect of the present invention, it is possible to use two or more kinds of constitutional units having at least two lactone structures in combination. When two or more kinds of repeating units having at least two lactone structures are contained, the total content of the constituent units having at least two lactone structures is preferably within the above range.

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

Content of a structural unit having at least one selected from the group consisting of a lactone structure, a sultone structure and a carbonate structure contained in the resin (A) (selected from the group consisting of a lactone structure, a sultone structure and a carbonate structure. When there are a plurality of constitutional units having at least one kind, the total thereof is preferably 5 mol% to 70 mol%, and 10 mol% to 65 mol% with respect to all the constitutional units of the resin (A). Is more preferable, and 20 mol% to 60 mol% is further preferable.

[Structural Unit Having Polar Group]
The resin (A) preferably has a structural unit having a polar group.
Examples of the polar group include a hydroxyl group, a cyano group, and a carboxy group.
The constituent unit having a polar group is preferably a constituent unit having an alicyclic hydrocarbon structure substituted with a polar group. Moreover, it is preferable that the structural unit having a polar group does not have an acid-decomposable group. In the alicyclic hydrocarbon structure substituted with a polar group, the alicyclic hydrocarbon structure is preferably an adamantyl group or a norbornyl group.

Specific examples of the monomer corresponding to the structural unit having a polar group are shown below, but the present invention is not limited to these specific examples. Although the following specific examples are described as methacrylic acid ester compounds, acrylic acid ester compounds may be used.

In addition to these, specific examples of the structural unit having a polar group include the structural units disclosed in paragraphs 0415 to 0433 of US Patent Application Publication No. 2016/0070167.
The resin (A) may include one type of structural unit having a polar group, or may include two or more types in combination.
The content of the structural unit having a polar group is preferably 5 mol% to 40 mol%, more preferably 5 mol% to 30 mol%, and more preferably 10 mol% to 25% with respect to all the structural units in the resin (A). More preferred is mol %.

[Structural unit having neither acid-decomposable group nor polar group]
The resin (A) can further have a structural unit having neither an acid-decomposable group nor a polar group. The constituent unit having neither an acid-decomposable group nor a polar group preferably has an alicyclic hydrocarbon structure. Examples of the structural unit having neither an acid decomposable group nor a polar group include the structural units described in paragraphs 0236 to 0237 of US Patent Application Publication No. 2016/0026083. Preferred examples of the monomer corresponding to the structural unit having neither an acid-decomposable group nor a polar group are shown below.

In addition to this, specific examples of the structural unit having neither an acid-decomposable group nor a polar group include structural units disclosed in paragraph 0433 of U.S. Patent Application Publication No. 2016/0070167. it can.
The resin (A) may include one type of structural unit having neither an acid-decomposable group nor a polar group, or may include two or more types in combination.
The content of the structural unit having neither an acid-decomposable group nor a polar group is preferably 5 to 40 mol%, more preferably 5 to 30 mol%, based on all the structural units in the resin (A). 5 to 25 mol% is more preferable.

[Repeating unit (a1)]
The resin (A) can further have the following repeating unit (a1).
The repeating unit (a1) is a repeating unit derived from a monomer (also referred to as “monomer a1”) having a glass transition temperature of 50° C. or lower when formed into a homopolymer.
The repeating unit (a1) is a non-acid-decomposable repeating unit. Therefore, the repeating unit (a1) does not have an acid-decomposable group.

(Method of measuring glass transition temperature of homopolymer)
The glass transition temperature of the homopolymer is a catalog value or a literature value if there is a literature value, and if not, it is measured by a differential scanning calorimetry (DSC) method. The weight average molecular weight (Mw) of the homopolymer used for Tg measurement is 18000, and the dispersity (Mw/Mn) is 1.7. As the DSC device, a thermal analysis DSC differential scanning calorimeter Q1000 type manufactured by TA Instruments Japan Co., Ltd. is used, and the temperature rising rate is measured at 10° C./min.
The homopolymer used for the measurement of Tg may be synthesized by a known method using a corresponding monomer, for example, a general dropping polymerization method. An example is shown below.
54 parts by mass of propylene glycol monomethyl ether acetate (PGMEA) was heated to 80° C. under a nitrogen stream. While stirring this solution, 125 parts by mass of a PGMEA solution containing 21% by mass of the corresponding monomer and 0.35% by mass of dimethyl 2,2′-azobisisobutyrate was added dropwise over 6 hours. After the completion of dropping, the mixture was stirred at 80° C. for 2 hours. After allowing the reaction solution to cool, it is reprecipitated with a large amount of methanol/water (mass ratio 9:1), filtered, and the obtained solid is dried to obtain a homopolymer (Mw: 18000, Mw/Mn: 1.7). Got The obtained homopolymer was subjected to DSC measurement. The DSC device and the heating rate were as described above.

The monomer a1 is not particularly limited as long as it has a glass transition temperature (Tg) of 50° C. or less when it is a homopolymer, and improves the resolution of the dot pattern and the roughness of the side wall of the resist pattern that may occur during etching. From the viewpoint of suppression, the Tg of the homopolymer is preferably 30° C. or lower. The lower limit of Tg when the monomer a1 is a homopolymer is not particularly limited, but is preferably −80° C. or higher, more preferably −70° C. or higher, further preferably −60° C. or higher, and particularly preferably Is -50°C or higher. By setting the lower limit of Tg when the monomer a1 is a homopolymer within the above range, the fluidity of the pattern during heating is suppressed and the verticality of the dot pattern is further improved, which is preferable.

The repeating unit (a1) is a repeating unit having a non-acid-decomposable alkyl group having 2 or more carbon atoms, which may contain a hetero atom in the chain, from the viewpoint that the residual solvent can be more easily volatilized. Is preferred. In the present specification, “non-acid decomposable” means that the acid generated by the photo-acid generator does not cause elimination/decomposition reaction.
That is, the "non-acid-decomposable alkyl group" is, more specifically, an alkyl group that is not eliminated from the resin (A) by the action of an acid generated by the photo-acid generator, or a photo-acid generator is generated. An alkyl group which is not decomposed by the action of an acid is mentioned.
The non-acid-decomposable alkyl group may be linear or branched.
The repeating unit having a non-acid-decomposable alkyl group having 2 or more carbon atoms, which may contain a hetero atom in the chain, will be described below.

The non-acid-decomposable alkyl group having 2 or more carbon atoms which may contain a hetero atom in the chain is not particularly limited, and examples thereof include an alkyl group having 2 to 20 carbon atoms and a hetero group in the chain. Examples thereof include an alkyl group having 2 to 20 carbon atoms and containing an atom.
Examples of the alkyl group having a hetero atom in the chain and having 2 to 20 carbon atoms include, for example, one or more --CH ₂ --, --O--, --S--, --CO--, --NR ₆ --. Or an alkyl group substituted with a divalent organic group, which is a combination of two or more thereof. R ₆ represents a hydrogen atom or an alkyl group having 1 to 6 carbon atoms.
The non-acid-decomposable alkyl group having 2 or more carbon atoms, which may contain a hetero atom in the chain, specifically includes a methyl group, an ethyl group, a propyl group, a butyl group, a pentyl group, a hexyl group, Heptyl group, octyl group, nonyl group, decyl group, lauryl group, stearyl group, isobutyl group, sec-butyl group, 1-ethylpentyl group, 2-ethylhexyl group, and one or more of these- An example is a monovalent alkyl group in which CH ₂ — is replaced with —O— or —O—CO—.

The number of carbon atoms of the non-acid-decomposable alkyl group having 2 or more carbon atoms, which may contain a hetero atom in the chain, is preferably 2 or more and 16 or less, and more preferably 2 or more and 10 or less. It is more preferably 2 or more and 8 or less. The lower limit of the carbon number of the non-acid-decomposable alkyl group having 2 or more carbon atoms is preferably 4 or more.
The non-acid-decomposable alkyl group having 2 or more carbon atoms may have a substituent (for example, the substituent T).

The repeating unit (a1) is preferably a repeating unit represented by the following general formula (1-2).

In formula (1-2), R ₁ represents a hydrogen atom, a halogen atom, an alkyl group, or a cycloalkyl group. R ₂ represents a non-acid-decomposable alkyl group having 2 or more carbon atoms, which may contain a hetero atom in the chain.

The halogen atom represented by R ₁ is not particularly limited, and examples thereof include a fluorine atom, a chlorine atom, a bromine atom and an iodine atom.
The alkyl group represented by R ₁ is not particularly limited, but examples thereof include an alkyl group having 1 to 10 carbon atoms, and specific examples thereof include a methyl group, an ethyl group, and a tert-butyl group. .. Of these, an alkyl group having 1 to 3 carbon atoms is preferable, and a methyl group is more preferable.
The cycloalkyl group represented by R ₁ is not particularly limited, but examples thereof include a cycloalkyl group having 5 to 10 carbon atoms, and more specifically, a cyclohexyl group and the like.
Among them, R ₁ is preferably a hydrogen atom or a methyl group.

The definition and preferred embodiments of the non-acid-decomposable alkyl group having 2 or more carbon atoms, which may contain a hetero atom in the chain represented by R ₂ , are as described above.

Further, the repeating unit (a1) is a non-acid-decomposable alkyl group having a carboxy group or a hydroxyl group, which may contain a hetero atom in the chain, or a ring member, because the residual solvent can be more easily volatilized. It may be a repeating unit having a non-acid-decomposable cycloalkyl group having a carboxy group or a hydroxyl group, which may contain a hetero atom.
Hereinafter, may contain a hetero atom in the chain, a non-acid-decomposable alkyl group having a carboxy group or a hydroxyl group, or may contain a hetero atom in the ring member, a non-acid decomposing having a carboxy group or a hydroxyl group The repeating unit having a volatile cycloalkyl group will be described.

The non-acid-decomposable alkyl group may be linear or branched.
The number of carbon atoms of the non-acid decomposable alkyl group is preferably 2 or more, and the upper limit of the number of carbon atoms of the non-acid decomposable alkyl group is, for example, 20 or less, from the viewpoint that the Tg of the homopolymer is 50° C. or less. preferable.

The non-acid-decomposable alkyl group which may contain a hetero atom in the chain is not particularly limited, and examples thereof include an alkyl group having 2 to 20 carbon atoms, and a carbon number containing a hetero atom in the chain. There may be mentioned 2 to 20 alkyl groups. At least one hydrogen atom in the alkyl group is substituted with a carboxy group or a hydroxyl group.
Examples of the alkyl group having a hetero atom in the chain and having 2 to 20 carbon atoms include, for example, one or more --CH ₂ --, --O--, --S--, --CO--, --NR ₆ --. Or an alkyl group substituted with a divalent organic group, which is a combination of two or more thereof. R ₆ represents a hydrogen atom or an alkyl group having 1 to 6 carbon atoms.

The number of carbon atoms of the non-acid-decomposable alkyl group, which may contain a hetero atom in the chain, is preferably 2 to 16 and more preferably 2 to 10 from the viewpoint of being more excellent in crack resistance (hard to generate cracks). Preferred is 2 to 8 and more preferred.
The non-acid-decomposable alkyl group may have a substituent (for example, the substituent T).
Specific examples of the repeating unit having a non-acid-decomposable alkyl group having a carboxy group and containing a hetero atom in the chain include the repeating unit having the following structure.

The number of carbon atoms of the non-acid decomposable cycloalkyl group is preferably 5 or more, and the upper limit of the number of carbon atoms of the non-acid decomposable cycloalkyl group is, for example, 20 or less, from the viewpoint that the Tg of the homopolymer is 50° C. or less. It is preferably 16 or less, more preferably 10 or less.

The non-acid-decomposable cycloalkyl group that may contain a hetero atom as a ring member is not particularly limited, and examples thereof include a cycloalkyl group having 5 to 20 carbon atoms (more specifically, a cyclohexyl group), and And a cycloalkyl group having 5 to 20 carbon atoms containing a hetero atom as a ring member. At least one hydrogen atom in the cycloalkyl group is substituted with a carboxy group or a hydroxyl group.
Examples of the cycloalkyl group having a hetero atom as a ring member and having 5 to 20 carbon atoms include, for example, one or more --CH ₂ --, --O--, --S--, --CO--, --NR ₆ Or a cycloalkyl group substituted with a divalent organic group, which is a combination of two or more thereof. R ₆ represents a hydrogen atom or an alkyl group having 1 to 6 carbon atoms.
The non-acid-decomposable cycloalkyl group may have a substituent (for example, the substituent T).

The chain may contain a heteroatom, a non-acid-decomposable alkyl group having a carboxy group or a hydroxyl group, or a ring member may contain a hetero atom, a non-acid-decomposable cyclo group having a carboxy group or a hydroxyl group. As the repeating unit having an alkyl group, a repeating unit represented by the following general formula (1-3) is preferable, because the effect of the present invention is excellent.

In formula (1-3), R ₃ represents a hydrogen atom, a halogen atom, an alkyl group, or a cycloalkyl group. R ₄ is a non-acid-decomposable alkyl group having a carboxy group or a hydroxyl group, which may contain a hetero atom in the chain, or a non-acid group having a carboxy group or a hydroxyl group, which may contain a hetero atom as a ring member. Represents an acid-decomposable cycloalkyl group.

In formula (1-3), R ₃ has the same meaning as R ₁ described above, and the preferred embodiments are also the same.

A non-acid-decomposable alkyl group having a carboxy group or a hydroxyl group, which may contain a hetero atom in the chain represented by R ₄ , or a carboxy group or a hydroxyl group, which may contain a hetero atom as a ring member. The definition and preferred embodiments of the non-acid-decomposable cycloalkyl group have are as described above.
Among them, R ₄ is preferably a non-acid-decomposable cycloalkyl group having a carboxy group or a hydroxyl group, which may contain a hetero atom as a ring member. Examples of this embodiment include a repeating unit having the following structure.

Examples of the monomer a1 include ethyl acrylate (-22°C), n-propyl acrylate (-37°C), isopropyl acrylate (-5°C), n-butyl acrylate (-55°C), n-butyl methacrylate (20°C). ), n-hexyl acrylate (-57°C), n-hexyl methacrylate (-5°C), n-octyl methacrylate (-20°C), 2-ethylhexyl acrylate (-70°C), isononyl acrylate (- 82°C), lauryl methacrylate (-65°C), 2-hydroxyethyl acrylate (-15°C), 2-hydroxypropyl methacrylate (26°C), 1-[2-(methacryloyloxy)ethyl] succinate (9°C) , 2-ethylhexyl methacrylate (-10°C), sec-butyl acrylate (-26°C), methoxypolyethylene glycol monomethacrylate (n=2) (-20°C), hexadecyl acrylate (35°C) and the like. .. The value in parentheses represents Tg (° C.) when a homopolymer is used.

Note that methoxy polyethylene glycol monomethacrylate (n=2) is a compound with the following structure.

Monomers a1 are n-butyl acrylate, n-hexyl methacrylate, n-octyl methacrylate, 2-ethylhexyl methacrylate, 2-ethylhexyl acrylate, lauryl methacrylate, hexadecyl acrylate, 2-hydroxyethyl acrylate, and The compound represented by MA-5 is preferred.

The resin (A) may include only one type of repeating unit (a1) or may include two or more types of repeating unit (a1).
In the resin (A), the content of the repeating unit (a1) (when there are a plurality of repeating units (a1), the total thereof) is preferably 5 mol% or more based on all repeating units of the resin (A), 10 mol% or more is more preferable, 50 mol% or less is preferable, 40 mol% or less is more preferable, and 30 mol% or less is further preferable. Above all, the content of the repeating unit (a1) in the resin (A) (when a plurality of repeating units (a1) is present, the total thereof) is 5 to 50 mol% based on all the repeating units of the resin (A). Is preferred, 5 to 40 mol% is more preferred, and 5 to 30 mol% is even more preferred.

[Repeating unit (a4) having a phenolic hydroxyl group]
The resin (A) may have a repeating unit (a4) having a phenolic hydroxyl group.
Since the resin (A) contains the repeating unit (a4), the resin (A) is more excellent in dissolution rate during alkali development and is also excellent in etching resistance.

The repeating unit having a phenolic hydroxyl group is not particularly limited, and examples thereof include a hydroxystyrene repeating unit or a hydroxystyrene (meth)acrylate repeating unit. The repeating unit having a phenolic hydroxyl group is preferably a repeating unit represented by the following general formula (I).

In the formula,
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. However, R ₄₂ may combine with Ar ₄ to form a ring, in which case R ₄₂ represents a single bond or an alkylene group.
X ₄ represents a single bond, —COO—, or —CONR ₆₄ —, and R ₆₄ represents a hydrogen atom or an alkyl group.
L ₄ represents a single bond or a divalent linking group.
Ar ₄ represents an (n+1)-valent aromatic hydrocarbon group, and represents an (n+2)-valent aromatic hydrocarbon group when it is bonded to R ₄₂ to form a ring.
n represents an integer of 1 to 5.
For the purpose of making the repeating unit represented by the general formula (I) highly polar, it is also preferable that n is an integer of 2 or more, or X ₄ is —COO— or —CONR ₆₄ —.

Examples of the alkyl group represented by R ₄₁ , R ₄₂ , and R ₄₃ in the general formula (I) include a methyl group which may have a substituent, an ethyl group, a propyl group, an isopropyl group, an n-butyl group, An alkyl group having 20 or less carbon atoms such as a sec-butyl group, a hexyl group, a 2-ethylhexyl group, an octyl group, and a dodecyl group is preferable, an alkyl group having 8 or less carbon atoms is more preferable, and an alkyl group having 3 or less carbon atoms is preferable. More preferable.

The cycloalkyl group represented by R ₄₁ , R ₄₂ , and R ₄₃ in formula (I) may be monocyclic or polycyclic. A monocyclic cycloalkyl group having 3 to 8 carbon atoms such as a cyclopropyl group, a cyclopentyl group, and a cyclohexyl group which may have a substituent is preferable.
Examples of the halogen atom represented by R ₄₁ , R ₄₂ , and R ₄₃ in formula (I) include a fluorine atom, a chlorine atom, a bromine atom, and an iodine atom, and a fluorine atom is preferable.
The alkyl group contained in the alkoxycarbonyl group represented by R ₄₁ , R ₄₂ , and R ₄₃ in the general formula (I) is preferably the same as the alkyl group in R ₄₁ , R ₄₂ , and R ₄₃ above.

Examples of preferred substituents in the above groups include, for example, alkyl groups, cycloalkyl groups, aryl groups, amino groups, amide groups, ureido groups, urethane groups, hydroxyl groups, carboxyl groups, halogen atoms, alkoxy groups, thioether groups, and acyl groups. Group, an acyloxy group, an alkoxycarbonyl group, a cyano group, a nitro group and the like, and the substituent preferably has 8 or less carbon atoms.

Ar ₄ represents an (n+1)-valent aromatic hydrocarbon group. The divalent aromatic hydrocarbon group in the case where n is 1 may have a substituent, and examples thereof include an arylene having 6 to 18 carbon atoms such as a phenylene group, a tolylene group, a naphthylene group, and an anthracenylene group. Groups or aromatic hydrocarbon groups containing heterocycles such as thiophene, furan, pyrrole, benzothiophene, benzofuran, benzopyrrole, triazine, imidazole, benzimidazole, triazole, thiadiazole, and thiazole are preferred.

Specific examples of the (n+1)-valent aromatic hydrocarbon group in the case where n is an integer of 2 or more include (n-1) arbitrary aromatic groups from the above-mentioned specific examples of the divalent aromatic hydrocarbon group. A group obtained by removing a hydrogen atom can be preferably mentioned.
The (n+1)-valent aromatic hydrocarbon group may further have a substituent.

Examples of the substituent that the above-described alkyl group, cycloalkyl group, alkoxycarbonyl group and (n+1)-valent aromatic hydrocarbon group may have include, for example, R ₄₁ , R ₄₂ and R ₄₃ in the general formula (I). Examples thereof include an alkyl group mentioned above; an alkoxy group such as a methoxy group, an ethoxy group, a hydroxyethoxy group, a propoxy group, a hydroxypropoxy group, and a butoxy group; an aryl group such as a phenyl group;
_-CONR 64 represented by X ₄ - _{(R 64} represents a hydrogen atom or an alkyl group) The alkyl group for _{R 64} in, which may have a substituent, a methyl group, an ethyl group, a propyl group Alkyl groups having 20 or less carbon atoms, such as isopropyl group, n-butyl group, sec-butyl group, hexyl group, 2-ethylhexyl group, octyl group, and dodecyl group are preferable, and alkyl groups having 8 or less carbon atoms are more preferable. ..
As X ₄ , a single bond, —COO—, or —CONH— is preferable, and a single bond or —COO— is more preferable.

The divalent linking group as L ₄ is preferably an alkylene group, and as the alkylene group, a methylene group, an ethylene group, a propylene group, a butylene group, a hexylene group, which may have a substituent, And an alkylene group having 1 to 8 carbon atoms such as an octylene group are preferred.
As Ar ₄ , an aromatic hydrocarbon group having 6 to 18 carbon atoms which may have a substituent is preferable, and a benzene ring group, a naphthalene ring group or a biphenylene ring group is more preferable. Among them, the repeating unit represented by the general formula (I) is preferably a repeating unit derived from hydroxystyrene. That is, Ar ₄ is preferably a benzene ring group.

Specific examples of the repeating unit having a phenolic hydroxyl group are shown below, but the present invention is not limited thereto. In the formula, a represents 1 or 2.

The resin (A) may have one type of repeating unit (a4) alone, or may have two or more types in combination.
In the resin (A), the content of the repeating unit (a4) is preferably 40 mol% or more, more preferably 50 mol% or more, still more preferably 60 mol% or more, based on all the repeating units in the resin (A). preferable. Further, the content of the repeating unit (a4) is preferably 85 mol% or less, and more preferably 80 mol% or less, based on all the repeating units in the resin (A).

The resin (A) controls the dry etching resistance, standard developer suitability, substrate adhesion, resist profile, and general necessary properties of the resist such as resolving power, heat resistance, and sensitivity in addition to the above structural units. It is possible to have various building blocks for the purpose. Examples of such a structural unit include structural units corresponding to other monomers, but are not limited thereto.

The other monomer has, for example, one addition-polymerizable unsaturated bond selected from acrylic acid esters, methacrylic acid esters, acrylamides, methacrylamides, allyl compounds, vinyl ethers, and vinyl esters. A compound etc. can be mentioned.
In addition, any addition-polymerizable unsaturated compound that is copolymerizable with the monomers corresponding to the above-mentioned various constitutional units may be copolymerized.
In the resin (A), the content molar ratio of each structural unit is appropriately set in order to adjust various performances.

When the actinic ray-sensitive or radiation-sensitive resin composition according to the present invention is for exposure to fluorine-argon (ArF) laser, the resin (A) is substantially an aromatic group from the viewpoint of ArF light transmission. It is preferable not to have. More specifically, in all the constituent units of the resin (A), the constituent unit having an aromatic group is preferably 5 mol% or less, more preferably 3 mol% or less, and ideally Is more preferably 0 mol%, that is, does not have a constitutional unit having an aromatic group. The resin (A) preferably has a monocyclic or polycyclic alicyclic hydrocarbon structure.

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

When the actinic ray-sensitive or radiation-sensitive resin composition according to the present invention is for krypton fluoride (KrF) exposure, electron beam (EB) exposure or extreme ultraviolet (EUV) exposure, the resin (A) is It is preferable to include a constitutional unit having an aromatic hydrocarbon group. It is more preferable that the resin (A) contains a structural unit having a phenolic hydroxyl group.
Examples of the structural unit having a phenolic hydroxyl group include the repeating unit (a4) described above.
When the actinic ray-sensitive or radiation-sensitive resin composition according to the present invention is for KrF exposure, EB exposure or EUV exposure, the resin (A) has a hydrogen atom of a phenolic hydroxyl group decomposed by the action of an acid. It is preferable to have a structure protected by a group capable of leaving (leaving group).
The content of the structural unit having an aromatic hydrocarbon group contained in the resin (A) is preferably 30 mol% to 100 mol%, and more preferably 40 mol% to 100 mol, based on all the structural units in the resin (A). % Is more preferable, and 50 mol% to 100 mol% is further preferable.

The weight average molecular weight of the resin (A) is preferably 1,000 to 200,000, more preferably 2,000 to 20,000, further preferably 3,000 to 15,000, and 3,000 to 11,000. Particularly preferred.
The dispersity (Mw/Mn) is preferably 1.0 to 3.0, more preferably 1.0 to 2.6, further preferably 1.0 to 2.0, and 1.1 to 2. 0 is particularly preferred.

Specific examples of the resin (A) include, but are not limited to, the resins A-1 to A-13 used in the examples.

The resin (A) may be used alone or in combination of two or more.
The content of the resin (A) is preferably 20% by mass or more, more preferably 40% by mass or more, and 60% by mass or more based on the total solid content of the actinic ray-sensitive or radiation-sensitive resin composition according to the present invention. Is more preferable, and 80% by mass or more is particularly preferable. The upper limit is not particularly limited, but is preferably 99.5% by mass or less, more preferably 99% by mass or less, and further preferably 97% by mass or less.

[Alkali-soluble resin having phenolic hydroxyl group]
When the actinic ray-sensitive or radiation-sensitive resin composition according to the present invention contains a crosslinking agent (G) described below, the actinic ray-sensitive or radiation-sensitive resin composition according to the present invention has a phenolic hydroxyl group. It is preferable to contain an alkali-soluble resin (hereinafter, also referred to as “resin (C)”). The resin (C) preferably has a structural unit having a phenolic hydroxyl group.
In this case, typically, a negative pattern is preferably formed.
The cross-linking agent (G) may be supported on the resin (C).
Among the resins (C), those corresponding to a resin whose polarity increases by the action of an acid are treated as a resin whose polarity increases by the action of an acid. In that case, the actinic ray-sensitive or radiation-sensitive resin composition according to the present invention may contain, as the resin (C), a resin whose polarity is increased by the action of an acid, and the polarity is increased by the action of an acid. It is also possible to include at least a resin (C) other than the above resin and a resin whose polarity increases due to the action of an acid.
The resin (C) may contain the above-mentioned acid-decomposable group.
The structural unit having a phenolic hydroxyl group contained in the resin (C) is not particularly limited, but is preferably the repeating unit (a4).

The resin (C) may be used alone or in combination of two or more.
The content of the resin (C) in the total solid content of the actinic ray-sensitive or radiation-sensitive resin composition according to the present invention is preferably 30% by mass or more, and more preferably 40% by mass or more. Is more preferably 50% by mass or more. The upper limit is not particularly limited, but is preferably 99% by mass or less, more preferably 90% by mass or less, and further preferably 85% by mass or less.
As the resin (C), the resins disclosed in paragraphs 0142 to 0347 of US Patent Application Publication No. 016/0282720 can be preferably used.

[Hydrophobic resin]
The actinic ray-sensitive or radiation-sensitive resin composition according to the present invention also preferably contains a hydrophobic resin (also referred to as “hydrophobic resin (E)”).
The actinic ray-sensitive or radiation-sensitive resin composition according to the present invention contains at least a hydrophobic resin (E) other than a resin whose polarity increases by the action of an acid, and a resin whose polarity increases by the action of an acid. Is preferred.
Since the actinic ray-sensitive or radiation-sensitive resin composition according to the present invention contains the hydrophobic resin (E), the static/dynamic contact angle on the surface of the actinic ray-sensitive or radiation-sensitive film can be improved. Can be controlled. This makes it possible to improve the developing characteristics, suppress outgassing, improve the immersion liquid following ability in the immersion exposure, and reduce the immersion defects.
The hydrophobic resin (E) is preferably designed so as to be unevenly distributed on the surface of the resist film, but unlike a surfactant, it does not necessarily have to have a hydrophilic group in the molecule, and a polar/nonpolar substance is not necessary. It may not contribute to uniform mixing.
In addition, in the present invention, the resin having a fluorine atom is treated as a hydrophobic resin and a fluorine-containing resin described later. Further, it is preferable that the resin having the structural unit having an acid-decomposable group does not have a fluorine atom.

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

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

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

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

The content of the structural unit having a group (y), which is decomposed by the action of the alkaline developer to increase the solubility in the alkaline developer, is 1 to 100 mol% based on all the structural units in the hydrophobic resin (E). Is preferred, 3 to 98 mol% is more preferred, and 5 to 95 mol% is even more preferred.

The constitutional unit having a group (z) which is decomposed by the action of an acid in the hydrophobic resin (E) is the same as the constitutional unit having an acid decomposable group mentioned in the resin (A). The constituent unit having a group (z) that decomposes by the action of an acid may have at least one of a fluorine atom and a silicon atom. The content of the structural unit having a group (z) that decomposes by the action of an acid is preferably 1 mol% to 80 mol%, and preferably 10 mol% to 80 mol% with respect to all the structural units in the resin (E). More preferably, 20 mol% to 60 mol% is still more preferable.

The hydrophobic resin (E) may further have a constitutional unit different from the constitutional unit described above.

The constituent unit containing a fluorine atom is preferably 10 mol% to 100 mol%, more preferably 30 mol% to 100 mol%, based on all the constituent units contained in the hydrophobic resin (E). In addition, the constituent unit containing a silicon atom is preferably 10 mol% to 100 mol% and more preferably 20 mol% to 100 mol% with respect to all the constituent units contained in the hydrophobic resin (E).

On the other hand, in particular, when the hydrophobic resin (E) has a CH ₃ partial structure in the side chain portion, it is also preferable that the hydrophobic resin (E) contains substantially no fluorine atom or silicon atom. Further, it is preferable that the hydrophobic resin (E) is substantially constituted only by constitutional units constituted only by atoms selected from carbon atom, oxygen atom, hydrogen atom, nitrogen atom and sulfur atom.

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

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

As the hydrophobic resin (E), known resins can be used alone or as a mixture thereof, appropriately selected and used. For example, the known resins disclosed in paragraphs 0451 to 0704 of U.S. Patent Application Publication No. 2015/0168830 and paragraphs 0340 to 0356 of U.S. Patent Application Publication No. 2016/0274458 are used as the hydrophobic resin (E). It can be used preferably. In addition, the structural units disclosed in paragraphs 0177 to 0258 of US Patent Application Publication No. 2016/0237190 are also preferable as the structural units constituting the hydrophobic resin (E).

-Fluorine-containing resin-
The hydrophobic resin (E) is preferably a resin containing a fluorine atom (also referred to as “fluorine-containing resin”).
When the hydrophobic resin (E) contains a fluorine atom, it may be a resin having a fluorine atom-containing alkyl group, a fluorine atom-containing cycloalkyl group, or a fluorine atom-containing aryl group as the fluorine atom-containing partial structure. preferable.

The alkyl group having a fluorine atom is a linear or branched alkyl group in which at least one hydrogen atom is substituted with a fluorine atom, and preferably has 1 to 10 carbon atoms, and more preferably 1 to 4 carbon atoms.
The cycloalkyl group having a fluorine atom is a monocyclic or polycyclic cycloalkyl group in which at least one hydrogen atom is substituted with a fluorine atom.
Examples of the aryl group having a fluorine atom include a phenyl group and an aryl group such as a naphthyl group in which at least one hydrogen atom is substituted with a fluorine atom.

As the alkyl group having a fluorine atom, the cycloalkyl group having a fluorine atom, and the aryl group having a fluorine atom, groups represented by formulas F2 to F4 are preferable.

In formulas F2 to F4,
R ⁵⁷ to R ⁶⁸ each independently represent a hydrogen atom, a fluorine atom or an alkyl group (linear or branched). However, at least one of R ⁵⁷ to R ⁶¹ , at least one of R ⁶² to R ⁶⁴ , and at least one of R ⁶⁵ to R ⁶⁸ are each independently a fluorine atom or at least one hydrogen atom is a fluorine atom. Represents a substituted alkyl group.
It is preferable that all of R ⁵⁷ to R ⁶¹ and R ⁶⁵ to R ⁶⁷ are fluorine atoms. R ⁶² , R ⁶³ and R ⁶⁸ are preferably an alkyl group having at least one hydrogen atom substituted with a fluorine atom (preferably having a carbon number of 1 to 4), and a perfluoroalkyl group having a carbon number of 1 to 4 More preferably. R ⁶² and R ⁶³ may combine with each other to form a ring.

Among them, the fluorine-containing resin preferably has alkali decomposability because the effect of the present invention is more excellent.
Fluorine-containing resin having alkali decomposability means that 100 mg of fluorine-containing resin is added to a mixed solution of 2 mL of pH 10 buffer solution and 8 mL of THF, and allowed to stand at 40° C. and decomposed in the fluorine-containing resin after 10 minutes. It means that 30 mol% or more of the total amount of the functional groups is hydrolyzed. The decomposition rate can be calculated from the ratio of the raw material and the decomposed product by NMR analysis.

The fluorine-containing resin is represented by the formula X from the viewpoint of tolerance of depth of focus, pattern linearity, improvement of development characteristics, suppression of outgas, improvement of immersion liquid followability in immersion exposure, and reduction of immersion defects. It is preferable to have a structural unit that
In addition, the actinic ray-sensitive or radiation-sensitive resin composition according to the present invention has tolerance of depth of focus, pattern linearity, improvement of developing characteristics, suppression of outgas, improvement of immersion liquid following property in immersion exposure, and From the viewpoint of reducing liquid immersion defects, it is preferable to further include a fluorine-containing resin having a structural unit represented by Formula X.

In formula X, Z represents a halogen atom, a group represented by R ¹¹ OCH ₂ — or a group represented by R ¹² OC(═O)CH ₂ —, and R ¹¹ and R ¹² are each independently. Represents a substituent, and X represents an oxygen atom or a sulfur atom. L represents a (n+1)-valent linking group, R ¹⁰ represents a group having a group that is decomposed by the action of an alkaline aqueous solution to increase the solubility of the fluororesin in the alkaline aqueous solution, and n is a positive integer. And when n is 2 or more, a plurality of R ^10's may be the same as or different from each other.

Examples of the halogen atom for Z include a fluorine atom, a chlorine atom, a bromine atom, and an iodine atom, and a fluorine atom is preferable.
The substituents as R ¹¹ and R ¹² include, for example, an alkyl group (preferably having a carbon number of 1 to 4), a cycloalkyl group (preferably having a carbon number of 6 to 10), and an aryl group (preferably having a carbon number of 6 to 10). ) Is mentioned. Further, the substituent as R ¹¹ and R ¹² may further have a substituent, and examples of such a further substituent include an alkyl group (preferably having 1 to 4 carbon atoms), a halogen atom and a hydroxyl group. , An alkoxy group (preferably having 1 to 4 carbon atoms), and a carboxy group.
The linking group as L is preferably a divalent or trivalent linking group (in other words, n is preferably 1 or 2), and more preferably a divalent linking group (in other words, n is 1). Is preferable). The linking group as L is preferably a linking group selected from the group consisting of an aliphatic group, an aromatic group and a combination thereof.
For example, when n is 1 and the linking group as L is a divalent linking group, examples of the divalent aliphatic group include an alkylene group, an alkenylene group, an alkynylene group, and a polyalkyleneoxy group. Among them, an alkylene group or an alkenylene group is preferable, and an alkylene group is more preferable.
The divalent aliphatic group may have a chain structure or a cyclic structure, but the chain structure is preferred to the cyclic structure, and the straight chain structure is preferred to the branched chain structure. Is preferred. The divalent aliphatic group may have a substituent, and as the substituent, a halogen atom (fluorine atom, chlorine atom, bromine atom, iodine atom), a hydroxyl group, a carboxyl group, an amino group, a cyano group, Examples thereof include an aryl group, an alkoxy group, an aryloxy group, an acyl group, an alkoxycarbonyl group, an aryloxycarbonyl group, an acyloxy group, a monoalkylamino group, a dialkylamino group, an arylamino group, and a diarylamino group.
An arylene group is mentioned as a bivalent aromatic group. Of these, a phenylene group and a naphthylene group are preferable.
The divalent aromatic group may have a substituent, and examples thereof include an alkyl group in addition to the examples of the substituent in the divalent aliphatic group.
L is a divalent group obtained by removing two hydrogen atoms at arbitrary positions from the structures represented by the formulas LC1-1 to LC1-21 or the formulas SL1-1 to SL-3. May be.
When n is 2 or more, specific examples of the (n+1)-valent linking group include groups obtained by removing any (n-1) hydrogen atoms from the above-mentioned specific examples of the divalent linking group. Are listed.
Specific examples of L include the following linking groups.

Note that these linking groups may further have a substituent, as described above.

As R ¹⁰ , a group represented by the following formula W is preferable.
-YR ²⁰ type W

In the above formula W, Y represents a group that is decomposed by the action of the alkaline aqueous solution to increase the solubility in the alkaline aqueous solution. R ²⁰ represents an electron-withdrawing group.

Y is a carboxylic acid ester group (—COO— or OCO—), an acid anhydride group (—C(O)OC(O)—), an acid imide group (—NHCONH—), a carboxylic acid thioester group (—COS). -), a carbonic acid ester group (-OC(O)O-), a sulfuric acid ester group (-OSO ₂ O-), and a sulfonic acid ester group (-SO ₂ O-), and a carboxylic acid ester group is preferable. ..

As the electron-withdrawing group, a partial structure represented by the following formula EW is preferable. * In the formula EW represents a bond directly connected to the group Y in the formula W.

In formula EW,
n ^ew is the repeating number of the linking group represented by —C(R ^ew1 )(R ^ew2 )— and represents an integer of 0 or 1. When n ^ew is 0, it represents a single bond, which ^means that Y ^ew1 is directly bonded.
Y ^ew1 is a halogen atom, a cyano group, a nitro group, a halo(cyclo)alkyl group represented by —C(R ^f1 )(R ^f2 )—R ^f3 described later, a haloaryl group, an oxy group, a carbonyl group, a sulfonyl group , Sulfinyl groups, and combinations thereof. (However, when Y ^ew1 is a halogen atom, a cyano group or a nitro group, n ^ew is 1.)
R ^ew1 and R ^ew2 each independently represent an arbitrary group, for example, a hydrogen atom, an alkyl group (preferably having a carbon number of 1 to 8), a cycloalkyl group (preferably having a carbon number of 3 to 10) or an aryl group ( It preferably has 6 to 10 carbon atoms.
At least two ^{members out} of R ^ew1 , R ^ew2 and Y ^ew1 may be linked to each other to form a ring.
The "halo(cyclo)alkyl group" represents an alkyl group and a cycloalkyl group which are at least partially halogenated, and the "haloaryl group" represents an aryl group which is at least partially halogenated.

As Y ^ew1 , a halogen atom, a halo(cyclo)alkyl group represented by —C(R ^f1 )(R ^f2 )—R ^f3 , or a haloaryl group is preferable.

R ^f1 represents a halogen atom, a perhaloalkyl group, a perhalocycloalkyl group, or a perhaloaryl group, preferably a fluorine atom, a perfluoroalkyl group or a perfluorocycloalkyl group, more preferably a fluorine atom or a trifluoromethyl group. preferable.
R ^f2 and R ^f3 each independently represent a hydrogen atom, a halogen atom or an organic group, and R ^f2 and R ^f3 may be linked to each other to form a ring. Examples of the organic group include an alkyl group, a cycloalkyl group, and an alkoxy group, which may be substituted with a halogen atom (preferably a fluorine atom). R ^f2 and R ^f3 are preferably a (halo)alkyl group or a (halo)cycloalkyl group. It is more preferable that R ^f2 represents the same group as R ^f1 , or that R ^f2 is linked to R ^f3 to form a ring.
^{Examples of} the ring formed by connecting R ^f2 and R ^f3 include a (halo)cycloalkyl ring.

The (halo)alkyl group in R ^f1 to R ^f3 may be linear or branched, and the linear (halo)alkyl group preferably has 1 to 30 carbon atoms, and more preferably 1 to 20 carbon atoms. preferable.

The (halo)cycloalkyl group in R ^f1 to R ^f3 or in the ring formed by connecting R ^f2 and R ^f3 may be monocyclic or polycyclic. In the case of polycyclic type, the (halo)cycloalkyl group may be bridged. That is, in this case, the (halo)cycloalkyl group may have a bridge structure.
Examples of these (halo)cycloalkyl groups include groups represented by the following formulas, and halogenated groups thereof. In addition, a part of carbon atoms in the cycloalkyl group may be substituted with a hetero atom such as an oxygen atom.

The (halo)cycloalkyl group in R ^f2 and R ^f3 or in the ring formed by linking R ^f2 and R ^f3 is fluorocyclo represented by —C _(n) F _(2n-2) H. Alkyl groups are preferred. Here, the carbon number n is not particularly limited, but is preferably 5 to 13, and more preferably 6.

^Examples of the (per)haloaryl group in Y ^ew1 or R ^f1 include a perfluoroaryl group represented by —C _(n) F _(n-1) . Here, the carbon number n is not particularly limited, but is preferably 5 to 13, and more preferably 6.

The ^ring which at least two ^{members out} of R ^ew1 , R ^ew2 and Y ^ew1 may be linked to each other to form, is preferably a cycloalkyl group or a heterocyclic group.

Each group and each ring constituting the partial structure represented by the above formula EW may further have a substituent.

In the above formula W, R ²⁰ is preferably an alkyl group substituted with one or more selected from the group consisting of a halogen atom, a cyano group and a nitro group, and an alkyl group substituted with a halogen atom (haloalkyl group ) Is more preferable, and a fluoroalkyl group is still more preferable. The alkyl group substituted with one or more selected from the group consisting of a halogen atom, a cyano group and a nitro group preferably has 1 to 10 carbon atoms, and more preferably 1 to 5 carbon atoms.
More specifically, R ²⁰ is an atom represented by —C(R′ ¹ )(R′ ^f1 )(R′ ^f2 ), or —C(R′ ¹ )(R′ ² )(R′ ^f1 ). It is preferably a group. R ^'1 and R' ² are independently a hydrogen atom, or not substituted with an electron-withdrawing group (preferably unsubstituted) alkyl group. ^R'f1 and ^R'f2 each independently represent a halogen atom, a cyano group, a nitro group, or a perfluoroalkyl group.
The alkyl group as R′ ¹ and R′ ² may be linear or branched and preferably has 1 to 6 carbon atoms.
The perfluoroalkyl group represented by R′ ^f1 and R′ ^f2 may be linear or branched and preferably has 1 to 6 carbon atoms.
Specific preferred examples of R ²⁰ include -CF ₃ , -C ₂ F ₅ , -C ₃ F ₇ , -C ₄ F ₉ , -CF(CF ₃ ) ₂ , -CF(CF ₃ )C ₂ F ₅ , -CF ₂ CF(CF ₃ ) ₂ , -C(CF ₃ ) ₃ , -C ₅ F ₁₁ , -C ₆ F ₁₃ , -C ₇ F ₁₅ , -C ₈ F ₁₇ , -CH ₂ CF ₃ , -CH. _{_{_{_{2 C 2 F 5, -CH 2}}}} C 3 F 7, -CH (CF 3) 2, -CH (CF 3) C 2 F 5, -CH 2 CF (CF 3) 2, and, are _-CH 2 CN Can be mentioned. Among them, -CF ₃ , -C ₂ F ₅ , -C ₃ F ₇ , -C ₄ F ₉ , -CH ₂ CF ₃ , -CH ₂ C ₂ F ₅ , -CH ₂ C ₃ F ₇ , -CH(CF ₃ ) ₂ or —CH ₂ CN is preferable, and —CH ₂ CF ₃ , —CH ₂ C ₂ F ₅ , —CH ₂ C ₃ F ₇ , —CH(CF ₃ ) ₂ or —CH ₂ CN is More preferred is —CH ₂ C ₂ F ₅ , —CH(CF ₃ ) ₂ or —CH ₂ CN, and —CH ₂ C ₂ F ₅ or —CH(CF ₃ ) ₂ is particularly preferred.

As the constitutional unit represented by the formula X, a constitutional unit represented by the following formula X-1 or formula X-2 is preferable, and a constitutional unit represented by the formula X-1 is more preferable.

In formula X-1, R ²⁰ represents an electron-withdrawing group, L ² represents a divalent linking group, X ² represents an oxygen atom or a sulfur atom, and Z ² represents a halogen atom.
In formula X-2, R ²⁰ represents an electron-withdrawing group, L ³ represents a divalent linking group, X ³ represents an oxygen atom or a sulfur atom, and Z ³ represents a halogen atom.

Specific examples and preferred examples of the divalent linking group as L ² and L ³ are the same as those described for L as the divalent linking group in formula X above.
The electron withdrawing group as R ² and R ³ is preferably a partial structure represented by the above formula EW, and specific examples and preferable examples are also as described above, but a halo(cyclo)alkyl group is more preferable.

In the above formula X-1, L ² and R ² do not bond to each other to form a ring, and in the above formula X-2, L ³ and R ³ bond to each other to form a ring. There is no such thing.

As X ² and X ³ , an oxygen atom is preferable.
As Z ² and Z ³ , a fluorine atom or a chlorine atom is preferable, and a fluorine atom is more preferable.

Further, as the constitutional unit represented by the formula X, the constitutional unit represented by the formula X-3 is also preferable.

In formula X-3, R ²⁰ represents an electron-withdrawing group, R ²¹ represents a hydrogen atom, an alkyl group, or an aryl group, L ⁴ represents a divalent linking group, and X ⁴ represents It represents an oxygen atom or a sulfur atom, and m represents 0 or 1.

Specific examples and preferred examples of the divalent linking group as L ⁴ are the same as those described in L as the divalent linking group of formula X.
The electron-withdrawing group as R ⁴ is preferably a partial structure represented by the above formula EW, and specific examples and preferable examples are also as described above, but a halo(cyclo)alkyl group is more preferable.

In the above formula X-3, L ⁴ and R ⁴ do not bond to each other to form a ring.
As X ⁴ , an oxygen atom is preferable.

As the constitutional unit represented by the formula X, a constitutional unit represented by the formula Y-1 or a constitutional unit represented by the formula Y-2 is also preferable.

In formula Y-1 and formula Y-2, Z represents a halogen atom, a group represented by R ¹¹ OCH ₂ —, or a group represented by R ¹² OC(═O)CH ₂ —, and R ¹¹ And R ¹² each independently represent a substituent, and R ²⁰ represents an electron-withdrawing group.

The electron withdrawing group as R ²⁰ is preferably a partial structure represented by the above formula EW, and specific examples and preferable examples are also as described above, but a halo(cyclo)alkyl group is more preferable.

Specific examples and preferable examples of the halogen atom, the group represented by R ¹¹ OCH ₂ —, and the group represented by R ¹² OC(═O)CH ₂ — as Z are the same as those described in the above formula 1. Is the same as.

The content of the structural unit represented by the formula X is preferably 10 mol% to 100 mol%, more preferably 20 mol% to 100 mol%, and further preferably 30 mol% to 100 mol, based on all the structural units of the fluororesin. % Is more preferable.

Preferable examples of the constituent units constituting the hydrophobic resin (E) are shown below.
Preferred examples of the hydrophobic resin (E) include, but are not limited to, resins in which these constituent units are arbitrarily combined or resins F-1 to F-3 used in the examples.

The hydrophobic resin (E) may be used alone or in combination of two or more.
It is preferable to mix and use two or more kinds of hydrophobic resins (E) having different surface energies, from the viewpoint of achieving both the immersion liquid following property in the immersion exposure and the developing characteristics.
The content of the hydrophobic resin (E) in the composition is preferably 0.01% by mass to 10% by mass, based on the total solid content of the actinic ray-sensitive or radiation-sensitive resin composition according to the present invention, and 0 More preferably, it is 0.05% by mass to 8% by mass.

<Photo acid generator>
The composition according to the present invention preferably contains a photoacid generator (hereinafter, also referred to as “photoacid generator (B)”).
The photo-acid generator is a compound that generates an acid upon irradiation with actinic rays or radiation.
As the photoacid generator, a compound that generates an organic acid upon irradiation with actinic rays or radiation is preferable. Examples thereof include sulfonium salt compounds, iodonium salt compounds, diazonium salt compounds, phosphonium salt compounds, imide sulfonate compounds, oxime sulfonate compounds, diazodisulfone compounds, disulfone compounds, and o-nitrobenzyl sulfonate compounds.

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

[Compounds represented by Formulas ZI, ZII and ZIII]
Suitable examples of the photoacid generator (B) include compounds represented by the following formulas ZI, ZII and ZIII.

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

[Cation in Compound Represented by Formula ZI]
Suitable examples of the cation in formula ZI include the corresponding groups in compounds (ZI-1), (ZI-2), (ZI-3) and (ZI-4) described later.
The photoacid generator (C) may be a compound having a plurality of structures represented by formula ZI. For example, at least one of ^R 201 ^{~ R 203} of the compound represented by the formula ZI, through at least one and is a single bond or a linking group ^R 201 ^{~ R 203} of another compound represented by formula ZI It may be a compound having a bonded structure.

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

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

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

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

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

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

In formula ZI-3, R ^1c to R ^5c are each independently a hydrogen atom, an alkyl group, a cycloalkyl group, an aryl group, an alkoxy group, an aryloxy group, an alkoxycarbonyl group, an alkylcarbonyloxy group, a cycloalkylcarbonyloxy group. , A halogen atom, a hydroxyl group, a nitro group, an alkylthio group or an arylthio group, R ^6c and R ^7c each independently represent a hydrogen atom, an alkyl group, a cycloalkyl group, a halogen atom, a cyano group or an aryl group, and R ^x And R ^y each independently represents an alkyl group, a cycloalkyl group, a 2-oxoalkyl group, a 2-oxocycloalkyl group, an alkoxycarbonylalkyl group, an allyl group or a vinyl group.

Any two or more of R ^1c to R ^5c , R ^5c and R ^6c , R ^6c and R ^7c , R ^5c and R ^x , and R ^x and R ^y may be bonded to each other to form a ring structure. Of course, each of the ring structures may independently contain an oxygen atom, a sulfur atom, a ketone group, an ester bond, or an amide bond.
Examples of the ring structure include an aromatic or non-aromatic hydrocarbon ring, an aromatic or non-aromatic heterocycle, and a polycyclic fused ring formed by combining two or more of these rings. Examples of the ring structure include a 3-membered ring to a 10-membered ring, preferably a 4-membered ring to an 8-membered ring, and more preferably a 5-membered ring or a 6-membered ring.

^{Examples of} the group formed by combining any two or more of R ^1c to R ^5c , R ^6c and R ^7c , and R ^x and R ^y include a butylene group and a pentylene group.
The group formed by combining R ^5c and R ^6c and R ^5c and R ^x is preferably a single bond or an alkylene group. Examples of the alkylene group include a methylene group and an ethylene group.
Zc ^- represents an anion.

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

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

In formula ZI-4, the alkyl group of R ¹³ , R ¹⁴ and R ¹⁵ is linear or branched, and preferably has 1 to 10 carbon atoms, and includes a methyl group, an ethyl group, an n-butyl group, Alternatively, a t-butyl group or the like is more preferable.

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

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

[Anion in Compounds Represented by Formulas ZI to ZIII]
Z in formula ZI ^-, Z in formula ZII ^-, Zc in Formula ZI-3 ^-, and Z in Formula ZI-4 ^- as is preferably the anion of the following formula An-1.

In formula An-1, pf represents an integer of 0 to 10, qf represents an integer of 0 to 10, rf represents an integer of 1 to 3, Xf represents each independently a fluorine atom or at least one of When rf represents an alkyl group substituted with a fluorine atom and rf is an integer of 2 or more, a plurality of —C(Xf) ₂ — may be the same or different, and R ⁴ and R ⁵ are each independently , A hydrogen atom, a fluorine atom, an alkyl group, or an alkyl group substituted with at least one fluorine atom, and when pf is an integer of 2 or more, a plurality of —CR ^4f R ^5f — are the same or different. L ^f represents a divalent linking group, and when qf is an integer of 2 or more, a plurality of L ^f may be the same or different, and W is an organic compound containing a cyclic structure. Represents a group.

Xf represents a fluorine atom or an alkyl group substituted with at least one fluorine atom. The alkyl group preferably has 1 to 10 carbon atoms, more preferably 1 to 4 carbon atoms. The alkyl group substituted with at least one fluorine atom is preferably a perfluoroalkyl group.
Xf is preferably a fluorine atom or a perfluoroalkyl group having 1 to 4 carbon atoms. More preferably, Xf is a fluorine atom or CF ₃ . Particularly, it is preferable that both Xf's are fluorine atoms.

R ^4f and R ^5f 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 ^4f and R ^5f are present, they may be the same or different.
The alkyl group as R ^4f and R ^5f may have a substituent and preferably has 1 to 4 carbon atoms. R ^4f and R ^5f are preferably hydrogen atoms.
Specific examples and preferred embodiments of the alkyl group substituted with at least one fluorine atom are the same as the specific examples and preferred embodiments of Xf in the formula An-1.

L ^f represents a divalent linking group, and when a plurality of L ^{f s} are present, L ^f may be the same or different.
Examples of the divalent linking group include -COO-(-C(=O)-O-), -OCO-, -CONH-, -NHCO-, -CO-, -O-, -S-, -. SO—, —SO ₂ —, alkylene group (preferably having 1 to 6 carbon atoms), cycloalkylene group (preferably having 3 to 15 carbon atoms), alkenylene group (preferably having 2 to 6 carbon atoms), and combinations thereof. And a divalent linking group. Among these, -COO-, -OCO-, -CONH-, -NHCO-, -CO-, -O-, -SO ₂ -, -COO-alkylene group-, -OCO-alkylene group-, -CONH- alkylene group - or -NHCO- alkylene group - are preferred, -COO -, - OCO -, - CONH -, - SO 2 -, - COO- alkylene group - or -OCO- alkylene group - is more preferable.

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

The aryl group may be monocyclic or polycyclic. Examples of this aryl group include a phenyl group, a naphthyl group, a phenanthryl group, and an anthryl group.
The heterocyclic group may be monocyclic or polycyclic. The polycyclic type can suppress the diffusion of acid more. Further, the heterocyclic group may have aromaticity or may not have aromaticity. Examples of the heterocyclic ring having aromaticity include a furan ring, a thiophene ring, a benzofuran ring, a benzothiophene ring, a dibenzofuran ring, a dibenzothiophene ring, and a pyridine ring. Examples of the heterocycle having no aromaticity include a tetrahydropyran ring, a lactone ring, a sultone ring and a decahydroisoquinoline ring. Examples of the lactone ring and the sultone ring include the lactone structure and the sultone structure exemplified in the above resin. A furan ring, a thiophene ring, a pyridine ring, or a decahydroisoquinoline ring is particularly preferable as the heterocycle in the heterocyclic group.

The above cyclic organic group may have a substituent. This substituent may be, for example, an alkyl group (which may be linear or branched and preferably has 1 to 12 carbon atoms) and a cycloalkyl group (which may be monocyclic, polycyclic or spiro ring). Well, preferably 3 to 20 carbon atoms), aryl group (preferably 6 to 14 carbon atoms), hydroxyl group, alkoxy group, ester group, amide group, urethane group, ureido group, thioether group, sulfonamide group, and sulfonic acid. An ester group may be mentioned. The carbon constituting the cyclic organic group (carbon contributing to ring formation) may be carbonyl carbon.

Examples of the anion represented by the formula An-1 include SO ₃ ^— —CF ₂ —CH ₂ —OCO—(L ^f )q′-W, SO ₃ ^— —CF ₂ —CHF—CH ₂ —OCO—(L ^f ) Q′-W, SO ₃ ^— —CF ₂ —COO—(L ^f )q′-W, SO ₃ ^— —CF ₂ —CF ₂ —CH ₂ —CH ₂ —(L ^f ) _qf —W, SO ₃ ^{_{_{- -CF 2 -CH (CF 3)}}} -OCO- (L f) q'-W can be mentioned as preferred. Here, L ^f , qf, and W are the same as those in the expression An-1. q'represents an integer of 0 to 10.

In one embodiment, Z in formula ZI ^-, Z in formula ZII ^-, Zc in Formula ZI-3 ^-, and Z in Formula ZI-4 ^- as an anion is also preferably represented by formula 4 below.

In Formula 4, X ^B1 and X ^B2 each independently represent a hydrogen atom or a monovalent organic group having no fluorine atom. X ^B1 and X ^B2 are preferably hydrogen atoms.
X ^B3 and X ^B4 each independently represent a hydrogen atom or a monovalent organic group. At least one of X ^B3 and X ^B4 is preferably a fluorine atom or a monovalent organic group having a fluorine atom, and both X ^B3 and X ^B4 are a fluorine atom or a monovalent organic group having a fluorine atom. Is more preferable. More preferably, both X ^B3 and X ^B4 are fluorine-substituted alkyl groups.
L ^f , qf, and W are the same as in Equation 3.

Z in formula ZI ^-, Z in formula ZII ^-, Zc in Formula ZI-3 ^-, and Z in Formula ZI-4 ^- as is preferably the anion of the following formula 5.

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

Z in formula ZI ^-, Z in formula ZII ^-, Zc in Formula ZI-3 ^-, and Z in Formula ZI-4 ^- may be a benzenesulfonic acid anion, it is substituted by a branched alkyl group or a cycloalkyl group The benzene sulfonate anion is preferred.

Z in formula ZI ^-, Z in formula ZII ^-, Zc in Formula ZI-3 ^-, and Z in Formula ZI-4 ^- as also preferred aromatic sulfonate anion represented by the formula SA1 below.

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

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

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

R ^B represents a hydrocarbon group.

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

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

Preferred examples of the anion Z ⁻ in formula ZI, formula ZII, Zc ⁻ in formula ZI-3, and Z ⁻ in formula ZI-4 are shown below.

Any combination of the above cations and anions can be used as a photoacid generator.
Among them, the photoacid generator is an ionic compound containing a cation and an anion, and the anion contains an ion represented by any one of the above formula An-1, the following formula An-2 and the following formula An-3. Is preferred.

In formulas An-2 and An-3, Rfa's each independently represent a monovalent organic group having a fluorine atom, and a plurality of Rfa's may be bonded to each other to form a ring.

Rfa is preferably an alkyl group substituted with at least one fluorine atom. The alkyl group preferably has 1 to 10 carbon atoms, more preferably 1 to 4 carbon atoms. The alkyl group substituted with at least one fluorine atom is preferably a perfluoroalkyl group.
Moreover, it is preferable that a plurality of Rfas are bonded to each other to form a ring.

The compounds C-1 to C-42 used in the examples are also preferable as the photoacid generator, but the photoacid generator is not limited thereto.

The photo-acid generator may be in the form of a low molecular weight compound or may be incorporated in a part of the polymer. Moreover, you may use together the form of a low molecular compound and the form incorporated in a part of polymer.
The photo-acid generator is preferably in the form of a low molecular compound.
When the photoacid generator is in the form of a low molecular weight compound, the molecular weight is preferably 3,000 or less, more preferably 2,000 or less, still more preferably 1,000 or less.
When the photo-acid generator is in the form of being incorporated in a part of the polymer, it may be incorporated in a part of the resin (A) described above, or may be incorporated in a resin different from the resin (A). ..
The photoacid generator may be used alone or in combination of two or more.
The content of the photo-acid generator in the composition (when a plurality of kinds are present, the total thereof) is preferably 0.1% by mass to 35% by mass, and 0.5% by mass, based on the total solid content of the composition. Is more preferably from 25% by mass to 25% by mass, further preferably from 2% by mass to 20% by mass, particularly preferably from 2.5% by mass to 20% by mass.
When the compound represented by the above formula ZI-3 or formula ZI-4 is contained as the photoacid generator, the content of the photoacid generator contained in the composition (when there are plural kinds, the total thereof) is 5% by mass to 35% by mass is preferable, and 7% by mass to 30% by mass is more preferable, based on the total solid content of the composition.

<Acid diffusion control agent>
The actinic ray-sensitive or radiation-sensitive resin composition according to the present invention preferably contains an acid diffusion controller (also referred to as “acid diffusion controller (D)”).
The acid diffusion control agent (D) acts as a quencher that traps the acid generated from the acid generator or the like during exposure and suppresses the reaction of the acid-decomposable resin in the unexposed portion due to the excess generated acid. .. For example, a basic compound (DA), a basic compound (DB) whose basicity decreases or disappears upon irradiation with actinic rays or radiation, an onium salt (DC) which becomes a weak acid relative to an acid generator, and a nitrogen atom. A low molecular weight compound (DD) having a group capable of leaving by the action of an acid or an onium salt compound (DE) having a nitrogen atom in the cation portion can be used as an acid diffusion controller.
Among them, the actinic ray-sensitive or radiation-sensitive resin composition according to the present invention preferably contains a nitrogen-containing compound as the acid diffusion controller from the viewpoint of the linearity of the pattern obtained after aging, and nitrogen-containing basicity. More preferably, it comprises a compound.
In the actinic ray-sensitive or radiation-sensitive resin composition according to the present invention, a known acid diffusion controlling agent can be appropriately used. For example, paragraphs 0627 to 0664 of U.S. Patent Application Publication No. 2016/0070167, paragraphs 0095 to 0187 of U.S. Patent Application Publication No. 2015/0004544, and paragraph 0403 of U.S. Patent Application Publication No. 2016/0237190. The known compounds disclosed in paragraphs 0259 to 0328 of U.S. Pat. App. Pub. No. 2016/0274458, can be suitably used as the acid diffusion controller (D).

[Basic compound (DA)]
The basic compound (DA) is preferably a compound having a structure represented by the following formulas A to E.

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

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

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

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

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

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

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

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

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

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

[Onium salt (DC) that becomes a weak acid relative to the photoacid generator]
In the actinic ray-sensitive or radiation-sensitive resin composition according to the present invention, an onium salt (DC), which is a weak acid relative to the photoacid generator, can be used as another acid diffusion controller.
When a photoacid generator and an onium salt that generates an acid that is a relatively weak acid with respect to the acid generated from the photoacid generator are mixed and used, the photoacid generator is exposed to actinic rays or radiation. When the acid generated from the compound collides with an onium salt having an unreacted weak acid anion, salt exchange causes the weak acid to be released to give an onium salt having a strong acid anion. In this process, the strong acid is exchanged with a weak acid having a lower catalytic activity, so that the acid is apparently deactivated and the acid diffusion can be controlled.

The actinic ray-sensitive or radiation-sensitive resin composition according to the present invention is selected from the group consisting of compounds represented by the formulas d1-1 to d1-3 from the viewpoint of the depth of focus tolerance and the pattern linearity. It is preferable to further include at least one compound.

In formulas d1-1 to d1-3, R ⁵¹ represents a hydrocarbon group which may have a substituent, and Z ^2c represents a hydrocarbon group which may have a substituent and has 1 to 30 carbon atoms. R ⁵² represents an organic group, Y ³ represents a linear, branched or cyclic alkylene group or arylene group, and Rf represents a carbon atom adjacent to the S atom. Represents a hydrocarbon group containing a fluorine atom, and M ⁺ each independently represents an ammonium cation, a sulfonium cation or an iodonium cation.

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

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

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

The substituent having 1 or more carbon atoms in R ¹ to R ³ is an alkyl group, a cycloalkyl group, an aryl group, an alkyloxycarbonyl group, a cycloalkyloxycarbonyl group, an aryloxycarbonyl group, an alkylaminocarbonyl group, a cycloalkylamino group. Examples thereof include a carbonyl group and an arylaminocarbonyl group. Preferably, it is an alkyl group, a cycloalkyl group, or an aryl group.

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

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

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

As R ^b , a linear or branched alkyl group, a cycloalkyl group, or an aryl group is preferable, and a linear or branched alkyl group or a cycloalkyl group is more preferable.
Examples of the ring formed by connecting two R ^b to each other include alicyclic hydrocarbons, aromatic hydrocarbons, heterocyclic hydrocarbons and derivatives thereof.
Specific structures of the group represented by formula d-1 include, but are not limited to, the structures disclosed in paragraph 0466 of US Patent Application Publication No. 2012/0135348.

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

In equation 6,
l represents an integer of 0 to 2, m represents an integer of 1 to 3, and satisfies l+m=3.
^Ra represents a hydrogen atom, an alkyl group, a cycloalkyl group, an aryl group or an aralkyl group. When l is 2, two R ^a's may be the same or different, and the two R ^a's may be linked to each other to form a heterocycle with the nitrogen atom in the formula. This heterocycle may contain a heteroatom other than the nitrogen atom in the formula.
R ^b has the same meaning as ^{R b} in the formula d-1, and preferred examples are also the same.
In Equation 6, the alkyl group as R ^a, a cycloalkyl group, an aryl group, and aralkyl group each independently an alkyl group as R ^b, cycloalkyl group, aryl group and aralkyl group, may be substituted It may be substituted with a group similar to the above-mentioned groups.

Specific examples of the alkyl group, cycloalkyl group, aryl group, and aralkyl group for R ^a (these groups may be substituted with the above groups) include the same groups as those described above for R ^b. Are listed.
Specific structures of the compound (DD) particularly preferred in the present invention include the compounds disclosed in paragraph 0475 of US Patent Application Publication No. 2012/0135348, but are not limited thereto. Absent.

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

Favorable examples of other acid diffusion control agents are shown below.

In the actinic ray-sensitive or radiation-sensitive resin composition according to the present invention, the other acid diffusion controlling agent may be used alone or in combination of two or more kinds.
The content of the acid diffusion controlling agent in the composition (when plural kinds are present, the total thereof) is preferably 0.1% by mass to 10% by mass, based on the total solid content of the composition, and 0.1% by mass. It is more preferably to 5% by mass.

<Solvent>
Hereinafter, in the solvents shown as specific examples, those corresponding to the compound represented by the general formula (1) or the general formula (2) are excluded.
The actinic ray-sensitive or radiation-sensitive resin composition according to the present invention preferably contains a solvent (also referred to as “solvent (F)”), and more preferably contains an organic solvent.
In the actinic ray-sensitive or radiation-sensitive resin composition according to the present invention, known resist solvents can be appropriately used. For example, paragraphs 0665 to 0670 of US Patent Application Publication No. 2016/0070167, paragraphs 0210 to 0235 of US Patent Application Publication No. 2015/0004544, and paragraph 0424 of US Patent Application Publication No. 2016/0237190. ˜0426, and known solvents disclosed in paragraphs 0357 to 0366 of US Patent Application Publication No. 2016/0274458 can be preferably used.
Examples of the solvent that can be used when preparing the composition include alkylene glycol monoalkyl ether carboxylate, alkylene glycol monoalkyl ether, alkyl lactate ester, alkyl alkoxypropionate, cyclic lactone (preferably having 4 to 10 carbon atoms), Examples of the organic solvent include a monoketone compound which may have a ring (preferably having 4 to 10 carbon atoms), alkylene carbonate, alkyl alkoxyacetate, and alkyl pyruvate.

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

The solid content concentration of the actinic ray-sensitive or radiation-sensitive resin composition according to the present invention is not particularly limited, but is preferably 0.5% by mass to 50% by mass, and 1.0% by mass to 45% by mass. % Is more preferable, and 1.0% by mass to 40% by mass is further preferable.
The solid content concentration is a mass percentage of the mass of other resist components excluding the solvent with respect to the total mass of the composition.

<Crosslinking agent>
The actinic ray-sensitive or radiation-sensitive resin composition according to the present invention may contain a compound that crosslinks the resin by the action of an acid (hereinafter, also referred to as a crosslinker (G)).
As the cross-linking agent (G), a known compound can be appropriately used. For example, known compounds disclosed in paragraphs 0379 to 0431 of US Patent Application Publication No. 2016/0147154 and paragraphs 0064 to 0141 of US Patent Application Publication No. 2016/0282720 are suitable as the crosslinking agent (G). Can be used for
The cross-linking agent (G) is a compound having a cross-linkable group capable of cross-linking the resin, and as the cross-linkable group, a hydroxymethyl group, an alkoxymethyl group, an acyloxymethyl group, an alkoxymethyl ether group, an oxirane ring, And an oxetane ring.
The crosslinkable group is preferably a hydroxymethyl group, an alkoxymethyl group, an oxirane ring or an oxetane ring.
The crosslinking agent (G) is preferably a compound (including a resin) having two or more crosslinking groups.
The cross-linking agent (G) is more preferably a phenol derivative having a hydroxymethyl group or an alkoxymethyl group, a urea compound (a compound having a urea structure) or a melamine compound (a compound having a melamine structure).
The crosslinking agent may be used alone or in combination of two or more.
The content of the cross-linking agent (G) is preferably 1% by mass to 50% by mass, more preferably 3% by mass to 40% by mass, further preferably 5% by mass to 30% by mass based on the total solid content of the composition. preferable.

<Surfactant>
The actinic ray-sensitive or radiation-sensitive resin composition according to the present invention may or may not contain a surfactant (also referred to as “surfactant (H)”). In the case of containing a surfactant, a fluorine-based or silicone-based surfactant (specifically, a fluorine-based surfactant, a silicone-based surfactant, or a surfactant having both a fluorine atom and a silicon atom) It is preferable to contain at least one.

Since the actinic ray-sensitive or radiation-sensitive resin composition according to the present invention contains a surfactant, when an exposure light source having a wavelength of 250 nm or less, particularly 220 nm or less is used, good sensitivity and resolution are achieved, and adhesion is improved. It is possible to obtain a resist pattern with less property and development defects.
Examples of the fluorine-based or silicone-based surfactants include the surfactants described in paragraph 0276 of US Patent Application Publication No. 2008/0248425.
Further, surfactants other than the fluorine-based or silicone-based surfactants described in paragraph 0280 of US Patent Application Publication No. 2008/0248425 can also be used.

These surfactants may be used alone or in combination of two or more.
When the actinic ray-sensitive or radiation-sensitive resin composition according to the present invention contains a surfactant, the content of the surfactant is 0.0001% by mass to 2% by mass based on the total solid content of the composition. % Is preferable, and 0.0005% by mass to 1% by mass is more preferable.
On the other hand, when the content of the surfactant is 0.0001% by mass or more based on the total solid content of the composition, the uneven distribution of the surface of the hydrophobic resin is increased. As a result, the surface of the actinic ray-sensitive or radiation-sensitive film can be made more hydrophobic, and the water following property during immersion exposure is improved.

<Other additives>
The actinic ray-sensitive or radiation-sensitive resin composition according to the present invention may further contain other known additives.
Examples of other additives include acid proliferating agents, dyes, plasticizers, photosensitizers, light absorbers, alkali-soluble resins, dissolution inhibitors, and dissolution accelerators.

The actinic ray-sensitive or radiation-sensitive resin composition according to the present invention is obtained by dissolving the above components in a predetermined organic solvent, preferably the mixed solvent, and filtering the resulting solution, and then, for example, a predetermined support (substrate). ) It is preferable to apply it on the above.
The pore size (pore diameter) of the filter used for filter filtration is preferably 0.2 μm or less, more preferably 0.05 μm or less, still more preferably 0.03 μm or less.
Further, when the actinic ray-sensitive or radiation-sensitive resin composition has a high solid content concentration (for example, 25% by mass or more), the pore size of the filter used for filter filtration is preferably 3 μm or less, and more preferably 0.5 μm or less. It is preferably 0.3 μm or less, and more preferably 0.3 μm or less.
The filter is preferably made of polytetrafluoroethylene, polyethylene, or nylon. In the filter filtration, for example, as disclosed in JP-A-2002-62667, cyclic filtration may be performed, or a plurality of types of filters may be connected in series or in parallel to perform filtration. Also, the composition may be filtered multiple times. Further, the composition may be subjected to deaeration treatment or the like before and after filtration with a filter.

The thickness of the resist film comprising the actinic ray-sensitive or radiation-sensitive resin composition according to the present invention is not particularly limited, but from the viewpoint of improving resolution, 90 nm or less is preferable, and 85 nm or less is more preferable. Such a film thickness can be obtained by setting the solid content concentration in the composition to an appropriate range to give an appropriate viscosity and improving the coating property or film forming property.

<Use>
The actinic ray-sensitive or radiation-sensitive resin composition according to the present invention is an actinic ray-sensitive or radiation-sensitive resin composition that reacts upon irradiation with light to change its properties. More specifically, the actinic ray-sensitive or radiation-sensitive resin composition according to the present invention is applied to a semiconductor manufacturing process such as IC (Integrated Circuit), a circuit board such as a liquid crystal or a thermal head, and an imprint mold structure. The present invention relates to an actinic ray-sensitive or radiation-sensitive resin composition used for production, other photofabrication process, or production of a lithographic printing plate or an acid-curable composition. The resist pattern formed by the actinic ray-sensitive or radiation-sensitive resin composition according to the present invention includes an etching step, an ion implantation step, a bump electrode forming step, a rewiring forming step, and a MEMS (Micro Electro Mechanical Systems). Etc. can be used.

(Resist film)
The resist film according to the present invention is a resist film formed from the actinic ray-sensitive or radiation-sensitive resin composition according to the present invention. The resist film according to the present invention is a solidified product of the actinic ray-sensitive or radiation-sensitive resin composition according to the present invention.
The solidified product in the present invention may be one obtained by removing at least a part of the solvent from the actinic ray-sensitive or radiation-sensitive resin composition according to the present invention.
Specifically, the resist film according to the present invention can be obtained, for example, by applying the actinic ray-sensitive or radiation-sensitive resin composition according to the present invention on a support such as a substrate and then drying.
The drying means removing at least a part of the solvent contained in the actinic ray-sensitive or radiation-sensitive resin composition according to the present invention.
The drying method is not particularly limited, and known methods can be used, and examples include drying by heating (for example, 70° C. to 130° C., 30 seconds to 300 seconds).
The heating method is not particularly limited, and known heating means can be used, and examples thereof include a heater, an oven, a hot plate, an infrared lamp, and an infrared laser.

The components contained in the resist film according to the present invention are the same as the components excluding the solvent among the components contained in the actinic ray-sensitive or radiation-sensitive resin composition according to the present invention, and the preferred embodiments are also the same. ..
The content of each component contained in the resist film according to the present invention is the description of "total solid content" in the description of the content of each component other than the solvent of the actinic ray-sensitive or radiation-sensitive resin composition according to the present invention. Is read as “total mass of resist film”.

The thickness of the resist film according to the present invention is not particularly limited, but it is preferably 50 nm to 150 nm, more preferably 80 nm to 130 nm.
Further, when it is desired to form a thick resist film as the memory device becomes three-dimensional, the thickness is, for example, preferably 2 μm or more, more preferably 2 μm or more and 50 μm or less, and further preferably 2 μm or more and 20 μm or less. More preferable.

(Pattern forming method)
The pattern forming method according to the present invention,
A step of exposing the resist film according to the present invention to actinic rays or radiation (exposure step), and
It includes a step of developing the resist film after the exposing step using a developing solution (developing step).
Further, the pattern forming method according to the present invention is a step of forming a resist film on a support with the actinic ray-sensitive or radiation-sensitive resin composition according to the present invention (film forming step),
A step of exposing the resist film to actinic rays or radiation (exposure step), and
The method may include a step of developing the resist film after the exposing step using a developing solution (developing step).

<Film forming process>
The pattern forming method according to the present invention may include a film forming step. Examples of the method of forming the resist film in the film forming step include the method of forming the resist film by drying described in the item of the resist film above.

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

<Exposure process>
The exposure step is a step of exposing the resist film with light.
The exposure method may be immersion exposure.
The pattern forming method according to the present invention may include the exposure step a plurality of times.
The type of light (actinic ray or radiation) used for exposure may be selected in consideration of the characteristics of the photo-acid generator and the pattern shape to be obtained, but infrared light, visible light, ultraviolet light, far ultraviolet light , Extreme ultraviolet light (EUV), X-rays, electron beams and the like, and far ultraviolet light is preferable.
For example, an actinic ray having a wavelength of 250 nm or less is preferable, 220 nm or less is more preferable, and 1 to 200 nm is further preferable.
The light used is, specifically, KrF excimer laser (248 nm), ArF excimer laser (193 nm), F ₂ excimer laser (157 nm), X-ray, EUV (13 nm), electron beam, or the like. , EUV or electron beam is preferred.
Above all, the exposure in the exposing step is preferably performed by liquid immersion exposure using an argon fluoride laser.
The exposure amount is preferably 5 mJ/cm ² to 200 mJ/cm ² , and more preferably 10 mJ/cm ² to 100 mJ/cm ² .

<Developing process>
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), and is preferably an alkaline aqueous solution.

[Alkaline developer]
As the alkali developing solution, a quaternary ammonium salt represented by tetramethylammonium hydroxide is preferably used. In addition to this, inorganic alkalis, primary to tertiary amines, alkanolamines, cyclic amines, etc. An aqueous alkaline solution can also be used.
Further, the alkaline developer may contain an appropriate amount of at least one of alcohols and surfactants. The alkali concentration of the alkali developer is preferably 0.1% by mass to 20% by mass. The pH of the alkaline developer is preferably 10-15.
The time for developing with an alkaline developer is preferably 10 seconds to 300 seconds.
The alkali concentration, pH, and development time of the alkali developing solution can be appropriately adjusted according to the pattern to be formed.

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

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

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

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

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

-Surfactant-
The organic developer may contain a known surfactant in an appropriate amount, if necessary.
The content of the surfactant is preferably 0.001% by mass to 5% by mass, more preferably 0.005% by mass to 2% by mass, and 0.01% by mass to 0.1% by mass based on the total mass of the developer. 5% by mass is more preferable.

-Acid diffusion control agent-
The organic developer may contain the above-mentioned acid diffusion control agent.

[Development method]
Examples of the developing method include a method of immersing the substrate in a tank filled with the developing solution for a certain period of time (dip method), a method of raising the developing solution on the surface of the substrate by surface tension and resting for a certain period of time (paddle method), and a substrate. A method of spraying the developing solution on the surface (spray method) or a method of continuously discharging the developing solution while scanning the developing solution discharge nozzle at a constant speed on the substrate rotating at a constant speed (dynamic dispensing method) is applied. can do.

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

<Pre-heating step, post-exposure heating step>
The pattern forming method according to the present invention preferably includes a pre-heating (PB: PreBake) step before the exposure step.
The pattern forming method according to the present invention may include the preheating step a plurality of times.
The pattern forming method according to the present invention preferably includes a post exposure bake (PEB: Post Exposure Bake) step after the exposure step and before the development step.
The pattern forming method according to the present invention may include the post-exposure heating step a plurality of times.
The heating temperature is preferably 70° C. to 130° C., and more preferably 80° C. to 120° C. in both the pre-heating step and the post-exposure heating step.
In both the pre-heating step and the post-exposure heating step, the heating time is preferably 30 seconds to 300 seconds, more preferably 30 seconds to 180 seconds, and further preferably 30 seconds to 90 seconds.
The heating can be performed by means provided in the exposure device and the developing device, and may be performed using a hot plate or the like.

<Resist lower layer film forming step>
The pattern forming method according to the present invention may further include a step of forming a resist underlayer film (resist underlayer film forming step) before the film forming step.
The resist underlayer film forming step is a step of forming a resist underlayer film (for example, SOG (Spin On Glass), SOC (Spin On Carbon), antireflection film, etc.) between the resist film and the support. A known organic or inorganic material can be appropriately used for the resist lower layer film.

<Protective film forming process>
The pattern forming method according to the present invention may further include a step of forming a protective film (protective film forming step) before the developing step.
The protective film forming step is a step of forming a protective film (top coat) on the upper layer of the resist film. Known materials can be appropriately used for the protective film. For example, U.S. Patent Application Publication No. 2007/0178407, U.S. Patent Application Publication No. 2008/0085466, U.S. Patent Application Publication No. 2007/0275326, U.S. Patent Application Publication No. 2016/0299432, The protective film-forming composition disclosed in U.S. Patent Application Publication No. 2013/0244438 and International Publication No. 2016/157988 can be preferably used. The protective film-forming composition preferably contains the above-mentioned acid diffusion control agent.
A protective film may be formed on the resist film containing the hydrophobic resin described above.

<Rinse process>
The pattern forming method according to the present invention preferably includes a step of washing with a rinse liquid (rinse step) after the developing step.

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

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

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

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

The rinse liquid may contain an appropriate amount of a surfactant.
In the rinsing step, the substrate that has been developed with the organic developing solution is washed with a rinsing solution containing an organic solvent. The method of cleaning treatment is not particularly limited, but for example, a method of continuously discharging the rinse liquid onto the substrate rotating at a constant speed (spin coating method), or immersing the substrate in a bath filled with the rinse liquid for a certain period of time A method (dip method), a method of spraying a rinse liquid on the substrate surface (spray method), or the like can be applied. Above all, it is preferable to perform the cleaning treatment by the spin coating method, and after the cleaning, rotate the substrate at a rotation speed of 2,000 rpm to 4,000 rpm (rotation/minute) to remove the rinse liquid from the substrate. It is also preferable to include a heating step (Post Bake) after the rinse step. By this heating process, the developing solution and the rinsing solution remaining between the patterns and inside the pattern are removed. In the heating step after the rinse step, the heating temperature is preferably 40 to 160°C, more preferably 70 to 95°C. The heating time is preferably 10 seconds to 3 minutes, more preferably 30 seconds to 90 seconds.

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

(Method of manufacturing electronic device)
The method for manufacturing an electronic device according to the present invention includes the pattern forming method according to the present invention. The electronic device manufactured by the method for manufacturing an electronic device according to the present invention is suitable for electrical and electronic equipment (for example, home appliances, OA (Office Automation) related equipment, media related equipment, optical equipment, communication equipment, etc.). It will be installed.

The embodiment of the present invention will be described more specifically with reference to the following examples. The materials, usage amounts, ratios, processing contents, processing procedures, and the like shown in the following examples can be appropriately changed without departing from the spirit of the embodiments of the present invention. Therefore, the scope of the embodiments of the present invention is not limited to the following specific examples. In addition, "part" and "%" are based on mass unless otherwise specified.

<Resin (A)>
The structures of the resins (A-1 to A-37) used are shown below.
The weight average molecular weight (Mw), number average molecular weight (Mn), and dispersity (Mw/Mn) of the resin were measured by GPC (carrier: tetrahydrofuran (THF)) as described above (polystyrene conversion amount). Moreover, the composition ratio (mol% ratio) of the resin was measured by ¹³ C-NMR (Nuclear Magnetic Resonance).

The unit of the content ratio of each repeating unit of the above resin is mol %.

When a homopolymer of the monomer a1 corresponding to the repeating unit (a1) derived from the monomer (monomer a1) having a glass transition temperature (Tg) of 50° C. or lower when used as a homopolymer in the present specification and examples For the glass transition temperature (Tg) value of, the description in PCT/JP2018/018239 can be referred to.

<Photo acid generator>
The structures of the photo-acid generators (C-1 to C-42) used are shown below.

<Acid diffusion control agent>
The structure of the acid diffusion control agent used is shown below.

The structure of the cross-linking agent used is shown below.

The structure of the hydrophobic resin used is shown below. The weight average molecular weight (Mw), number average molecular weight (Mn), and dispersity (Mw/Mn) of the hydrophobic resin were measured by GPC (carrier: tetrahydrofuran (THF)) as described above (polystyrene conversion amount). ). Moreover, the composition ratio (mol% ratio) of the resin was measured by ¹³ C-NMR (Nuclear Magnetic Resonance).

The structure and molecular weight of the compound (P) used (also referred to as a specific additive) are shown in Table 1 below.

The structures and molecular weights of the compounds AEC-1 to AEC-4 and AAC-1 used in Comparative Examples are shown in Table 2 below.

The surfactant (E) used is shown below.

E-2: Megafac R-41 (manufactured by DIC Corporation)
E-3: KF-53 (manufactured by Shin-Etsu Chemical Co., Ltd.)
E-4: Megafac F176 (manufactured by DIC Corporation)
E-5: Megafac R08 (manufactured by DIC Corporation)
E-6: Troisol S366 (manufactured by Troy Corporation)

The compounds (H-1) to (H-4) used are shown below.

The solvent used is shown below.
S-1: Propylene glycol monomethyl ether acetate (PGMEA)
S-2: Propylene glycol monomethyl ether (PGME)
S-3: Ethyl lactate S-4: Ethyl 3-ethoxypropionate S-5: 2-Heptanone S-6: Methyl 3-methoxypropionate S-7: 3-Methoxybutyl acetate S-8: Butyl acetate S- 9: cyclohexanone S-10: propylene carbonate S-11: cycloheptanone S-12: propylene glycol monoethyl ether

(Examples 1 to 318 and Comparative Examples 1 to 10)
<Preparation of actinic ray-sensitive or radiation-sensitive resin composition> (KrF exposure)
(Examples 1 to 7, 15 to 18, 23 to 29, 36, 127 to 246, Comparative Examples 1, 2, 5 to 10)
The components shown in Tables 3 and 4 were mixed so as to have the solid content concentrations (% by mass) shown in Tables 3 and 4 to obtain solutions. Then, the resulting solution was filtered through a polyethylene filter having a pore size of 3 μm to prepare an actinic ray-sensitive or radiation-sensitive resin composition (resist composition).
In the resist composition of the present embodiment, the solid content means all components other than the solvent and the specific additive. The resist composition obtained was used in Examples and Comparative Examples.
In the table, the content (% by mass) of each component other than the solvent means the content ratio with respect to the total solid content. Further, the content ratio (mass%) of the solvent used to all the solvents is described in the table.

<Measurement of content of specific additive of actinic ray-sensitive or radiation-sensitive resin composition>
Specific additives in the actinic ray-sensitive or radiation-sensitive resin compositions shown in Tables 3 and 4 were added at the contents shown in Tables 3 and 4.
The content of the specific additive was measured as follows.
(Compound represented by the general formula (1))
A 10 mass% acetonitrile solution of the resist solution was prepared and filtered through a PTFE filter (DISMIC-25JP, manufactured by ADVANTEC) having a pore size of 0.20 μm to obtain a WAX column (DB-HeavyWAX (#123-7162), Agilent Technologies). The product was analyzed by a GC (gas chromatograph) device (Agilent-6890A, manufactured by Agilent Technologies) of an FID detector (Agilent-6890A, manufactured by Agilent Technologies). The content of the compound represented by the general formula (1) was quantified by the absolute calibration curve method using the standard reagent of each compound.
The standard reagent is a mixture of a compound represented by the general formula (1) to be quantified with a known concentration and acetonitrile with a known concentration. A commercial item can be used as said acetonitrile.
The contents of the compounds (AEC-1 to AEC-4) similar to the compound represented by the general formula (1) shown in Comparative Example were also measured in the same manner.

(Compound represented by the general formula (2))
3 mL of a 20 mass% acetonitrile solution of a resist solution, 1 mL of a 1 N acetonitrile solution of phosphoric acid, and 1 mL of a 0.1% acetonitrile solution of 2,4-dinitrophenylhydrazine (DNPH) were mixed, and an ultrasonic device (tabletop ultrasonic cleaning Ultrasonic waves were applied for 3 minutes using a vessel (#5510), manufactured by Bransonic. The obtained mixed solution was filtered with a 0.20 μm pore size PTFE filter (DISMIC-25JP, manufactured by ADVANTEC), and UV detection using a reverse phase column (Shim-pack CLC-ODS(M), manufactured by Shimadzu GLC) It analyzed by the liquid chromatograph apparatus (Agilent 1100 HPLC G1311A, made by Agilent Technologies) of the instrument (Agilent 1100 HPLC G1315B, made by Agilent Technologies). The content of the compound represented by the general formula (2) was quantified by the absolute calibration curve method using the standard reagent of each compound.
The standard reagent is a mixture of the compound represented by the general formula (2) whose concentration is known and the DNPH whose concentration is known.
The content of the compound (AAC-1) similar to the compound represented by the general formula (2) shown in Comparative Example was also measured in the same manner.

<Pattern forming method (1): KrF exposure, alkaline aqueous solution development>
An antireflection layer is formed on an 8-inch Si substrate (manufactured by Advanced Materials Technology (hereinafter, also referred to as “substrate”)) that has been subjected to hexamethyldisilazane treatment using a spin coater “ACT-8” manufactured by Tokyo Electron. The resist compositions shown in Tables 3 and 4 prepared above were dropped in the state where the substrate was stationary. After the dropping, the substrate was rotated, the rotation speed was maintained at 500 rpm for 3 seconds, then 100 rpm for 2 seconds, further 500 rpm for 3 seconds, and again 100 rpm for 2 seconds, and then the film thickness setting rotation. Increased to a number (1200 rpm) and held for 60 seconds. Then, it was heated and dried at 130° C. for 60 seconds on a hot plate to form a positive resist film having a film thickness of 12 μm.
With respect to this resist film, a KrF excimer laser scanner (ASML) is used through a mask having a line-and-space pattern such that the space width of the pattern formed after reduction projection exposure and development is 4.5 μm and the pitch width is 25 μm. (Manufactured by PAS5500/850C, wavelength 248 nm) was used for pattern exposure under the exposure conditions of NA=0.60 and σ=0.75. After irradiation, it was baked at 120° C. for 60 seconds, immersed in a 2.38 mass% tetramethylammonium hydroxide (TMAH) aqueous solution for 60 seconds, rinsed with pure water for 30 seconds and dried, and then at 110° C. After baking for 60 seconds, an isolated space pattern having a space width of 4.5 μm and a pitch width of 25 μm was formed.
The pattern exposure is exposure through a mask having a line-and-space pattern such that the space width after reduction projection exposure is 4.5 μm and the pitch width is 25 μm, and the exposure amount is 4. The optimum exposure dose (sensitivity) (mJ/cm ² ) for forming an isolated space pattern having a pitch width of 5 μm and a pitch width of 25 μm was set. In the determination of the sensitivity, a scanning electron microscope (SEM: Scanning Electron Microscope) (Hitachi High-Technologies Corporation 9380II) was used to measure the space width of the pattern.
By the above procedure, an evaluation pattern wafer having the substrate and the pattern formed on the substrate surface was obtained.

<Performance evaluation>
[Stability over time]
After storing the resist composition at 40° C. for 4 weeks, an isolated pattern was formed in the same manner as above. The sensitivity of the obtained isolated space pattern was determined in the same manner as above, and the sensitivity of the isolated space pattern formed by using the resist composition before storage with time and the resist composition after storage (4 weeks at 40° C.) The difference with the sensitivity of the isolated space pattern formed by using, that is, the degree of sensitivity variation was evaluated according to the following criteria.
(Criteria)
A: Sensitivity variation observed is 1 mJ / cm ² less B: sensitivity observed variation is 1 mJ / cm ² or more 2 mJ / cm ² less than C: sensitivity observed variation is 2 mJ / cm ² or more 3 mJ / cm ² less than D : Observed sensitivity variation is 3 mJ/cm ² or more

[Rectangularity]
The cross-sectional shape of the line-and-space pattern having a line width of 20.5 μm/thickness of 12 μm was observed, and the line width Lb at the bottom of the resist pattern was observed using a length scanning electron microscope (SEM Hitachi S-9380II). Then, the line width La at the upper part of the resist pattern is measured. If 0.95≦(La/Lb)≦1.05, then “A”, and 0.90≦(La/Lb)<0.95 Or 1.05<(La/Lb)≦1.10, “B” and 0.85≦(La/Lb)<0.90, or 1.10<(La/Lb) When it was ≦1.15, it was evaluated as “C”, and when it was out of the above range of “A”, “B” and “C”, it was evaluated as “D”.

<Preparation of actinic ray-sensitive or radiation-sensitive resin composition> (ArF exposure)
(Examples 8 to 10, 19 to 20, 30 to 31, 247 to 318, Comparative Example 3)
Various components shown in Tables 3 and 4 were mixed and mixed so as to have the solid content concentration (mass %) shown in Tables 3 and 4 to obtain a solution. The obtained liquid was first filtered in the order of a polyethylene filter having a pore size of 50 nm, a nylon filter having a pore size of 10 nm, and finally a polyethylene filter having a pore size of 5 nm. The resulting actinic ray-sensitive or radiation-sensitive resin composition (resist composition) was used in Examples and Comparative Examples.
In the resist composition of the present embodiment, the solid content means all components other than the solvent and the specific additive.
In the table, the content (% by mass) of each component other than the solvent means the content ratio with respect to the total solid content. Further, the content ratio (mass%) of the solvent used to all the solvents is described in the table.
The content of the specific additive was measured in the same manner as above.

<Pattern forming method (2): ArF immersion exposure, alkaline aqueous solution development (positive)>
An organic antireflection film-forming composition SOC9110D and a Si-containing antireflection film-forming composition HM9825 were applied on a silicon wafer to form an antireflection film. A resist composition was applied onto the obtained antireflection film and baked at 100° C. for 60 seconds (PB: Prebake) to form a resist film having a film thickness of 100 nm.
The obtained wafer was subjected to an ArF excimer laser immersion scanner (manufactured by ASML; XT1700i, NA0.85, Annular, outer sigma 0.9, inner sigma 0.6) in a 1:1 line and space pattern with a line width of 100 nm. Exposed through a 6% halftone mask. Ultrapure water was used as the immersion liquid. Then, baking PEB (Post Exposure Bake) was performed at 90° C. for 60 seconds. Then, a tetramethylammonium hydroxide aqueous solution (2.38% by mass) as a developing solution is paddle-developed for 30 seconds to develop, and rinsed with pure water to form a 1:1 line and space (LS) pattern having a line width of 100 nm. Formed.
The optimum exposure amount (sensitivity) (mJ/cm ² ) for forming a 1:1 line and space (LS) pattern having a line width of 100 nm was used. In the determination of the sensitivity, a scanning electron microscope (SEM: Scanning Electron Microscope) (Hitachi High-Technologies Corporation 9380II) was used to measure the space width of the pattern.
By the above procedure, an evaluation pattern wafer having the substrate and the pattern formed on the substrate surface was obtained.
<Pattern forming method (3): ArF immersion exposure, organic solvent development (negative)>
An organic antireflection film-forming composition SOC9110D and a Si-containing antireflection film-forming composition HM9825 were applied on a silicon wafer to form an antireflection film. A resist composition was applied onto the obtained antireflection film and baked at 100° C. for 60 seconds (PB: Prebake) to form a resist film having a film thickness of 100 nm.
The obtained wafer was subjected to an ArF excimer laser immersion scanner (manufactured by ASML; XT1700i, NA0.85, Annular, outer sigma 0.9, inner sigma 0.6) with a line width of 100 nm in a 1:1 line and space pattern. Exposed through a 6% halftone mask. Ultrapure water was used as the immersion liquid. Then, it baked at 90 degreeC for 60 second(Post Exposure Bake). Then, it was padded with butyl acetate as a developing solution for 30 seconds for development, and rinsed with methylisobutylcarbinol (MIBC) to form a 1:1 line and space (LS) pattern having a line width of 100 nm.
The optimum exposure dose (sensitivity) (mJ/cm ² ) for forming a 1:1 line and space (LS) pattern having a line width of 100 nm was used. In the determination of the sensitivity, a scanning electron microscope (SEM: Scanning Electron Microscope) (Hitachi High-Technologies Corporation 9380II) was used to measure the space width of the pattern.
According to the above procedure, an evaluation pattern wafer having a substrate and a pattern formed on the substrate surface was obtained.

<Performance evaluation>
[Stability over time]
After storing the resist composition at 40° C. for 4 weeks, a line and space pattern was formed in the same manner as above. The sensitivity of the obtained line-and-space pattern was determined in the same manner as described above, and the sensitivity of the line-and-space pattern formed using the resist composition before storage with time and the resist after storage with time (40° C. for 4 weeks) The difference from the sensitivity of the line and space pattern formed by using the composition, that is, the degree of sensitivity variation was evaluated according to the following criteria.
(Criteria)
A: Sensitivity variation observed is 1 mJ / cm ² less B: sensitivity observed variation is 1 mJ / cm ² or more 2 mJ / cm ² less than C: sensitivity observed variation is 2 mJ / cm ² or more 3 mJ / cm ² less than D : Observed sensitivity variation is 3 mJ/cm ² or more

[Rectangularity]
The cross-sectional shape of the line-and-space pattern having a line width of 100 nm/film thickness of 100 nm was observed, and the line width Lb at the bottom of the resist pattern was measured using a length-measuring scanning electron microscope (SEM Corporation Hitachi S-9380II). The line width La at the upper part of the resist pattern is measured, and when 0.95≦(La/Lb)≦1.05, “A”, 0.90≦(La/Lb)<0.95, or , 1.05<(La/Lb)≦1.10, “B” and 0.85≦(La/Lb)<0.90, or 1.10<(La/Lb)≦1 It was evaluated as “C” when it was 0.15 and as “D” when it was out of the range of the above “A”, “B” and “C”.

<Preparation of actinic ray-sensitive or radiation-sensitive resin composition> (EUV exposure)
(Examples 11 to 12, 21, 32 to 33, Comparative Example 4)
Various components shown in Tables 3 and 4 were mixed and mixed so as to have the solid content concentration (mass %) shown in Tables 3 and 4 to obtain a solution. The obtained liquid was first filtered in the order of a polyethylene filter having a pore size of 50 nm, a nylon filter having a pore size of 10 nm, and finally a polyethylene filter having a pore size of 5 nm. The resulting actinic ray-sensitive or radiation-sensitive resin composition (resist composition) was used in Examples and Comparative Examples.
In the resist composition of the present embodiment, the solid content means all components other than the solvent and the specific additive.
In the table, the content (% by mass) of each component other than the solvent means the content ratio with respect to the total solid content. Further, the content ratio (mass%) of the solvent used to all the solvents is described in the table.
The content of the specific additive was measured in the same manner as above.

<Pattern forming method (4): EUV exposure, alkaline development (positive)>
AL412 (manufactured by Brewer Science) was applied onto a silicon wafer and baked at 205° C. for 60 seconds to form a lower layer film having a film thickness of 30 nm. A resist composition was applied thereon and baked (PB) at 120° C. for 60 seconds to form a resist film having a film thickness of 30 nm.
This resist film was subjected to pattern irradiation using an EUV exposure apparatus (Micro Exposure Tool, NA0.3, Quadrupol, outer sigma 0.68, inner sigma 0.36, manufactured by Exitech Co.). As the reticle, a mask having a line size=40 nm and a line:space=1:1 was used.
The resist film after exposure was baked (PEB) at 120° C. for 60 seconds, developed with a tetramethylammonium hydroxide aqueous solution (TMAH, 2.38 mass %) for 30 seconds, and then rinsed with pure water for 30 seconds. The silicon wafer was rotated at a rotation speed of 4000 rpm for 30 seconds and further baked at 90° C. for 60 seconds to obtain a line-and-space pattern having a pitch of 80 nm and a line width of 40 nm (space width of 40 nm).
The optimum exposure amount (sensitivity) (mJ/cm ² ) for forming a line-and-space (LS) pattern having a line width of 40 nm was set. In the determination of the sensitivity, a scanning electron microscope (SEM: Scanning Electron Microscope) (9380II manufactured by Hitachi High-Technologies Corporation) was used to measure the space width of the pattern.
By the above procedure, an evaluation pattern wafer having the substrate and the pattern formed on the substrate surface was obtained.

<Pattern forming method (5): EUV exposure, organic solvent development (negative)>
AL412 (manufactured by Brewer Science) was applied onto a silicon wafer and baked at 205° C. for 60 seconds to form a lower layer film having a film thickness of 30 nm. The resist composition shown in the table was applied thereon and baked (PB) at 120° C. for 60 seconds to form a resist film having a film thickness of 30 nm.
This resist film was subjected to pattern irradiation using an EUV exposure apparatus (Micro Exposure Tool, NA0.3, Quadrupol, outer sigma 0.68, inner sigma 0.36, manufactured by Exitech Co.). As the reticle, a mask having a line size=40 nm and a line:space=1:1 was used.
The exposed resist film was baked (PEB) at 120° C. for 60 seconds and then developed with butyl acetate for 30 seconds. The silicon wafer was rotated at a rotation speed of 4000 rpm for 30 seconds and further baked at 90° C. for 60 seconds to obtain a line-and-space pattern having a pitch of 80 nm and a line width of 40 nm (space width of 40 nm).
The optimum exposure amount (sensitivity) (mJ/cm ² ) for forming a line-and-space (LS) pattern having a line width of 40 nm was set. In the determination of the sensitivity, a scanning electron microscope (SEM: Scanning Electron Microscope) (9380II manufactured by Hitachi High-Technologies Corporation) was used to measure the space width of the pattern.
By the above procedure, an evaluation pattern wafer having the substrate and the pattern formed on the substrate surface was obtained.

[Rectangularity]
By observing the cross-sectional shape of the line-and-space pattern having a line width of 40 nm/thickness of 30 nm, the line width Lb at the bottom of the resist pattern was measured by using a length scanning electron microscope (SEM Hitachi S-9380II). The line width La at the upper part of the resist pattern is measured, and when 0.95≦(La/Lb)≦1.05, “A”, 0.90≦(La/Lb)<0.95, or , 1.05<(La/Lb)≦1.10, “B” and 0.85≦(La/Lb)<0.90, or 1.10<(La/Lb)≦1 It was evaluated as “C” when it was 0.15 and as “D” when it was out of the range of the above “A”, “B” and “C”.

<Preparation of actinic ray-sensitive or radiation-sensitive resin composition> (EB exposure)
(Examples 13, 14, 22, 34, 35, 37 to 126)
Various components shown in Tables 3 and 4 were mixed and mixed so as to have the solid content concentration (mass %) shown in Tables 3 and 4 to obtain a solution. The resulting solution was filtered through a polytetrafluoroethylene filter having a pore size of 0.03 μm to obtain an actinic ray-sensitive or radiation-sensitive resin composition (resist composition).
In the resist composition of the present embodiment, the solid content means all components other than the solvent and the specific additive.
In the table, the content (% by mass) of each component other than the solvent means the content ratio with respect to the total solid content. Further, the content ratio (mass%) of the solvent used to all the solvents is described in the table.
The content of the specific additive was measured in the same manner as above.

<Pattern forming method (6): EB exposure, alkali development (positive)>
The resist composition shown in Tables 3 and 4 was applied onto a 6-inch wafer using a spin coater Mark8 manufactured by Tokyo Electron Ltd., and baked (PB) on a hot plate at 110° C. for 90 seconds to give a film thickness of 80 nm. A resist film of was obtained.
The resist film was subjected to pattern irradiation by using an electron beam drawing apparatus (manufactured by Elionix Co., Ltd.; ELS-7500, accelerating voltage 50 KeV). As the reticle, a mask having a line size=100 nm and a line:space=1:1 was used. After the irradiation, baking (PEB) was performed on a hot plate at 110° C. for 90 seconds, and it was immersed in a 2.38 mass% tetramethylammonium hydroxide aqueous solution as a developing solution for 60 seconds, and then rinsed with pure water for 30 seconds. By drying, a line and space pattern having a pitch of 200 nm and a line width of 100 nm (space width 100 nm) was obtained.
The optimum exposure dose (sensitivity) (μC/cm ² ) for forming a line-and-space (LS) pattern having a line width of 100 nm was used. In the determination of the sensitivity, a scanning electron microscope (SEM: Scanning Electron Microscope) (9380II manufactured by Hitachi High-Technologies Corporation) was used to measure the space width of the pattern.
By the above procedure, an evaluation pattern wafer having the substrate and the pattern formed on the substrate surface was obtained.

<Performance evaluation>
[Stability over time]
After storing the resist composition at 40° C. for 4 weeks, a line and space pattern was formed in the same manner as above. The sensitivity of the obtained line-and-space pattern was determined in the same manner as described above, and the sensitivity of the line-and-space pattern formed using the resist composition before storage with time and the resist after storage with time (40° C. for 4 weeks) The difference from the sensitivity of the line and space pattern formed by using the composition, that is, the degree of sensitivity variation was evaluated according to the following criteria.
(Criteria)
A: Observed sensitivity variation is less than 1 μC/cm ² B: Observed sensitivity variation is 1 μC/cm ² or more and less than ² μC/cm ² C: Observed sensitivity variation is ² μC/cm ² or more and less than 3 μC/cm ² D : Observed sensitivity fluctuation is 3 μC/cm ² or more

[Rectangularity]
By observing the cross-sectional shape of the line-and-space pattern having a line width of 100 nm/a film thickness of 80 nm, the line width Lb at the bottom of the resist pattern was measured using a length scanning electron microscope (SEM Hitachi S-9380II). The line width La at the upper part of the resist pattern is measured, and when 0.95≦(La/Lb)≦1.05, “A”, 0.90≦(La/Lb)<0.95, or , 1.05<(La/Lb)≦1.10, “B” and 0.85≦(La/Lb)<0.90, or 1.10<(La/Lb)≦1 It was evaluated as “C” when it was 0.15 and as “D” when it was out of the range of the above “A”, “B” and “C”.

Table 5 shows the obtained evaluation results.

From the results in Table 5, it can be seen that the pattern cross-sectional shape obtained from the composition of the present invention has excellent rectangularity, and the composition of the present invention has excellent stability over time.

Although the present invention has been described in detail and with reference to particular embodiments, it will be apparent to those skilled in the art that various changes and modifications can be made without departing from the spirit and scope of the invention.
This application is based on the Japanese patent application filed on December 28, 2018 (Japanese Patent Application No. 2018-248645) and the Japanese patent application filed on July 26, 2019 (Japanese Patent Application No. 2019-138319), the contents of which are as follows. Incorporated here as a reference.

Claims

An actinic ray-sensitive or radiation-sensitive resin composition containing a compound represented by the following general formula (1) and a compound (P) which is at least one of the compounds represented by the following general formula (2): ,
The content of the compound (P) is 1 ppm or more and 1000 ppm or less with respect to the total mass of the actinic ray-sensitive or radiation-sensitive resin composition,
An actinic ray-sensitive or radiation-sensitive resin composition, wherein the compound (P) has a molecular weight of 500 or less.

In the general formula (1),
R 1 and R 2 each independently represent a hydrogen atom or a substituent.
L represents a divalent linking group, and the group represented by L has 1 to 5 carbon atoms.
n represents an integer of 1 or more. However, when n represents 1, the carbon number of L is 1 or 2.
When n represents an integer of 2 or more, a plurality of Ls may be the same or different.
In the general formula (2),
R 3 represents a hydrogen atom or a substituent. However, when R 3 represents a substituent, the atom bonded to H—C(═O)— in R 3 is a carbon atom.
The actinic ray-sensitive or radiation-sensitive resin composition according to claim 1, wherein the compound (P) is a compound represented by the following general formula (3) or the following general formula (4).

In the general formula (3),
R 4 and R 5 each independently represent a hydrogen atom or a substituent.
n represents an integer of 1 or more.
In the general formula (4),
R 6 and R 7 each independently represent a hydrogen atom or a substituent.
n1 represents an integer of 1 or more.
n2 represents an integer of 1 or more.
The actinic ray-sensitive or radiation-sensitive material according to claim 1 or 2, wherein the content of the compound (P) is 1 ppm or more and 500 ppm or less based on the total mass of the actinic ray-sensitive or radiation-sensitive resin composition. Resin composition.
4. The activity-sensitive material according to claim 1, wherein the content of the compound (P) is 1 ppm or more and 200 ppm or less based on the total mass of the actinic ray-sensitive or radiation-sensitive resin composition. Ray- or radiation-sensitive resin composition.
The activity-sensitive material according to any one of claims 1 to 4, wherein the content of the compound (P) is 1 ppm or more and 100 ppm or less based on the total mass of the actinic ray-sensitive or radiation-sensitive resin composition. Ray- or radiation-sensitive resin composition.
The actinic ray-sensitive or radiation-sensitive resin composition according to any one of claims 1 to 5, further comprising an acid diffusion controller.
A resist film formed from the actinic ray-sensitive or radiation-sensitive resin composition according to any one of claims 1 to 6.
A pattern forming method, comprising: a step of exposing the resist film according to claim 7; and a step of developing the exposed resist film with a developing solution.
A method for manufacturing an electronic device, comprising the pattern forming method according to claim 8.