JP7295886B2 - Actinic ray-sensitive or radiation-sensitive resin composition, resist film, pattern forming method, and method for manufacturing electronic device - Google Patents

Description

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

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

For the miniaturization of semiconductor devices, the wavelength of the exposure light source is shortened and the numerical aperture (NA) of the projection lens is increased. Currently, an exposure machine using an ArF excimer laser with a wavelength of 193 nm as a light source has been developed. ing. As a technique for further improving the resolution, there is a method of filling a high refractive index liquid (hereinafter also referred to as "immersion liquid") between the projection lens and the sample (that is, the immersion method).

Various conventional resist compositions are known, and for example, the composition 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 under the action of an acid, a radiation-sensitive acid generator, and a solvent.

Japanese Patent Application Laid-Open No. 2015-57638

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

An object of the present invention is to provide an actinic ray- or radiation-sensitive resin composition that achieves both excellent rectangular cross-sectional shape of the obtained pattern and excellent stability over time at a high level.
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 actinic ray-sensitive or radiation-sensitive resin composition.

＜２＞
上記化合物（Ｐ）の含有量が、感活性光線性又は感放射線性樹脂組成物の全質量に対して、１ｐｐｍ以上５００ｐｐｍ以下である、＜１＞に記載の感活性光線性又は感放射線性樹脂組成物。
＜３＞
上記化合物（Ｐ）の含有量が、感活性光線性又は感放射線性樹脂組成物の全質量に対して、１ｐｐｍ以上２００ｐｐｍ以下である、＜１＞又は＜２＞に記載の感活性光線性又は感放射線性樹脂組成物。
＜４＞
上記化合物（Ｐ）の含有量が、感活性光線性又は感放射線性樹脂組成物の全質量に対して、１ｐｐｍ以上１００ｐｐｍ以下である、＜１＞～＜３＞のいずれか１項に記載の感活性光線性又は感放射線性樹脂組成物。
＜５＞
＜１＞～＜４＞のいずれか１項に記載の感活性光線性又は感放射線性樹脂組成物により形成されたレジスト膜。
＜６＞
＜５＞に記載のレジスト膜を露光する工程、及び、露光された上記レジスト膜を、現像液を用いて現像する工程を含むパターン形成方法。
＜７＞
＜６＞に記載のパターン形成方法を含む、電子デバイスの製造方法。
本発明は、上記＜１＞～＜７＞に係る発明であるが、以下、それ以外の事項（例えば、下記［１］～［９］）についても記載している。 Means for solving the above problems include the following aspects.
<1>
a resin (A) whose polarity increases under the action of an acid;
An actinic ray-sensitive or radiation-sensitive resin composition containing a compound (B) that generates an acid upon exposure to actinic rays or radiation, and a compound (P) that is a compound represented by any of the following,
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 composition further contains an acid diffusion controller, and the acid diffusion controller is a basic compound .

<2>
The actinic ray-sensitive or radiation-sensitive resin according to <1>, wherein the content of the compound (P) is 1 ppm or more and 500 ppm or less with respect to the total mass of the actinic ray-sensitive or radiation-sensitive resin composition. Composition.
< 3 >
Actinic ray-sensitive or according to <1> or <2> , wherein 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 A radiation-sensitive resin composition.
< 4 >
Any one of <1> to <3> , wherein 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. Actinic ray-sensitive or radiation-sensitive resin composition .
<5>
A resist film formed from the actinic ray-sensitive or radiation-sensitive resin composition according to any one of <1> to <4> .
< 6 >
A pattern forming method comprising the steps of: exposing the resist film according to <5> ; and developing the exposed resist film using a developer.
< 7 >
A method for manufacturing an electronic device, including the pattern forming method according to <6> .
The present invention relates to the above <1> to <7> , but other matters (for example, the following [1] to [9]) are also described below.

[1]
An actinic ray-sensitive or radiation-sensitive resin composition containing a compound (P) which is at least one of a compound represented by the following general formula (1) and a compound 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,
Actinic ray-sensitive or radiation-sensitive resin composition, wherein the compound (P) has a molecular weight of 500 or less.

In 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, multiple L's may be the same or different.
In general formula (2),
_R3 represents a hydrogen atom or a substituent. However, when R ₃ represents a substituent, the atom bonded to HC(=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 (4).

In general formula (3),
_R4 and _R5 each independently represent a hydrogen atom or a substituent.
n represents an integer of 1 or more.
In general formula (4),
_R6 and _R7 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 or according to [1] or [2], wherein the content of the compound (P) is 1 ppm or more and 500 ppm or less with respect to the total mass of the actinic ray-sensitive or radiation-sensitive resin composition A 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]. 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]. 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], further comprising 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 the steps of: exposing the resist film according to [7]; and developing the exposed resist film using a developer.
[9]
A method for manufacturing an electronic device, 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 in cross-sectional shape of the obtained pattern and excellent stability over time at a high level.
According to the present invention, it is also possible to provide a resist film, a pattern forming method and an electronic device manufacturing method using the actinic ray-sensitive or radiation-sensitive resin composition.

The contents of the present invention will be described in detail below.
The description of the constituent elements described below may be made based on representative embodiments of the present invention, but the present invention is not limited to such embodiments.
Regarding the notation of groups (atomic groups) in the present specification, notations that do not describe substitution and unsubstituted include not only those not having substituents but also those having substituents. For example, an "alkyl group" includes not only an alkyl group having no substituent (unsubstituted alkyl group) but also an alkyl group having a substituent (substituted alkyl group). Also, the term "organic group" as used herein refers to a group containing at least one carbon atom.

Moreover, in the present specification, the type of substituent, the position of the substituent, and the number of substituents are not particularly limited when it is said that it may have a substituent. The number of substituents can be, for example, one, two, three, or more. Examples of substituents include monovalent nonmetallic atomic groups excluding hydrogen atoms, and can be selected from the following substituents T, for example.

(substituent T)
The substituent T includes halogen atoms such as a fluorine atom, a chlorine atom, a bromine atom and an iodine atom; 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 groups such as methoxycarbonyl group, butoxycarbonyl group and phenoxycarbonyl group; acyloxy groups such as acetoxy group, propionyloxy group and benzoyloxy group; acetyl group, benzoyl group, isobutyryl group, acryloyl group, methacryloyl group and methoxalyl group, etc. Alkylsulfanyl groups such as a methylsulfanyl group and a tert-butylsulfanyl group; Arylsulfanyl groups such as a phenylsulfanyl group and a p-tolylsulfanyl group; Alkyl groups; Cycloalkyl groups; carboxy group; formyl group; sulfo group; cyano group; alkylaminocarbonyl group; arylaminocarbonyl group; sulfonamide group; silyl group; amino group; and combinations thereof.

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

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

As used herein, the amount of each component in the composition refers to the total amount of the corresponding multiple substances present in the composition when there are multiple substances corresponding to each component in the composition, unless otherwise specified. means.
As used herein, the term "process" includes not only independent processes but also processes that cannot be clearly distinguished from other processes as long as the intended purpose of the process is achieved.
As used herein, "total solid content" refers to the total mass of components excluding the solvent from the total composition of the composition. Moreover, as described above, the “solid content” is a component excluding the solvent, and may be solid or liquid at 25° C., for example.
In the present specification, "% by mass" and "% by weight" are synonymous, and "parts by mass" and "parts by weight" are synonymous.
Moreover, in the present specification, a combination of two or more preferred aspects is a more preferred 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 is
An actinic ray-sensitive or radiation-sensitive resin composition containing a compound (P) which is at least one of a compound represented by the general formula (1) described later and a compound represented by the general formula (2) described later. hand,
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,
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 temporal stability at a high level.
Although the reason is not clear, it is presumed as follows.
First, the present inventors added at least one of the compound represented by the general formula (1) and the compound represented by the general formula (2) to the actinic ray-sensitive or radiation-sensitive resin composition as described above. By containing the compound (P) 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 it to be something. This is because the actinic ray-sensitive or radiation-sensitive resin composition contains the compound (P) in the above-mentioned extremely small amount range, and although the exact reason is unknown, the exposed portion of the resist film It is presumed that this is because, for example, the excessive diffusion of the acid generated by the exposure to the unexposed area was suppressed.
Further, by setting 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, the molecular weight of the compound (P) is more than 500, the improvement in the flexibility of the resist film is considered to be suppressed. As a result, the acid generated in the exposed area of the resist film is prevented from diffusing too much into the unexposed area. From this point of view as well, it is presumed that the rectangularity of the cross-sectional shape of the pattern is extremely excellent. 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 extremely small amount range, so that the actinic ray-sensitive or radiation-sensitive resin composition The fact that the stability over time can be further improved is a finding obtained by the present inventors through intensive studies, but the reason for this 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. Moreover, 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, details of each component contained in the actinic ray-sensitive or radiation-sensitive resin composition (also referred to simply 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) (hereinafter also referred to as "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). ).

In 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, multiple L's may be the same or different.
In general formula (2),
_R3 represents a hydrogen atom or a substituent. However, when R ₃ represents a substituent, the atom bonded to HC(=O)- in R ₃ is a carbon atom.

Substituents for R ₁ and R ₂ are not particularly limited, and examples thereof include monovalent organic groups. Specific examples of monovalent organic groups include alkyl groups, alkenyl groups, cycloalkyl groups, aryl groups, heterocyclic groups, and acyl groups.

Examples of the alkyl group include alkyl groups having 1 to 20 carbon atoms, which may be linear or branched, preferably alkyl groups having 1 to 10 carbon atoms, and alkyl groups having 1 to 5 carbon atoms. more preferred.
Examples of alkenyl groups include alkenyl groups having 2 to 5 carbon atoms, which may be linear or branched, and alkenyl groups having 2 to 3 carbon atoms are preferred.
The cycloalkyl group includes, for example, a cycloalkyl group having 3 to 10 carbon atoms, preferably a cycloalkyl group having 3 to 6 carbon atoms.
The cycloalkyl group may have a heteroatom between the carbon-carbon bonds. Heteroatoms include, for example, oxygen atoms, sulfur atoms, and nitrogen atoms.
The aryl group includes, for example, an aryl group having 6 to 14 carbon atoms, preferably an aryl group having 6 to 10 carbon atoms.
A heterocyclic group may be monocyclic or polycyclic. The polycyclic type can further suppress acid diffusion. Moreover, the heterocyclic group may or may not have aromaticity. Heterocyclic rings having aromaticity include, for example, furan ring, thiophene ring, benzofuran ring, benzothiophene ring, dibenzofuran ring, dibenzothiophene ring, and pyridine ring. Non-aromatic heterocycles include, for example, tetrahydropyran, lactone, sultone and decahydroisoquinoline rings. Examples of the lactone ring and sultone ring include the lactone structure and sultone structure exemplified in the resins described above. The heterocyclic ring in the heterocyclic group is particularly preferably a furan ring, a thiophene ring, a pyridine ring, or a decahydroisoquinoline ring.

The acyl group includes, for example, acyl groups having 1 to 4 carbon atoms, specifically an acetyl group.

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

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, but includes an alkylene group having 1 to 5 carbon atoms, which may be linear or branched, preferably an alkylene group having 1 to 3 carbon atoms, and further 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 substituent T described above.
The number of carbon atoms in the group represented by L is 1-5.

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, L has 1 or 2 carbon atoms. If this is not satisfied, it tends to be difficult to improve stability over time and pattern rectangularity.
Although the upper limit of n is not particularly limited, it is 10, for example.
n is preferably 1 to 4, more preferably 1 to 3.

The substituent for R ₃ is not particularly limited, and examples thereof include monovalent organic groups. Specific examples of monovalent organic groups include alkyl groups, alkenyl groups, cycloalkyl groups, aryl groups, heterocyclic groups, and acyl groups.

Examples of the alkyl group include alkyl groups having 1 to 20 carbon atoms, which may be linear or branched, preferably alkyl groups having 1 to 10 carbon atoms, and alkyl groups having 1 to 5 carbon atoms. more preferred.
Examples of alkenyl groups include alkenyl groups having 2 to 5 carbon atoms, which may be linear or branched, and alkenyl groups having 2 to 3 carbon atoms are preferred.
The cycloalkyl group includes, for example, a cycloalkyl group having 3 to 10 carbon atoms, preferably a cycloalkyl group having 3 to 6 carbon atoms.
The cycloalkyl group may have a heteroatom between the carbon-carbon bonds. Heteroatoms include, for example, oxygen atoms, sulfur atoms, and nitrogen atoms.

The aryl group includes, for example, an aryl group having 6 to 14 carbon atoms, preferably an aryl group having 6 to 10 carbon atoms.
A heterocyclic group may be monocyclic or polycyclic. The polycyclic type can further suppress acid diffusion. Moreover, the heterocyclic group may or may not have aromaticity. Heterocyclic rings having aromaticity include, for example, furan ring, thiophene ring, benzofuran ring, benzothiophene ring, dibenzofuran ring, dibenzothiophene ring, and pyridine ring. Non-aromatic heterocycles include, for example, tetrahydropyran, lactone, sultone and decahydroisoquinoline rings. Examples of the lactone ring and sultone ring include the lactone structure and sultone structure exemplified in the resins described above. The heterocyclic ring in the heterocyclic group is particularly preferably a furan ring, a thiophene ring, a pyridine ring, or a decahydroisoquinoline ring.

The acyl group includes, for example, acyl groups having 1 to 4 carbon atoms, specifically an acetyl 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, but examples thereof include the above-mentioned substituent T, alkyl group, halogen atom (eg, fluorine atom, chlorine atom, bromine atom, iodine atom), nitro group, formyl group, and the like.

When R ₃ represents a substituent, the atom bonded to HC(=O)- in R ₃ is a carbon atom. If this is not satisfied, it tends to be difficult to improve stability over time and pattern rectangularity.

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

In general formula (3),
_R4 and _R5 each independently represent a hydrogen atom or a substituent.
n represents an integer of 1 or more.
In general formula (4),
_R6 and _R7 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.

Specific examples of the substituent for R ₄ are the same as the specific examples of the substituent for R ₁ in formula (1) above, and the preferred range is 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.
Although the upper limit of n is not particularly limited, it is 10, for example.
n is preferably 1 to 4, more preferably 1 to 3.

Specific examples of the substituent for R ₆ are the same as the specific examples of the substituent for R ₁ in the 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 preferred range is also the same.
n1 represents an integer of 1 or more.
Although the upper limit of n1 is not particularly limited, it is 5, for example.
n1 is preferably 1 to 4, preferably 1 or 2.

n2 represents an integer of 1 or more.
Although the upper limit of n2 is not particularly limited, it is 5, for example.
n2 is preferably 1 to 2, more preferably 1.

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

Specific examples of 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 compound (P) (the total when there are multiple compounds (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.
If the content of the compound (P) (the total if there are multiple compounds (P)) is less than 1 ppm, the effect of the present invention cannot be exhibited. If the content of the compound (P) (the total if there are multiple compounds (P)) exceeds 1000 ppm, it is not possible to achieve both the rectangularity of the pattern shape and the stability over time.
The content of the compound (P) (in the case where there are a plurality of compounds (P), the total amount) is determined in the actinic ray-sensitive or radiation-sensitive resin composition from the viewpoint of the rectangularity of the resulting 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 even more preferably 1 ppm or more and 100 ppm or less, relative to the total mass of the substance.

The molecular weight of said compound (P) is 500 or less. In addition, when multiple compounds (P) exist, 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 exhibited, which promotes the diffusion of the acid generated in the exposed portion of the resist film, and reduces the rectangularity of the obtained pattern.
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 above compound (P), but may contain the compound represented by the above general formula (1), and the compound represented by the above general formula (2) and may contain a compound represented by the above general formula (1) and a compound represented by the above general formula (2).
When the composition of the present invention contains a compound represented by the general formula (1), the compound represented by the general formula (1) may be used singly or in combination of two or more. They may be used 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 singly or in combination of two or more. They may be used together.

The content of the 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 general formula (1))
A resist solution containing the compound represented by the general formula (1) was prepared, and an FID detector (Agilent-6890A, Agilent・Analyzed with a GC (gas chromatograph) device (Agilent-6890A, manufactured by Agilent Technologies) manufactured by Agilent Technologies, Inc.). The content of the compound represented by the general formula (1) was quantified by the absolute calibration curve method using standard reagents for each compound.
The standard reagent is a mixture of the compound represented by the general formula (1) with a known concentration to be quantified and acetonitrile with a known concentration. A commercial item can be used as said acetonitrile.

(Compound represented by general formula (2))
A resist solution containing the compound represented by the general formula (2) was prepared and subjected to ultrasonic irradiation for 3 minutes using an ultrasonic device (desktop ultrasonic cleaner (#5510), manufactured by Bransonic). The resulting solution was subjected to a liquid chromatograph (Agilent 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 standard reagents for each compound.
The standard reagent is a mixture of the compound represented by the general formula (2) with a known concentration, which is to be quantified, and DNPH with a known concentration.

<Resin whose polarity is increased by the action of acid>
The actinic ray-sensitive or radiation-sensitive resin composition according to the present invention is typically a resin (hereinafter also referred to as "resin (A)") whose polarity increases due to the action of an acid and the solubility in a developer changes. ) is preferably contained.

The resin (resin (A)) whose polarity is increased by the action of an 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, more preferably 1. Furthermore, the ethylenically unsaturated compound is preferably a monomeric monomer.
The molecular weight of the ethylenically unsaturated compound is preferably 28-1,000, more preferably 50-800, and particularly preferably 100-600.

Moreover, the resin whose polarity is increased by the action of an acid preferably has an acid-decomposable group, and more preferably a resin having a constitutional unit having an acid-decomposable group.
In this case, in the pattern forming method according to the present invention, which will be described later, when an alkaline developer is used as the developer, a positive pattern is preferably formed, and when an organic developer is used as the developer, A negative pattern is preferably formed.

[Structural Unit Having Acid-Decomposable Group]
Resin (A) preferably has a structural unit (also referred to as “repeating unit”) having an acid-decomposable group.

As the resin (A), known resins can be appropriately used. For example, paragraphs 0055-0191 of US Patent Application Publication No. 2016/0274458, paragraphs 0035-0085 of US Patent Application Publication No. 2015/0004544, paragraph 0045 of US Patent Application Publication No. 2016/0147150. 0090 can be suitably used as resin (A).

The acid-decomposable group preferably has a structure in which a polar group is protected by a group that decomposes and leaves by the action of an acid (leaving group).
Examples of polar groups include carboxy groups, phenolic hydroxyl groups, sulfonic acid groups, sulfonamide groups, sulfonylimide groups, (alkylsulfonyl)(alkylcarbonyl)methylene groups, (alkylsulfonyl)(alkylcarbonyl)imide groups, and bis(alkylcarbonyl) groups. ) methylene group, bis(alkylcarbonyl)imide group, bis(alkylsulfonyl)methylene group, bis(alkylsulfonyl)imide group, tris(alkylcarbonyl)methylene group, and acidic group such as tris(alkylsulfonyl)methylene group (2 .A group that dissociates in a 38% by mass tetramethylammonium hydroxide aqueous solution), an alcoholic hydroxyl group, and the like.

The alcoholic hydroxyl group is a hydroxyl group bonded to a hydrocarbon group, and refers to a hydroxyl group other than a hydroxyl group directly bonded to an aromatic ring (phenolic hydroxyl group). It excludes aliphatic alcohols substituted with functional groups (eg, hexafluoroisopropanol groups, etc.). The alcoholic hydroxyl group is preferably a hydroxyl group with a pKa (acid dissociation constant) of 12 or more and 20 or less.

Preferred polar groups include carboxy groups, phenolic hydroxyl groups, and sulfonic acid groups.

Preferred groups as acid-decomposable groups are groups in which the hydrogen atoms of these groups are substituted with groups (leaving groups) that leave under the action of acid.
Examples of groups that leave by the action of an acid (leaving groups) include -C(R ³⁶ )(R ³⁷ )(R ³⁸ ), -C(R ³⁶ )(R ³⁷ )(OR ³⁹ ), and - C(R ⁰¹ ) (R ⁰² ) (OR ³⁹ ) and the like.
In the formula, R ³⁶ to R ³⁹ each independently represent an alkyl group, cycloalkyl group, aryl group, aralkyl group or 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 groups of R ³⁶ to R ³⁹ , R ⁰¹ and R ⁰² are preferably alkyl groups having 1 to 8 carbon atoms, such as methyl, ethyl, propyl, n-butyl, sec-butyl, hexyl. groups, octyl groups, and the like.
Cycloalkyl groups of R ³⁶ to R ³⁹ , R ⁰¹ and R ⁰² may be monocyclic or polycyclic. As the monocyclic type, a cycloalkyl group having 3 to 8 carbon atoms is preferable, and examples thereof include a cyclopropyl group, a cyclobutyl group, a cyclopentyl group, a cyclohexyl group and a cyclooctyl group. As the polycyclic type, cycloalkyl groups having 6 to 20 carbon atoms are preferable, and examples thereof include adamantyl group, norbornyl group, isobornyl group, camphanyl group, dicyclopentyl group, α-pinel group, tricyclodecanyl group, and tetracyclododecyl. group, androstanyl group, and the like. At least one carbon atom in the cycloalkyl group may be substituted with a heteroatom such as an oxygen atom.
The aryl groups represented by R ³⁶ to R ³⁹ , R ⁰¹ and R ⁰² are preferably aryl groups having 6 to 10 carbon atoms, such as phenyl, naphthyl and anthryl groups.
Aralkyl groups represented by R ³⁶ to R ³⁹ , R ⁰¹ and R ⁰² are preferably aralkyl groups having 7 to 12 carbon atoms, such as benzyl, phenethyl and naphthylmethyl groups.
Alkenyl groups represented by R ³⁶ to R ³⁹ , R ⁰¹ and R ⁰² are preferably alkenyl groups having 2 to 8 carbon atoms, such as vinyl, allyl, butenyl and cyclohexenyl groups.
The ring formed by combining R ³⁶ and R ³⁷ is preferably a cycloalkyl group (monocyclic or polycyclic). Cycloalkyl groups include monocyclic cycloalkyl groups such as a cyclopentyl group and a cyclohexyl group, or polycyclic cycloalkyl groups such as a norbornyl group, a tetracyclodecanyl group, a tetracyclododecanyl group, and an adamantyl group. is preferred.

The acid-decomposable group is preferably a cumyl ester group, an enol ester group, an acetal ester group, or a tertiary alkyl ester group, and more preferably an acetal group or a tertiary alkyl ester group.

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, 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 combine to form a ring structure.

Examples of the divalent linking group for 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 methyl, ethyl, propyl and hydroxymethyl groups. The alkyl group of Xa ¹ is preferably a methyl group.

The alkyl groups of Rx ¹ , Rx ² and Rx ³ may be linear or branched and include methyl, ethyl, n-propyl, isopropyl, n-butyl and isobutyl. group, t-butyl group, and the like. The number of carbon atoms in the alkyl group is preferably 1-10, more preferably 1-5, and even more preferably 1-3. Some of the carbon-carbon bonds in the alkyl groups of Rx ¹ , Rx ² and Rx ³ may be double bonds.
Cycloalkyl groups for Rx ¹ , Rx ² and Rx ³ include monocyclic cycloalkyl groups such as cyclopentyl group and cyclohexyl group, norbornyl groups, tetracyclodecanyl groups, tetracyclododecanyl groups, adamantyl groups and the like. Polycyclic cycloalkyl groups are preferred.

The ring structure formed by combining Rx ¹ , Rx ² and Rx ³ includes monocyclic cycloalkane rings such as cyclopentyl ring, cyclohexyl ring, cycloheptyl ring and cyclooctane ring, norbornane ring, tetracyclo Polycyclic cycloalkyl rings such as decane ring, tetracyclododecane ring and adamantane ring are preferred. A cyclopentyl ring, a cyclohexyl ring, or an adamantane ring is more preferred. As the ring structure formed by combining two 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 Formula AI are 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 arbitrarily substituted with a hydrogen atom, a halogen atom other than a fluorine atom, or a monovalent organic group. .

Resin (A) also preferably has structural units described in paragraphs 0336 to 0369 of US Patent Application Publication No. 2016/0070167 as structural units having an acid-decomposable group.

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

Further, the resin (A) is a repeating unit having, as a repeating unit having an acid-decomposable group, a structure (acid-decomposable group) in which a phenolic hydroxyl group is protected by a leaving group that decomposes and leaves under the action of an acid. It is preferred to have In this specification, a phenolic hydroxyl group is a group obtained 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, such as a benzene ring and a naphthalene ring.

Examples of the leaving group that is decomposed and left 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 to Rx ₃ are more preferably each independently a repeating unit representing a linear or branched alkyl group, and Rx ₁ to Rx ₃ each independently represent a linear More preferably, it is a repeating unit representing an alkyl group.
Two of Rx ₁ to Rx ₃ may combine to form a monocyclic or polycyclic ring.
The alkyl group for 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 groups represented by Rx ₁ to Rx ₃ include monocyclic cycloalkyl groups such as cyclopentyl group and cyclohexyl group, or polycyclic groups such as norbornyl group, tetracyclodecanyl group, tetracyclododecanyl group and adamantyl group. is preferred.
Cycloalkyl groups formed by combining two of Rx ₁ to Rx ₃ include monocyclic cycloalkyl groups such as cyclopentyl and cyclohexyl groups, norbornyl, tetracyclodecanyl, and tetracyclododecanyl. and polycyclic cycloalkyl groups such as adamantyl groups. Among them, a monocyclic cycloalkyl group having 5 to 6 carbon atoms is more preferable.
A cycloalkyl group formed by combining two of Rx ₁ to Rx ₃ is, for example, a group in which one of the methylene groups constituting the ring has a heteroatom such as an oxygen atom or a heteroatom such as a carbonyl group. may be replaced.
In the groups represented by formulas (Y1) and (Y2), for example, Rx ₁ is a methyl group or an ethyl group, and Rx ₂ and Rx ₃ combine to form the above-described cycloalkyl group. 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. Monovalent organic groups include alkyl groups, cycloalkyl groups, aryl groups, aralkyl groups, and alkenyl groups. R ₃₆ is preferably a hydrogen atom.

In 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 a repeating unit having a structure in which a phenolic hydroxyl group is protected by a leaving group that decomposes and leaves under the action of an acid (acid-decomposable group), the 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.

As the repeating unit having a structure (acid-decomposable group) in which a phenolic hydroxyl group is protected by a leaving group that decomposes and leaves under the action of an acid, a repeating unit represented by the following general formula (AII) is preferable.

In the 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, _R62 may combine with _Ar6 to form a ring, in which case _R62 represents a single bond or an alkylene group.
X ₆ represents a single bond, -COO- or -CONR ₆₄ -. _R64 represents a hydrogen atom or an alkyl group.
_L6 represents a single bond or an alkylene group.
Ar ₆ represents an (n+1)-valent aromatic hydrocarbon group, and when combined with R ₆₂ to form a ring, represents an (n+2)-valent aromatic hydrocarbon group.
Each Y ₂ independently represents a hydrogen atom or a group leaving by the action of an acid when n≧2. However, at least one of _Y2 represents a group that leaves under the action of an acid. The group that is eliminated by the action of an acid as Y ₂ is preferably represented by formulas (Y1) to (Y4).
n represents an integer of 1-4.

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 preferred.

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

The content of structural units having an acid-decomposable group contained in the resin (A) (the total when there are a plurality of structural units having an acid-decomposable group) is 5 mol % to 90 mol % is preferred, 10 mol % to 80 mol % is more preferred, and 15 mol % to 70 mol % is even more preferred.
In addition, in the present invention, when the content of the "structural unit" is defined by the molar ratio, the above "structural unit" is synonymous with the "monomer unit". Further, in the present invention, the above-mentioned "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 a lactone structure, a sultone structure, and a carbonate structure]
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.

As the lactone structure or sultone structure, any structure having a lactone structure or sultone structure can be used. A membered lactone structure to which another ring structure is condensed to form a bicyclo structure or spiro structure, or a 5- to 7-membered sultone structure to which a bicyclo structure or spiro structure is formed to form another ring structure is more preferably a ring-condensed one. It is more preferable to have a structural unit having a lactone structure represented by any one of formulas LC1-1 to LC1-21 below or a sultone structure represented by any one of formulas SL1-1 to SL1-3 below. Also, the lactone structure or 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 and SL1-1.

The lactone structure portion or sultone structure portion may or may not have a substituent (Rb ² ). Preferred substituents (Rb ² ) include 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. , halogen atoms other than fluorine atoms, hydroxyl groups, cyano groups, and acid-decomposable groups. More preferred are alkyl groups having 1 to 4 carbon atoms, cyano groups, and acid-decomposable groups. n2 represents an integer of 0-4. When n2 is 2 or more, the multiple substituents (Rb ² ) may be the same or different. Also, a plurality of substituents (Rb ² ) may be bonded to each other to form a ring.

A structural unit having a lactone structure or a sultone structure is preferably a structural unit represented by Formula III below.
Moreover, the resin having a structural unit having an acid-decomposable group preferably contains a structural unit represented by Formula III below.

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 number of repetitions of the structure represented by -R ⁰ -Z- and represents an integer of 0 to 5, preferably 0 or 1, more preferably 0; When n is 0, -R ⁰ -Z- is absent and A and R ⁸ are joined by a single bond.
R ⁰ represents an alkylene group, a cycloalkylene group, or a combination thereof. When there are more than one R ⁰ , each independently represents an alkylene group, a cycloalkylene group, or a combination thereof.
Z represents a single bond, ether bond, ester bond, amide bond, urethane bond or urea bond. When Z is plural, each independently represents a single bond, an ether bond, an ester bond, an amide bond, a urethane bond or a urea bond.
^R8 represents a monovalent organic group having a lactone structure or a sultone structure.
^R7 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 structural unit represented by the formula III below, and specific examples of the monomer corresponding to the structural unit represented by the formula A-1 to be described later will be given, but the present invention is not limited to these specific examples. is not limited to The following specific examples correspond to cases 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 hydrogen atoms and halogen atoms other than fluorine atoms. , or a monovalent organic group.

In addition to the above monomers, monomers shown below are also suitably used as raw materials for the resin (A).

Resin (A) may have a structural unit having a carbonate structure. The carbonate structure is preferably a cyclic carbonate structure.
A structural unit having a cyclic carbonate 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 substituted 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 ) represents an atomic group that forms a monocyclic or polycyclic structure together with the group represented by —O—.

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

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 a structure in which at least two lactone structures are linked by a single bond or a linking group. good.
The lactone structure of the structural unit (a) is not particularly limited, but is preferably a 5- to 7-membered lactone structure, and the 5- to 7-membered lactone structure is fused with another ring structure to form a bicyclo structure or a spiro structure. A cyclic one is preferred.
The lactone structure preferably includes, for example, a lactone structure represented by any one 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 formula L-1 below.

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

Examples of the lactone structure possessed by 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. .
The structural unit (a1) having a structure in which at least two lactone structures are condensed and the 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-
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 a structure in which two lactone structures are condensed. is more preferred.
Examples of structural units 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 definition as Ra in formula L-1, Re ₁ to Re ₈ each independently represent a hydrogen atom or an alkyl group, Me ₁ is a single bond or a divalent linking group and Me ₂ and Me ₃ each independently represent a divalent linking group.

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

The divalent linking group for Me ₁ includes, for example, an alkylene group, a cycloalkylene group, -O-, -CO-, -COO-, -OCO-, and groups in which two or more of these groups are combined. be done.
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 preferably, for example, a methylene group or an ethylene group.
The alkylene group of Me ₁ may be linear or branched, for example methylene group, ethane-1,1-diyl group, ethane-1,2-diyl group, propane-1,1-diyl group, propane -1,3-diyl group, propane-2,2-diyl group, pentane-1,5-diyl group, hexane-1,6-diyl group and the like.
The cycloalkylene group of Me ₁ preferably has, for example, 5 to 10 carbon atoms, and more preferably 5 or 6 carbon atoms.
The cycloalkylene group of Me ₁ includes, for example, a cyclopentylene group, a cyclohexylene group, a cycloheptylene group, a cyclooctylene group, a cyclodecylene group and the like.
As the divalent linking group for Me ₁ , the group obtained by combining two or more groups described above includes, for example, a group obtained by combining an alkylene group and -COO-, and a group obtained by combining -OCO- and an alkylene group. preferable. Further, the group obtained by combining two or more groups is more preferably a group obtained by combining a methylene group and a -COO- group, and a group obtained by combining a -COO- group and a methylene group.

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

A monomer corresponding to the structural unit (a1) can be synthesized, for example, by the method described in JP-A-2015-160836.

Specific examples of the structural unit (a1) are shown below, but the present invention is not limited thereto. In each formula below, _R9 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-
A 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. A structure in which they are linked by a single bond or a linking group is more preferable.
The linking group includes, for example, the same groups as the linking group for _M2 in formula L-3 described later.
A 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)") is, for example, a structure represented by the following formula L-3 units.

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

The linking group of M ₁ includes, for example, 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 for M ₁ preferably has, for example, 1 to 10 carbon atoms.
The alkylene group of M ₁ may be linear or branched, for example methylene group, ethane-1,1-diyl group, ethane-1,2-diyl group, propane-1,1-diyl group, propane -1,3-diyl group, propane-2,2-diyl group, pentane-1,5-diyl group, hexane-1,6-diyl group and the like.
The cycloalkylene group for M ₁ preferably has, for example, 5 to 10 carbon atoms.
The cycloalkylene group of _M1 includes, for example, a cyclopentylene group, a cyclohexylene group, a cycloheptylene group, a cyclooctylene group, a cyclodecylene group and the like.
As the linking group for M ₁ , the group obtained by combining two or more groups described above is preferably, for example, a group obtained by combining an alkylene group and —COO— and a group obtained by combining —OCO— and an alkylene group. Further, the group obtained by combining two or more groups is more preferably a group obtained by combining a methylene group and a -COO- group, and a group obtained by combining a -COO- group and a methylene group.
Examples of the linking group for _M2 include the same groups as the linking groups for _M1 .

The lactone structure possessed by Lc ₁ is, for example, preferably a 5- to 7-membered lactone structure, and the 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 one of LC1-1 to LC1-21. More preferred 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 may be included in the lactone structure of Lc1 include the same substituents as the above-described substituent (Rb2) of the lactone structure.
The lactone structure possessed by _Lc2 includes, for example, the same structure as the lactone structure exemplified for the lactone structure possessed by _Lc1 .

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

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

The connecting group for Mf ₁ has the same meaning as the connecting group for M ₁ in formula L-3 above.
The connecting group for Mf ₂ has the same meaning as the connecting group for M ₂ in formula L-3 above.
Examples of alkyl groups for Rf ₁ include alkyl groups 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 substituents that the alkyl group of Rf ₁ may have include alkoxy groups such as a hydroxy group, a methoxy group and an ethoxy group, a cyano group, and a halogen atom such as a fluorine atom.
The alkyl group of _Rf2 and _Rf3 is synonymous with the alkyl group of _Rf1 .

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

Structural units having at least two lactone structures usually have optical isomers, and any optical isomers may be used. Moreover, one optical isomer may be used alone, or a plurality of optical isomers may be mixed and used. When one kind of optical isomer is mainly used, its optical purity (ee) is preferably 90% or more, more preferably 95% or more.

The content of structural units having at least two lactone structures is preferably 10 mol% to 60 mol%, more preferably 20 mol% to 50 mol%, still more preferably 30 mol % to 50 mol %.
In order to enhance the effects of the present invention, it is also possible to use two or more kinds of structural units having at least two lactone structures in combination. When two or more types of repeating units having at least two lactone structures are contained, the total content of structural units having at least two lactone structures is preferably within the above range.

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

The content of structural units 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 structural units having at least one type, the total) is preferably 5 mol% to 70 mol%, and 10 mol% to 65 mol%, based on the total structural units of the resin (A). and more preferably 20 mol % to 60 mol %.

[Structural Unit Having Polar Group]
Resin (A) preferably has a structural unit having a polar group.
Polar groups include hydroxyl, cyano, and carboxy groups.
A structural unit having a polar group is preferably a structural 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. Among the alicyclic hydrocarbon structures 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. Moreover, although the following specific examples are described as methacrylic acid ester compounds, they may be acrylic acid ester compounds.

In addition, specific examples of structural units having a polar group include structural units disclosed in paragraphs 0415 to 0433 of US Patent Application Publication No. 2016/0070167.
The resin (A) may contain one type of structural unit having a polar group alone, or may contain 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 10 mol% to 25% with respect to all structural units in the resin (A). Mole % is more preferred.

[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. A constituent unit having neither an acid-decomposable group nor a polar group preferably has an alicyclic hydrocarbon structure. Structural units having neither an acid-decomposable group nor a polar group include, for example, structural units described in paragraphs 0236 to 0237 of US Patent Application Publication No. 2016/0026083. Preferred examples of monomers corresponding to structural units having neither an acid-decomposable group nor a polar group are shown below.

In addition, specific examples of structural units having neither an acid-decomposable group nor a polar group include structural units disclosed in paragraph 0433 of US Patent Application Publication No. 2016/0070167. can.
The resin (A) may contain a structural unit having neither an acid-decomposable group nor a polar group, either singly or in combination of two or more.
The content of structural units having neither an acid-decomposable group nor a polar group is preferably 5 to 40 mol%, more preferably 5 to 30 mol%, based on the total structural units in the resin (A). 5 to 25 mol % is more preferred.

[Repeating unit (a1)]
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 homopolymerized.
Also, the repeating unit (a1) is a non-acid-decomposable repeating unit. Therefore, repeating unit (a1) does not have an acid-decomposable group.

(Method for measuring glass transition temperature of homopolymer)
If there is a catalog value or literature value, the glass transition temperature of the homopolymer is taken, 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 18,000, and the degree of dispersion (Mw/Mn) is 1.7. As a DSC device, a thermal analysis DSC differential scanning calorimeter Q1000 manufactured by TA Instruments Japan Co., Ltd. is used, and the temperature is measured at a rate of temperature increase of 10° C./min.
The homopolymer to be subjected to Tg measurement may be synthesized by a known method using corresponding monomers, for example, it can be synthesized by 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 liquid, 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 dropwise addition was completed, the mixture was further stirred at 80° C. for 2 hours. After allowing the reaction solution to cool, it was reprecipitated with a large amount of methanol/water (mass ratio 9:1), filtered, and the obtained solid was dried to give a homopolymer (Mw: 18000, Mw/Mn: 1.7). got The resulting homopolymer was subjected to DSC measurement. The DSC apparatus and 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 converted to a homopolymer, and improves the resolution of the dot pattern and reduces the roughness on 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, still more 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 flowability of the pattern during heating is suppressed, and the perpendicularity 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 heteroatom in the chain, in that the residual solvent can be more easily volatilized. is preferred. As used herein, the term "non-acid-degradable" means having a property of not undergoing a desorption/decomposition reaction by an acid generated by a photoacid generator.
That is, the "non-acid-decomposable alkyl group" more specifically means an alkyl group that does not detach from the resin (A) by the action of an acid generated by a photoacid generator, or a photoacid generator is generated. Alkyl groups that are not decomposed by the action of acids are exemplified.
The non-acid-decomposable alkyl group may be linear or branched.
The repeating unit having a non-acid-decomposable alkyl group with 2 or more carbon atoms, which may contain a heteroatom in the chain, is described below.

The non-acid-decomposable alkyl group having 2 or more carbon atoms, which may contain a heteroatom in the chain, is not particularly limited. Atom-containing alkyl groups having 2 to 20 carbon atoms are included.
Examples of alkyl groups having 2 to 20 carbon atoms containing heteroatoms in the chain include one or more —CH ₂ —, —O—, —S—, —CO—, and —NR ₆ —. , or an alkyl group substituted with a divalent organic group in which two or more of these are combined. R ₆ above represents a hydrogen atom or an alkyl group having 1 to 6 carbon atoms.
Specific examples of the non-acid-decomposable alkyl group having 2 or more carbon atoms which may contain a heteroatom in the chain include 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, and 2-ethylhexyl group, and one or more of these - A monovalent alkyl group in which CH ₂ — is substituted with —O— or —O—CO— is mentioned.

The carbon number of the non-acid-decomposable alkyl group having 2 or more carbon atoms, which may contain a heteroatom in the chain, is preferably 2 or more and 16 or less, more preferably 2 or more and 10 or less. , 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.
In addition, the non-acid-decomposable alkyl group having 2 or more carbon atoms may have a substituent (for example, a substituent T).

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

In general 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 heteroatom in the chain.

The halogen atom represented by R ₁ is not particularly limited, but 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 alkyl groups having 1 to 10 carbon atoms, and specific examples include methyl group, ethyl group, tert-butyl group, and the like. . Among them, an alkyl group having 1 to 3 carbon atoms is preferred, and a methyl group is more preferred.
The cycloalkyl group represented by R ₁ is not particularly limited, but includes, for example, a cycloalkyl group having 5 to 10 carbon atoms, more specifically a cyclohexyl group and the like.
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 heteroatom in the chain represented by R ₂ are as described above.

In addition, the repeating unit (a1) is a non-acid-decomposable alkyl group having a carboxy group or a hydroxyl group, which may contain a heteroatom in the chain, or 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 heteroatom.
Hereinafter, a non-acid-degradable alkyl group having a carboxy group or a hydroxyl group, which may contain a heteroatom in the chain, or a non-acid-degradable alkyl group having a carboxy group or a hydroxyl group, which may contain a heteroatom in the ring member A repeating unit having a cycloalkyl group will be described.

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

The non-acid-decomposable alkyl group, which may contain a heteroatom in the chain, is not particularly limited. 2 to 20 alkyl groups are included. At least one hydrogen atom in the alkyl group is substituted with a carboxy group or a hydroxyl group.
Examples of alkyl groups having 2 to 20 carbon atoms containing heteroatoms in the chain include one or more —CH ₂ —, —O—, —S—, —CO—, and —NR ₆ —. , or an alkyl group substituted with a divalent organic group in which two or more of these are combined. R ₆ above represents a hydrogen atom or an alkyl group having 1 to 6 carbon atoms.

The number of carbon atoms in the non-acid-decomposable alkyl group, which may contain a heteroatom in the chain, is preferably 2 to 16, more preferably 2 to 10, in terms of better crack resistance (less crack generation). 2 to 8 are more preferred.
In addition, the non-acid-decomposable alkyl group may have a substituent (for example, a substituent T).
Specific examples of repeating units having a heteroatom-containing non-acid-decomposable alkyl group having a carboxy group include repeating units having the following structures.

The number of carbon atoms in the non-acid-decomposable cycloalkyl group is preferably 5 or more, and the upper limit of the carbon number in 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. is preferred, 16 or less is more preferred, and 10 or less is even more preferred.

The non-acid-decomposable cycloalkyl group, which may contain a heteroatom as a ring member, is not particularly limited and includes, for example, a cycloalkyl group having 5 to 20 carbon atoms (more specifically, a cyclohexyl group), and , a cycloalkyl group having 5 to 20 carbon atoms containing a heteroatom as a ring member. At least one hydrogen atom in the cycloalkyl group is substituted with a carboxy group or a hydroxyl group.
Cycloalkyl groups having 5 to 20 carbon atoms containing a heteroatom in a ring member include, for example, one or more —CH ₂ —, —O—, —S—, —CO—, —NR ₆ -, or a cycloalkyl group substituted with a divalent organic group in which two or more of these are combined. R ₆ above represents a hydrogen atom or an alkyl group having 1 to 6 carbon atoms.
In addition, the non-acid-decomposable cycloalkyl group may have a substituent (for example, a substituent T).

A non-acid-degradable alkyl group having a carboxy or hydroxyl group, which may contain a heteroatom in the chain, or a non-acid-degradable cyclo having a carboxy or hydroxyl group, which may contain a heteroatom in the ring member. As the repeating unit having an alkyl group, a repeating unit represented by the following general formula (1-3) is particularly preferable because the effect of the present invention is superior.

In general 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 heteroatom in the chain, or a non-acid-degradable alkyl group having a carboxy group or a hydroxyl group, which may contain a heteroatom in a ring member. represents an acid-decomposable cycloalkyl group.

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

A non-acid-decomposable alkyl group having a carboxy group or a hydroxyl group, which may contain a heteroatom in the chain represented by _R4 , or a carboxy group or a hydroxyl group, which may contain a heteroatom in a ring member The definition and preferred embodiments of the non-acid-decomposable cycloalkyl group 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 heteroatom as a ring member. Examples of this aspect include repeating units having the following structures.

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 values in parentheses represent the Tg (°C) of a homopolymer.

Methoxypolyethylene glycol monomethacrylate (n=2) is a compound having the following structure.

Monomer a1 includes n-butyl acrylate, n-hexyl methacrylate, n-octyl methacrylate, 2-ethylhexyl methacrylate, 2-ethylhexyl acrylate, lauryl methacrylate, hexadecyl acrylate, 2-hydroxyethyl acrylate, and the following A compound represented by MA-5 is preferred.

The resin (A) may contain only one type of repeating unit (a1), or may contain two or more types of repeating units (a1).
In the resin (A), the content of the repeating unit (a1) (when there are a plurality of repeating units (a1), the total) is preferably 5 mol% or more based on the total 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 still more preferable. Among them, the content of the repeating unit (a1) in the resin (A) (the total when there are multiple repeating units (a1)) is 5 to 50 mol% with respect to the total 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]
Resin (A) may have a repeating unit (a4) having a phenolic hydroxyl group.
By containing the repeating unit (a4), the resin (A) is superior in dissolution rate during alkali development and in etching resistance.

The repeating unit having a phenolic hydroxyl group is not particularly limited, but includes a hydroxystyrene repeating unit or a hydroxystyrene (meth)acrylate repeating unit. As the repeating unit having a phenolic hydroxyl group, a repeating unit represented by the following general formula (I) is preferable.

During the ceremony,
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, _R42 may combine with _Ar4 to form a ring, in which case _R42 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.
_L4 represents a single bond or a divalent linking group.
Ar ₄ represents an (n+1)-valent aromatic hydrocarbon group, and when combined with R ₄₂ to form a ring, represents an (n+2)-valent aromatic hydrocarbon group.
n represents an integer of 1 to 5;
For the purpose of increasing the polarity of the repeating unit represented by general formula (I), n is preferably an integer of 2 or more, or X ₄ is -COO- or -CONR ₆₄ -.

The alkyl groups represented by R ₄₁ , R ₄₂ and R ₄₃ in the general formula (I) include optionally substituted methyl group, ethyl group, propyl group, isopropyl group, 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 preferred.

The cycloalkyl groups represented by R ₄₁ , R ₄₂ and R ₄₃ in general formula (I) may be monocyclic or polycyclic. An optionally substituted monocyclic cycloalkyl group having 3 to 8 carbon atoms, such as a cyclopropyl group, a cyclopentyl group and a cyclohexyl group, is preferred.
The halogen atoms represented by R ₄₁ , R ₄₂ and R ₄₃ in general formula (I) include fluorine, chlorine, bromine and iodine atoms, preferably fluorine.
As the alkyl group contained in the alkoxycarbonyl group represented by R ₄₁ , R ₄₂ and R ₄₃ in general formula (I), the same alkyl groups as those described above for R ₄₁ , R ₄₂ and R ₄₃ are preferred.

Preferred substituents for each of the above groups include, for example, an alkyl group, a cycloalkyl group, an aryl group, an amino group, an amido group, a ureido group, a urethane group, a hydroxyl group, a carboxyl group, a halogen atom, an alkoxy group, a thioether group, and an acyl group. group, acyloxy group, alkoxycarbonyl group, cyano group, nitro group, etc., and the number of carbon atoms in the substituent is preferably 8 or less.

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

Specific examples of the (n+1)-valent aromatic hydrocarbon group in the case where n is an integer of 2 or more include any (n-1) of the above 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 substituents that the alkyl group, cycloalkyl group, alkoxycarbonyl group and (n+1)-valent aromatic hydrocarbon group described above may have include R ₄₁ , R ₄₂ and R ₄₃ in general formula (I). alkoxy groups such as methoxy, ethoxy, hydroxyethoxy, propoxy, hydroxypropoxy, and butoxy; aryl groups such as phenyl;
The alkyl group for R ₆₄ in —CONR ₆₄ — (R ₆₄ represents a hydrogen atom or an alkyl group) represented by X ₄ is a methyl group, an ethyl group, or a propyl group, which may have a substituent. , isopropyl group, n-butyl group, sec-butyl group, hexyl group, 2-ethylhexyl group, octyl group, and dodecyl group. .
X ₄ is preferably a single bond, -COO- or -CONH-, more preferably a single bond or -COO-.

The divalent linking group for _L4 is preferably an alkylene group, and the alkylene group may be 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.
Ar ₄ is preferably an optionally substituted aromatic hydrocarbon group having 6 to 18 carbon atoms, more preferably a benzene ring group, a naphthalene ring group or a biphenylene ring group. Among them, the repeating unit represented by formula (I) is preferably a repeating unit derived from hydroxystyrene. That is, Ar ₄ is preferably a benzene ring group.

Specific examples of repeating units 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, and further preferably 60 mol% or more, based on the total repeating units in the resin (A). preferable. In addition, the content of the repeating unit (a4) is preferably 85 mol% or less, more preferably 80 mol% or less, relative to all repeating units in the resin (A).

Resin (A), in addition to the above structural units, adjusts dry etching resistance, suitability for standard developer, substrate adhesion, resist profile, and generally required properties of resist such as resolution, heat resistance, and sensitivity. It can have different building blocks for different purposes. Examples of such structural units include, but are not limited to, structural units corresponding to other monomers.

Other monomers having one addition-polymerizable unsaturated bond selected from, for example, acrylic acid esters, methacrylic acid esters, acrylamides, methacrylamides, allyl compounds, vinyl ethers, vinyl esters, etc. compound etc. can be mentioned.
In addition, any addition-polymerizable unsaturated compound that can be copolymerized with the monomers corresponding to the various structural units described above 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 fluorine argon (ArF) laser exposure, from the viewpoint of ArF light transmission, the resin (A) is substantially an aromatic group It is preferred not to have More specifically, in all structural units of the resin (A), the structural unit having an aromatic group is preferably 5 mol% or less, more preferably 3 mol% or less, ideally is 0 mol %, that is, it is more preferable not to have a constitutional unit having an aromatic group. Moreover, the resin (A) preferably has a monocyclic or polycyclic alicyclic hydrocarbon structure.

The resin (A) is preferably composed of (meth)acrylate-based structural units in all structural units. In this case, all structural units are methacrylate structural units, all structural units are acrylate structural units, and all structural units are methacrylate structural units and acrylate structural units. Although it can be used, it is preferable that the acrylate-based structural unit accounts for 50 mol % or less of the total 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 preferably contains a structural unit having an aromatic hydrocarbon group. More preferably, 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) is such that the hydrogen atoms of the phenolic hydroxyl groups are decomposed by the action of acid. It is preferable to have a structure protected by a group (leaving group) that leaves.
The content of the structural unit having an aromatic hydrocarbon group contained in the resin (A) is preferably 30 mol% to 100 mol%, preferably 40 mol% to 100 mol, based on the total structural units in the resin (A). %, more preferably 50 mol % to 100 mol %.

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

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

Resin (A) may be used individually by 1 type, and may use 2 or more types together.
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. Although the upper limit is not particularly limited, it is preferably 99.5% by mass or less, more preferably 99% by mass or less, and even more 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 cross-linking agent (G) described later, the actinic ray-sensitive or radiation-sensitive resin composition according to the present invention has a phenolic hydroxyl group. It preferably contains an alkali-soluble resin (hereinafter also referred to as "resin (C)"). 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 in the form supported by the resin (C).
Among the resins (C), resins whose polarity is increased by the action of acid are treated as resins whose polarity is increased by the action of 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, or the polarity of which is increased by the action of an acid. It is also possible to contain at least a resin (C) other than a resin that is capable of increasing polarity and a resin whose polarity is increased by the action of an acid.
Resin (C) may contain the acid-decomposable group described above.
The structural unit having a phenolic hydroxyl group contained in the resin (C) is not particularly limited, but is preferably the repeating unit (a4) described above.

Resin (C) may be used individually by 1 type, and may use 2 or more types together.
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, more preferably 40% by mass or more. , more preferably 50% by mass or more. Although the upper limit is not particularly limited, it is preferably 99% by mass or less, more preferably 90% by mass or less, and even more preferably 85% by mass or less.
Resins disclosed in paragraphs 0142 to 0347 of US Patent Application Publication No. 016/0282720 can be suitably used as the resin (C).

[Hydrophobic resin]
The actinic ray-sensitive or radiation-sensitive resin composition according to the present invention 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 under the action of an acid, and a resin whose polarity increases under the action of an acid. is preferred.
By containing the hydrophobic resin (E), the actinic ray-sensitive or radiation-sensitive resin composition according to the present invention reduces the static/dynamic contact angle on the surface of the actinic ray-sensitive or radiation-sensitive film. can be controlled. This makes it possible to improve development characteristics, suppress outgassing, improve immersion liquid followability in immersion exposure, reduce immersion defects, and the like.
The hydrophobic resin (E) is preferably designed so as to be unevenly distributed on the surface of the resist film. It does not have to contribute to uniform mixing.
Further, in the present invention, resins having fluorine atoms are treated as hydrophobic resins and fluorine-containing resins described later. Moreover, it is preferable that the resin having a constitutional 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 " _CH3 partial structure contained in the side chain portion 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 silicon atom, the fluorine atom or 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 group (x) to (z) below.
(x) an acid group; (y) a group that decomposes under the action of an alkaline developer to increase its solubility in the alkaline developer (hereinafter also referred to as a polarity conversion group);
(z) a group that decomposes under the action of an acid

The acid group (x) includes 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) ) methylene group and the like.
Preferred acid groups are fluorinated alcohol groups (preferably hexafluoroisopropanol), sulfonimide groups, or bis(alkylcarbonyl)methylene groups.

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

The content of the structural unit having a group (y) that decomposes under the action of an alkaline developer to increase the solubility in the alkaline developer is 1 to 100 mol% based on all 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.

Examples of the structural unit having a group (z) decomposable by the action of an acid in the hydrophobic resin (E) are the same as the structural units having an acid-decomposable group exemplified for the resin (A). A structural unit having a group (z) decomposable under 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) decomposable by the action of an acid is preferably 1 mol% to 80 mol%, more preferably 10 mol% to 80 mol%, based on the total structural units in the resin (E). More preferably, 20 mol % to 60 mol % is even more preferable.

The hydrophobic resin (E) may further have structural units other than the structural units described above.

The structural unit containing a fluorine atom is preferably 10 mol % to 100 mol %, more preferably 30 mol % to 100 mol %, relative to all structural units contained in the hydrophobic resin (E). Also, the structural unit containing a silicon atom is preferably 10 mol % to 100 mol %, more preferably 20 mol % to 100 mol %, based on the total structural units contained in the hydrophobic resin (E).

On the other hand, especially when the hydrophobic resin (E) contains a CH ₃ partial structure in the side chain portion, it is also preferable that the hydrophobic resin (E) does not substantially contain fluorine atoms and silicon atoms. Moreover, it is preferable that the hydrophobic resin (E) is substantially composed only of structural units composed only of atoms selected from carbon atoms, oxygen atoms, hydrogen atoms, nitrogen atoms and sulfur atoms.

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 residual monomers 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. Further, the dispersity (Mw/Mn) is preferably in the range of 1-5, more preferably in the range of 1-3.

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

- Fluorine-containing resin -
The hydrophobic resin (E) is preferably a resin containing fluorine atoms (also referred to as "fluorine-containing resin").
When the hydrophobic resin (E) contains a fluorine atom, the partial structure having a fluorine atom may be a resin having an alkyl group having a fluorine atom, a cycloalkyl group having a fluorine atom, or an aryl group having a fluorine atom. 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, more preferably 1 to 4 carbon atoms.
A 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.
Aryl groups having a fluorine atom include those in which at least one hydrogen atom of an aryl group such as a phenyl group and a naphthyl group 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 preferred.

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). provided that 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.
All of R ⁵⁷ to R ⁶¹ and R ⁶⁵ to R ⁶⁷ are preferably fluorine atoms. R ⁶² , R ⁶³ and R ⁶⁸ are preferably alkyl groups (preferably having 1 to 4 carbon atoms) in which at least one hydrogen atom is substituted with a fluorine atom, and are perfluoroalkyl groups having 1 to 4 carbon atoms. It is more preferable to have ^R62 and ^R63 may be linked together to form a ring.

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

The fluorine-containing resin is represented by the formula X from the viewpoint of latitude of depth of focus, pattern linearity, improvement of development characteristics, suppression of outgassing, improvement of immersion liquid followability in immersion exposure, and reduction of immersion defects. It is preferable to have a structural unit with
In addition, the actinic ray-sensitive or radiation-sensitive resin composition according to the present invention improves the tolerance of depth of focus, pattern linearity, development characteristics, suppresses outgassing, improves immersion liquid followability 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 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 decomposes under 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 may be the same or different.

The halogen atom for Z includes, for example, a fluorine atom, a chlorine atom, a bromine atom, and an iodine atom, with a fluorine atom being preferred.
Substituents for R ¹¹ and R ¹² include, for example, an alkyl group (preferably having 1 to 4 carbon atoms), a cycloalkyl group (preferably having 6 to 10 carbon atoms), and an aryl group (preferably having 6 to 10 carbon atoms). ). In addition, the substituents as R ¹¹ and R ¹² may further have a substituent, and examples of such further substituents 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 for L is preferably a divalent or trivalent linking group (in other words, n is preferably 1 or 2), more preferably a divalent linking group (in other words, n is 1 is preferred). The linking group for L is preferably a linking group selected from the group consisting of aliphatic groups, aromatic groups and combinations thereof.
For example, when n is 1 and the linking group for L is a divalent linking group, the divalent aliphatic group includes an alkylene group, an alkenylene group, an alkynylene group, or 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 a chain structure is preferable to a cyclic structure, and a linear structure is preferable to a branched chain structure. is preferred. The divalent aliphatic group may have a substituent, and the substituents include halogen atoms (fluorine atom, chlorine atom, bromine atom, iodine atom), hydroxyl group, carboxyl group, amino group, cyano group, 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 divalent aromatic group. Among them, a phenylene group and a naphthylene group are preferred.
The divalent aromatic group may have a substituent, and examples of substituents for the divalent aliphatic group include alkyl groups.
Further, L is a divalent group obtained by removing two hydrogen atoms at arbitrary positions from the structures represented by the above formulas LC1-1 to LC1-21 or SL1-1 to SL-3. may
When n is 2 or more, specific examples of the (n+1)-valent linking group include a group obtained by removing any (n-1) hydrogen atoms from the specific examples of the divalent linking group described above. is mentioned.
Specific examples of L include the following linking groups.

These linking groups may further have a substituent as described above.

R ¹⁰ is preferably a group represented by formula W below.
-YR ²⁰ Formula W

In the above formula W, Y represents a group that decomposes under the action of an alkaline aqueous solution to increase its solubility in the alkaline aqueous solution. ^R20 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 carbonate group (-OC(O)O-), a sulfate group (-OSO ₂ O-), and a sulfonate group (-SO ₂ O-), with the carboxylate group being preferred. .

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

In the 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 ^new is 0, it represents a single bond, indicating that ^Yew1 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 ^Yew1 is a halogen atom, a cyano group or a nitro group, ^new is 1.)
R ^ew1 and R ^ew2 each independently represent an arbitrary group, for example, a hydrogen atom, an alkyl group (preferably having 1 to 8 carbon atoms), a cycloalkyl group (preferably having 3 to 10 carbon atoms) or an aryl group ( It preferably represents 6 to 10 carbon atoms).
At least two of R ^ew1 , R ^ew2 and Y ^ew1 may be linked together to form a ring.
The term "halo(cyclo)alkyl group" refers to an at least partially halogenated alkyl group and cycloalkyl group, and the term "haloaryl group" refers to an at least partially halogenated aryl group.

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

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 combine to form a ring. Organic groups include alkyl groups, cycloalkyl groups, and alkoxy groups, which may be substituted with halogen atoms (preferably fluorine atoms). R ^f2 and R ^f3 are preferably (halo)alkyl groups or (halo)cycloalkyl groups. R ^f2 more preferably represents the same group as R ^f1 or is linked to R ^f3 to form a ring.
The ring formed by connecting R ^f2 and R ^f3 includes a (halo)cycloalkyl ring.

The (halo)alkyl group for R ^f1 to R ^f3 may be either linear or branched, and the linear (halo)alkyl group preferably has 1 to 30 carbon atoms, 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. If polycyclic, the (halo)cycloalkyl group may be bridged. That is, in this case, the (halo)cycloalkyl group may have a bridged structure.
These (halo)cycloalkyl groups include, for example, those represented by the following formulas and groups obtained by halogenating these. Some of the carbon atoms in the cycloalkyl group may be substituted with heteroatoms such as oxygen atoms.

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

The (per)haloaryl group for Y ^ew1 or R ^f1 includes a perfluoroaryl group represented by —C _(n) F _(n-1) . Although the number of carbon atoms n is not particularly limited, 5 to 13 is preferable, and 6 is more preferable.

A cycloalkyl group or a heterocyclic group is preferable as the ring which may be formed by combining at least two of ^Rew1 , ^Rew2 and ^Yew1 .

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

In formula W above, 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 ), more preferably a fluoroalkyl group. The alkyl group substituted with one or more selected from the group consisting of halogen atoms, cyano groups and nitro groups preferably has 1 to 10 carbon atoms, 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 ) Groups are preferred. R' ¹ and R' ² each independently represent a hydrogen atom or an alkyl group not substituted with an electron-withdrawing group (preferably unsubstituted). R' ^f1 and R' ^f2 each independently represent a halogen atom, a cyano group, a nitro group, or a perfluoroalkyl group.
The alkyl groups for R' ¹ and R' ² may be linear or branched, and preferably have 1 to 6 carbon atoms.
The perfluoroalkyl groups for R' ^f1 and R' ^f2 may be linear or branched, and preferably have 1 to 6 carbon atoms.
Preferred specific 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 , _-CF2CF ( _{CF3 ) 2 , -C} ( _CF3 ) ₃ , _{-C5F11 , -C6F13} , _-C7F15 , _{-C8F17 ,} -CH2CF3 _, -CH _{2C2F5 , -CH2C3F7} , _-CH ( _CF3 ) _{2 ,} -CH( _CF3 ) _{C2F5 , -CH2CF} ( _{CF3 ) 2} , and _-CH2CN are mentioned. Among others, -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 preferred, 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 -CH ₂ C ₂ F ₅ , -CH(CF ₃ ) ₂ or -CH ₂ CN is more preferred, and -CH ₂ C ₂ F ₅ or -CH(CF ₃ ) ₂ is particularly preferred.

As the structural unit represented by formula X, a structural unit represented by formula X-1 or X-2 below is preferable, and a structural unit represented by 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 for 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 preferred examples are as described above, but halo(cyclo)alkyl groups are more preferred.

In the above formula X-1, L ² and R ² are not bound together to form a ring, and in the above formula X-2, L ³ and R ³ are bound together to form a ring never.

X ² and X ³ are preferably oxygen atoms.
Z ² and Z ³ are preferably a fluorine atom or a chlorine atom, more preferably a fluorine atom.

As the structural unit represented by formula X, a structural unit represented by 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 is represents an oxygen atom or a sulfur atom; m represents 0 or 1;

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

In formula X-3 above, L ⁴ and R ⁴ do not combine to form a ring.
^X4 is preferably an oxygen atom.

As the structural unit represented by formula X, a structural unit represented by formula Y-1 or a structural unit represented by 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 preferred examples are as described above, but a halo(cyclo)alkyl group is more preferable.

Specific and preferred 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 those described in formula 1 above. is similar to

The content of the structural unit represented by formula X is preferably 10 mol% to 100 mol%, more preferably 20 mol% to 100 mol%, and 30 mol% to 100 mol%, based on the total structural units of the fluorine-containing resin. % is more preferred.

Preferred examples of structural units constituting the hydrophobic resin (E) are shown below.
As the hydrophobic resin (E), resins obtained by arbitrarily combining these constitutional units or resins F-1 to F-3 used in the examples are preferably mentioned, but not limited thereto.

The hydrophobic resin (E) may be used singly or in combination of two or more.
It is preferable to use a mixture of two or more types of hydrophobic resins (E) having different surface energies from the viewpoint of compatibility between immersion liquid followability and development characteristics in immersion exposure.
The content of the hydrophobic resin (E) in the composition is preferably 0.01% by mass to 10% by mass with respect to the total solid content of the actinic ray-sensitive or radiation-sensitive resin composition according to the present invention, and 0 0.05% to 8% by weight is more preferred.

<Photoacid generator>
The composition according to the present invention preferably contains a photoacid generator (hereinafter also referred to as "photoacid generator (B)").
A photoacid generator is a compound that generates an acid upon exposure to actinic rays or radiation.
As the photoacid generator, a compound that generates an organic acid upon exposure to actinic rays or radiation is preferred. Examples include sulfonium salt compounds, iodonium salt compounds, diazonium salt compounds, phosphonium salt compounds, imidosulfonate compounds, oximesulfonate compounds, diazodisulfone compounds, disulfone compounds, and o-nitrobenzylsulfonate compounds.

As the photoacid generator, a known compound that generates an acid upon exposure to actinic rays or radiation can be appropriately selected and used either singly or as a mixture thereof. For example, paragraphs 0125-0319 of US Patent Application Publication No. 2016/0070167, paragraphs 0086-0094 of US Patent Application Publication No. 2015/0004544, paragraph 0323 of US Patent Application Publication No. 2016/0237190. 0402 can be suitably used as the photoacid 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 formula ZI above,
R ²⁰¹ , R ²⁰² and R ²⁰³ each independently represent an organic group.
The number of carbon atoms in the organic groups as R ²⁰¹ , R ²⁰² and R ²⁰³ is preferably 1-30, more preferably 1-20.
Also, 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 of R ²⁰¹ to R ²⁰³ include an alkylene group (eg, a butylene group and a pentylene group) and —CH ₂ —CH ₂ —O—CH ₂ —CH ₂ —. can.
Z ⁻ represents an anion.

[Cation in Compound Represented by Formula ZI]
Preferred embodiments of the cation in formula ZI include corresponding groups in compounds (ZI-1), (ZI-2), (ZI-3) and (ZI-4) described below.
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 to R ²⁰³ of the compound represented by formula ZI and at least one of R ²⁰¹ to R ²⁰³ of another compound represented by formula ZI are connected via a single bond or a linking group. It may be a compound having a bound structure.

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

The aryl group 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. Heterocyclic structures include pyrrole residues, furan residues, thiophene residues, indole residues, benzofuran residues, benzothiophene residues, and the like. 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 optionally possessed by the arylsulfonium compound is a linear alkyl group having 1 to 15 carbon atoms, a branched alkyl group having 3 to 15 carbon atoms, or a cycloalkyl group having 3 to 15 carbon atoms. Groups such as methyl, ethyl, propyl, n-butyl, sec-butyl, t-butyl, cyclopropyl, cyclobutyl, and cyclohexyl groups are preferred.

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

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

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

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

In Formula ZI-3, R ^1c to R ^5c each independently represent a hydrogen atom, an alkyl group, a cycloalkyl group, an aryl group, an alkoxy group, an aryloxy group, an alkoxycarbonyl group, an alkylcarbonyloxy group, a cycloalkylcarbonyloxy group. , a halogen atom, 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 represent an alkyl group, a cycloalkyl group, a 2-oxoalkyl group, a 2-oxocycloalkyl group, an alkoxycarbonylalkyl group, an allyl group or a vinyl group.

Any two or more of R ^1c to R ^5c , R ^5c and R ^6c , R ^6c and R ^7c , R ^5c and R ^x , and R ^x and R ^y may each combine to form a ring structure. Each of these 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 aromatic or non-aromatic hydrocarbon rings, aromatic or non-aromatic heterocyclic rings, and polycyclic condensed rings in which two or more of these rings are combined. The ring structure includes a 3- to 10-membered ring, preferably a 4- to 8-membered ring, and more preferably a 5- or 6-membered ring.

Examples of groups formed by bonding two or more of R ^1c to R ^5c , R ^6c and R ^7c , and R ^x and R ^y include a butylene group 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, compound (ZI-4) will be described.
Compound (ZI-4) is represented by the following formula ZI-4.

In formula ZI-4, l represents an integer of 0 to 2, r represents an integer of 0 to 8, R ¹³ is a hydrogen atom, a fluorine atom, a hydroxyl group, an alkyl group, a cycloalkyl group, an alkoxy group, an alkoxycarbonyl group , or represents a group having a cycloalkyl group, these groups may have a substituent, and R ¹⁴ each independently represents a hydroxyl group, an alkyl group, a cycloalkyl group, an alkoxy group, an alkoxycarbonyl group, an alkylcarbonyl group , an alkylsulfonyl group, a cycloalkylsulfonyl group, or a group having a cycloalkyl group, these groups may have substituents, and each R ¹⁵ independently represents an alkyl group, a cycloalkyl group, or a naphthyl group. These groups may have substituents, and two R ¹⁵ may combine with each other to form a ring.
When two R ¹⁵ are combined to form a ring, the ring skeleton may contain a heteroatom such as an oxygen atom or a nitrogen atom. In one aspect, two R ¹⁵ are alkylene groups, preferably joined together to form a ring structure.
Z ⁻ represents an anion.

In Formula ZI-4, the alkyl groups of R ¹³ , R ¹⁴ and R ¹⁵ are linear or branched and preferably have 1 to 10 carbon atoms, and are methyl, ethyl, n-butyl, or t-butyl group and the like are more preferable.

[Cation in Compound Represented by Formula ZII or Formula ZIII]
Formulas ZII and ZIII will now be described.
In Formulas ZII and ZIII, R ²⁰⁴ to R ²⁰⁷ each independently represent an aryl group, an alkyl group or a cycloalkyl group.
The aryl group represented by R ²⁰⁴ to R ²⁰⁷ is preferably a phenyl group or a naphthyl group, more preferably a phenyl group. The aryl group of R ²⁰⁴ to R ²⁰⁷ may be an aryl group having a heterocyclic structure containing an oxygen atom, a nitrogen atom, a sulfur atom, or the like. Examples of skeletons of aryl groups having a heterocyclic structure include pyrrole, furan, thiophene, indole, benzofuran, and benzothiophene.
The alkyl group and cycloalkyl group represented by R ²⁰⁴ to R ²⁰⁷ 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, butyl group, and pentyl group), and cycloalkyl groups having 3 to 10 carbon atoms (eg, cyclopentyl group, cyclohexyl group, and norbornyl group).

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

[Anions 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 are preferably anions represented by Formula An-1 below.

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, and each Xf independently represents a fluorine atom or at least one represents an alkyl group substituted with a fluorine atom, and when rf is an integer of 2 or more, the plurality of —C(Xf) ₂ — may be the same or different, and R ⁴ and R ⁵ each independently , represents 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 — may be 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 represents a group.

Xf represents a fluorine atom or an alkyl group substituted with at least one fluorine atom. The number of carbon atoms in this alkyl group is preferably 1-10, more preferably 1-4. Also, the alkyl group substituted with at least one fluorine atom is preferably a perfluoroalkyl group.
Xf is preferably a fluorine atom or a C 1-4 perfluoroalkyl group. Xf is more preferably a fluorine atom or _CF3 . In particular, both Xf are preferably fluorine atoms.

^R4f and ^R5f each independently represent a hydrogen atom, a fluorine atom, an alkyl group, or an alkyl group substituted with at least one fluorine atom. R ^4f and R ^5f when there are more than one may be the same or different.
The alkyl groups for R ^4f and R ^5f may have a substituent and preferably have 1 to 4 carbon atoms. R ^4f and R ^5f are preferably hydrogen atoms.
Specific examples and preferred aspects of the alkyl group substituted with at least one fluorine atom are the same as the specific examples and preferred aspects of Xf in Formula An-1.

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

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

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

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

Examples of anions represented by 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 is preferred. Here, L ^f , qf and W are the same as in formula An-1. q' represents an integer from 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 are also preferably anions 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 preferred. 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 are preferably anions represented by Formula 5 below.

In Formula 5, each Xa independently represents a fluorine atom or an alkyl group substituted with at least one fluorine atom, and each Xb independently represents a hydrogen atom or an organic group having no fluorine atom. Definitions and preferred embodiments of rf, pf, qf, R ^4f , R ^5f , L ^f and W are the same as 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 benzenesulfonate anion, substituted by a branched alkyl group or a cycloalkyl group. It is preferably a benzenesulfonate anion.

Z ⁻ in Formula ZI, Z ⁻ in Formula ZII, Zc ⁻ in Formula ZI-3, and Z ⁻ in Formula ZI-4 are also preferably aromatic sulfonate anions represented by Formula SA1 below.

In Formula SA1, Ar represents an aryl group and may further have a substituent other than the sulfonate anion and --(DR ^B ). Substituents which may be further included include a fluorine atom and a hydroxyl group.

n represents an integer of 0 or more. n is preferably 1-4, more preferably 2-3, 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 consisting of a combination of two or more thereof. .

^RB represents a hydrocarbon group.

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

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

Preferable examples of the anion Z ⁻ in Formula ZI and 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 the 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 Formula An-2 and Formula An-3, each Rfa independently represents a monovalent organic group having a fluorine atom, and multiple Rfa's may combine with each other to form a ring.

Rfa is preferably an alkyl group substituted with at least one fluorine atom. The number of carbon atoms in this alkyl group is preferably 1-10, more preferably 1-4. Also, the alkyl group substituted with at least one fluorine atom is preferably a perfluoroalkyl group.
Moreover, it is preferable that a plurality of Rfa's are bonded to each other to form a ring.

As a photoacid generator, the compounds C-1 to C-42 used in the examples are also preferably mentioned, but not limited thereto.

The photoacid generator may be in the form of a low-molecular-weight compound, or may be in the form of being incorporated into a part of the polymer. Moreover, the form of a low-molecular-weight compound and the form incorporated into a part of a polymer may be used in combination.
The photoacid generator is preferably in the form of a low molecular weight compound.
When the photoacid generator is in the form of a low-molecular-weight compound, the molecular weight is preferably 3,000 or less, more preferably 2,000 or less, even more preferably 1,000 or less.
When the photoacid generator is in the form of being incorporated into part of the polymer, it may be incorporated into part of the resin (A) described above, or may be incorporated into a resin different from the resin (A). .
A photo-acid generator may be used individually by 1 type, and may use 2 or more types together.
The content of the photoacid generator in the composition (the total if multiple types are present) is preferably 0.1% by mass to 35% by mass, preferably 0.5% by mass, based on the total solid content of the composition. ~25% by mass is more preferable, 2% by mass to 20% by mass is even more preferable, and 2.5% by mass to 20% by mass is particularly preferable.
When the compound represented by the above formula ZI-3 or ZI-4 is included as a photoacid generator, the content of the photoacid generator contained in the composition (the total when multiple types are present) is 5% to 35% by weight is preferred, and 7% to 30% by weight is more preferred, based on the total solids 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) traps the acid generated from the acid generator or the like during exposure, and acts as a quencher that suppresses the reaction of the acid-decomposable resin in the unexposed area due to excess generated acid. . For example, a basic compound (DA), a basic compound (DB) whose basicity is reduced or lost by irradiation with actinic rays or radiation, an onium salt (DC) that becomes a relatively weak acid to an acid generator, and a nitrogen atom. and a low-molecular-weight compound (DD) having a group that leaves under the action of an acid, or an onium salt compound (DE) having a nitrogen atom in the cation portion, or the like can be used as an acid diffusion controller.
Among them, the actinic ray-sensitive or radiation-sensitive resin composition according to the present invention preferably contains a nitrogen-containing compound as an acid diffusion control agent from the viewpoint of the linearity of the pattern obtained after aging. More preferably, it contains a compound.
Known acid diffusion control agents can be appropriately used in the actinic ray-sensitive or radiation-sensitive resin composition according to the present invention. For example, paragraphs 0627-0664 of US Patent Application Publication No. 2016/0070167, paragraphs 0095-0187 of US Patent Application Publication No. 2015/0004544, paragraph 0403 of US Patent Application Publication No. 2016/0237190. 0423, paragraphs 0259 to 0328 of US Patent Application Publication No. 2016/0274458 can be suitably used as the acid diffusion control agent (D).

[Basic compound (DA)]
Preferred examples of the basic compound (DA) include compounds having structures represented by formulas A to E below.

In Formula A and Formula E,
R ²⁰⁰ , R ²⁰¹ and R ²⁰² may be the same or different and each independently represents a hydrogen atom, an alkyl group (preferably having 1 to 20 carbon atoms), a cycloalkyl group (preferably having 3 to 20 carbon atoms) or an aryl represents a group (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 represent an alkyl group having 1 to 20 carbon atoms.

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

As the basic compound (DA), guanidine, aminopyrrolidine, pyrazole, pyrazoline, piperazine, aminomorpholine, aminoalkylmorpholine, or piperidine are preferable, and imidazole structure, diazabicyclo structure, onium hydroxide structure, onium carboxylate structure, A compound having a trialkylamine structure, an aniline structure or a pyridine structure, an alkylamine derivative having a hydroxyl group 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 is reduced or lost by irradiation with actinic rays or radiation]
A basic compound (DB) whose basicity is reduced or lost by irradiation with actinic rays or radiation (hereinafter also referred to as "compound (DB)") has a proton acceptor functional group, and actinic rays or It is a compound whose proton acceptor property is reduced or lost, or whose proton acceptor property is changed to acidic by being decomposed by irradiation with radiation.

The proton-accepting functional group is a functional group having electrons or a group capable of electrostatically interacting with protons, for example, a functional group having a macrocyclic structure such as cyclic polyether, It means a functional group having a nitrogen atom with a non-contributing lone pair of electrons. A nitrogen atom having a lone pair of electrons that does not contribute to π-conjugation is, for example, a nitrogen atom having a partial structure represented by the following formula.

Preferred partial structures of proton acceptor functional groups include, for example, crown ether, azacrown ether, primary to tertiary amine, pyridine, imidazole, and pyrazine structures.

The compound (DB) is decomposed by exposure to actinic rays or radiation to reduce or eliminate its proton acceptor property, or to generate a compound whose proton acceptor property is changed to an acidic one. Here, the reduction or disappearance of proton acceptor property, or the change from proton acceptor property to acidity is a change in proton acceptor property due to the addition of protons to the proton acceptor functional group. means that when a proton adduct is produced from a compound (DB) having a proton-accepting functional group and a proton, the equilibrium constant in the chemical equilibrium decreases.
Proton acceptor properties can be confirmed by measuring pH.

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

The acid dissociation constant pKa means the acid dissociation constant pKa in an aqueous solution, and is defined, for example, in Kagaku Binran (II) (revised 4th edition, 1993, edited by The Chemical Society of Japan, Maruzen Co., Ltd.). A lower acid dissociation constant pKa indicates a higher acid strength. Specifically, the acid dissociation constant pKa in an aqueous solution can be measured by measuring the acid dissociation constant at 25° C. using an infinitely diluted aqueous solution. Alternatively, a value based on a database of Hammett's substituent constants and known literature values can be obtained by calculation using Software Package 1 described below. All pKa values described herein are calculated using this software package.

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

[Onium salt (DC) that becomes a relatively weak acid with respect 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 relatively weak acid relative to the photoacid generator, can be used as another acid diffusion control agent.
When a photo-acid generator and an onium salt that generates an acid that is relatively weak to the acid generated from the photo-acid generator are mixed and used, the photo-acid generator is exposed to actinic rays or radiation. When the acid generated from collides with an onium salt with an unreacted weak acid anion, salt exchange releases the weak acid to yield an onium salt with a strong acid anion. In this process, the strong acid is exchanged for a weak acid with a lower catalytic activity, so that the acid is apparently deactivated and 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 formulas d1-1 to d1-3 from the viewpoint of depth of focus tolerance and pattern linearity. preferably further comprises at least one compound.

In formulas d1-1 to d1-3, R ⁵¹ represents an optionally substituted hydrocarbon group, and Z ^2c represents an optionally substituted hydrocarbon group having 1 to 30 carbon atoms. wherein no fluorine atom is bonded to the carbon atom adjacent to the S atom, R ⁵² represents an organic group, Y ³ represents a linear, branched or cyclic alkylene group or arylene group, and Rf represents a hydrocarbon group containing a fluorine atom, and each M ⁺ 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 cations exemplified by Formula ZI and the iodonium cations exemplified by Formula ZII.

An onium salt (DC), which is a relatively weak acid with respect to a photoacid generator, is a compound having a cation site and an anion site in the same molecule, and the cation site and the anion site are linked by a covalent bond. (hereinafter also referred to as “compound (DCA)”).
The compound (DCA) is preferably a compound represented by any one 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 anionic moiety selected from —COO ⁻ , —SO ₃ ⁻ , —SO ₂ ⁻ , and —N ⁻ —R ⁴ . R ⁴ has a carbonyl group (-C(=O)-), a sulfonyl group (-S(=O) ₂ -), and a sulfinyl group (-S(=O)- ) represents a monovalent substituent having at least one of
R ¹ , R ² , R ³ , R ⁴ and L ¹ may combine with each other to form a ring structure. In formula C-3, two of R ¹ to R ³ together represent one divalent substituent, which may be bonded to the N atom via a double bond.

Examples of substituents having 1 or more carbon atoms for R ¹ to R ³ include an alkyl group, a cycloalkyl group, an aryl group, an alkyloxycarbonyl group, a cycloalkyloxycarbonyl group, an aryloxycarbonyl group, an alkylaminocarbonyl group, and a cycloalkylamino A carbonyl group, an arylaminocarbonyl group, and the like can be mentioned. An alkyl group, a cycloalkyl group, or an aryl group is preferred.

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, and two of these A group formed by combining the above and the like can be mentioned. 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 that leaves under the action of an acid]
A low-molecular-weight compound (DD) having a nitrogen atom and a group that leaves under the action of an acid (hereinafter also referred to as "compound (DD)") has a group that leaves under the action of an acid on the nitrogen atom. It is preferably an amine derivative having
The group that leaves by the action of an acid is preferably an acetal group, a carbonate group, a carbamate group, a tertiary ester group, a tertiary hydroxyl group, or a hemiaminal ether group, more preferably a carbamate group or a hemiaminal ether group. .
The molecular weight of the compound (DD) is preferably 100-1000, more preferably 100-700, even more preferably 100-500.
Compound (DD) may have a carbamate group with a protecting group on the nitrogen atom. A protecting group constituting a carbamate group can be represented by the following formula d-1.

In formula d-1,
Each R ^b is independently a hydrogen atom, an alkyl group (preferably having 1 to 10 carbon atoms), a cycloalkyl group (preferably having 3 to 30 carbon atoms), an aryl group (preferably having 3 to 30 carbon atoms), an aralkyl group ( preferably 1 to 10 carbon atoms) or an alkoxyalkyl group (preferably 1 to 10 carbon atoms). R ^b may be linked together 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, an oxo group, an alkoxy group, Or it may be substituted with a halogen atom. The same applies to the alkoxyalkyl group represented by ^Rb .

^Rb is preferably a linear or branched alkyl group, cycloalkyl group or aryl group, more preferably a linear or branched alkyl group or cycloalkyl group.
Examples of the ring formed by connecting two Rb ^'s 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, structures disclosed in paragraph 0466 of US Patent Application Publication No. 2012/0135348.

Compound (DD) preferably has a structure represented by Formula 6 below.

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, the two ^R'a 's may be the same or different, and the two ^R'a 's may be linked together to form a heterocyclic ring together with the nitrogen atom in the formula. This heterocyclic ring may contain a heteroatom other than the nitrogen atom in the formula.
R ^b has the same definition as R ^b in formula d-1 above, and preferred examples are also the same.
In Formula 6, the alkyl group, cycloalkyl group, aryl group, and aralkyl group as R ^a may be independently substituted with an alkyl group, cycloalkyl group, aryl group, and aralkyl group as R ^b . It may be substituted with the same groups as the groups described above.

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

The onium salt compound (DE) having a nitrogen atom in the cation moiety (hereinafter also referred to as "compound (DE)") is preferably a compound having a basic site containing a nitrogen atom in the cation moiety. The basic moiety is preferably an amino group, more preferably an aliphatic amino group. More preferably all of the atoms adjacent to the nitrogen atom in the basic moiety are hydrogen atoms or carbon atoms. Moreover, 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.
Preferred specific structures of compound (DE) include, but are not limited to, compounds disclosed in paragraph 0203 of US Patent Application Publication No. 2015/0309408.

Preferred 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, other acid diffusion control agents may be used singly or in combination of two or more.
The content of the acid diffusion control agent in the composition (the total if multiple types exist) is preferably 0.1% by mass to 10% by mass, preferably 0.1% by mass, based on the total solid content of the composition. ~5% by mass is more preferred.

<Solvent>
Among the solvents shown as specific examples below, those corresponding to the compounds 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.
Known resist solvents can be appropriately used in the actinic ray-sensitive or radiation-sensitive resin composition according to the present invention. For example, paragraphs 0665-0670 of US Patent Application Publication No. 2016/0070167, paragraphs 0210-0235 of US Patent Application Publication No. 2015/0004544, paragraph 0424 of US Patent Application Publication No. 2016/0237190. ˜0426, paragraphs 0357-0366 of US Patent Application Publication No. 2016/0274458 can be suitably used.
Solvents that can be used in preparing the composition include, for example, alkylene glycol monoalkyl ether carboxylates, alkylene glycol monoalkyl ethers, alkyl lactate esters, alkyl alkoxypropionates, cyclic lactones (preferably having 4 to 10 carbon atoms), Organic solvents such as monoketone compounds which may have a ring (preferably having 4 to 10 carbon atoms), alkylene carbonates, alkyl alkoxyacetates, and alkyl pyruvates can be mentioned.

As the organic solvent, a mixed solvent in which a solvent containing a hydroxyl group in its structure and a solvent containing no hydroxyl group are mixed may be used.
As the solvent containing a hydroxyl group and the solvent not containing a hydroxyl group, the above-described exemplary compounds can be appropriately selected. (PGME: 1-methoxy-2-propanol), propylene glycol monoethyl ether (PGEE), methyl 2-hydroxyisobutyrate, or ethyl lactate are more preferred. Further, as the solvent containing no hydroxyl group, alkylene glycol monoalkyl ether acetate, alkylalkoxypropionate, monoketone compound which may contain a ring, cyclic lactone, or alkyl acetate are preferable, and among these, propylene glycol monomethyl Ether acetate (PGMEA: 1-methoxy-2-acetoxypropane), ethylethoxypropionate, 2-heptanone, γ-butyrolactone, cyclohexanone, cyclopentanone or butyl acetate are more preferred, propylene glycol monomethyl ether acetate, γ-butyrolactone , ethyl ethoxypropionate, cyclohexanone, cyclopentanone or 2-heptanone are more preferred. Propylene carbonate is also preferred as the solvent containing no hydroxyl group. Among these, it is particularly preferable that the solvent contains γ-butyrolactone from the viewpoint of the uniformity of the layer to be formed.
The mixing ratio (mass ratio) of a solvent containing a hydroxyl group and a solvent not containing a hydroxyl group is 1/99 to 99/1, preferably 10/90 to 90/10, more preferably 20/80 to 60/40. preferable. A mixed solvent containing 50% by mass or more of a solvent 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 it is preferably 0.5% by mass to 50% by mass, and 1.0% by mass to 45% by mass. %, more preferably 1.0% by mass to 40% by mass.
The solid content concentration is the mass percentage of the mass of other resist components excluding the solvent relative 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 cross-links the resin by the action of an acid (hereinafter also referred to as a cross-linking agent (G)).
As the cross-linking agent (G), known compounds 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 crosslinkers (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 an oxetane ring.
The crosslinkable group is preferably a hydroxymethyl group, an alkoxymethyl group, an oxirane ring or an oxetane ring.
The cross-linking agent (G) is preferably a compound (including resin) having two or more cross-linkable groups.
The cross-linking agent (G) is more preferably a phenol derivative, a urea compound (compound having a urea structure) or a melamine compound (compound having a melamine structure) having a hydroxymethyl group or an alkoxymethyl group.
The cross-linking agents may be used singly 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, more preferably 5% by mass to 30% by mass, relative to 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)"). When a surfactant is contained, fluorine-based and silicone-based surfactants (specifically, fluorine-based surfactants, silicone-based surfactants, or surfactants having both fluorine atoms and silicon atoms) 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, adhesion can be achieved with good sensitivity and resolution when using an exposure light source with a wavelength of 250 nm or less, particularly 220 nm or less. It is possible to obtain a resist pattern with little resistance and development defects.
Fluorine-based or silicone-based surfactants may include surfactants described in paragraph 0276 of US Patent Application Publication No. 2008/0248425.
Also, other surfactants besides the fluoro- or silicone-based surfactants described in paragraph 0280 of US2008/0248425 can be used.

These surfactants may be used singly 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 with respect to the total solid content of the composition. %, more preferably 0.0005% by mass to 1% by mass.
On the other hand, when the content of the surfactant is 0.0001% by mass or more with respect to the total solid content of the composition, the uneven surface distribution of the hydrophobic resin increases. As a result, the surface of the actinic ray-sensitive or radiation-sensitive film can be made more hydrophobic, and the water followability 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.
Other additives include acid multipliers, dyes, plasticizers, photosensitizers, light absorbers, alkali-soluble resins, dissolution inhibitors, dissolution accelerators, and the like.

The actinic ray-sensitive or radiation-sensitive resin composition according to the present invention is prepared by dissolving the above components in a predetermined organic solvent, preferably in the above-described mixed solvent, filtering the solution through a filter, and applying it to a predetermined support (substrate). ) is preferably applied on the surface.
The pore size (pore size) of the filter used for filtration is preferably 0.2 µm or less, more preferably 0.05 µm or less, and even more preferably 0.03 µm or less.
In addition, when the solid content concentration of the actinic ray-sensitive or radiation-sensitive resin composition is high (for example, 25% by mass or more), the pore size of the filter used for filtering is preferably 3 μm or less, 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 filter filtration, for example, as disclosed in JP-A-2002-62667, cyclic filtration may be performed, or filtration may be performed by connecting multiple types of filters in series or in parallel. Also, the composition may be filtered multiple times. Furthermore, before and after filtering, the composition may be subjected to a degassing treatment or the like.

Although the film thickness of the resist film made of the actinic ray-sensitive or radiation-sensitive resin composition according to the present invention is not particularly limited, it is preferably 90 nm or less, more preferably 85 nm or less, from the viewpoint of improving resolution. 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 improve the coatability or film-forming property.

<Application>
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 with light irradiation to change its properties. More specifically, the actinic ray-sensitive or radiation-sensitive resin composition according to the present invention is used in semiconductor manufacturing processes such as ICs (Integrated Circuits), manufacturing circuit boards such as liquid crystals or thermal heads, and imprint mold structures. The present invention relates to actinic ray- or radiation-sensitive resin compositions used in fabrication, other photofabrication processes, or the manufacture of lithographic printing plates or acid-curable compositions. A resist pattern formed from the actinic ray-sensitive or radiation-sensitive resin composition according to the present invention is formed through an etching process, an ion implantation process, a bump electrode forming process, a rewiring forming process, and 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 obtained by removing at least part of the solvent from the actinic ray-sensitive or radiation-sensitive resin composition of the present invention.
Specifically, the resist film according to the present invention is obtained, for example, by applying the actinic ray-sensitive or radiation-sensitive resin composition according to the present invention onto a support such as a substrate and then drying.
The drying means removing at least 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 a known method can be used, including drying by heating (eg, 70° C. to 130° C., 30 seconds to 300 seconds).
The heating method is not particularly limited, and known heating means can be used. Examples thereof include heaters, ovens, hot plates, infrared lamps, infrared lasers, and the like.

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 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 "the total mass of the resist film".

Although the thickness of the resist film according to the present invention is not particularly limited, it is preferably 50 nm to 150 nm, more preferably 80 nm to 130 nm.
In addition, when it is desired to form a thick resist film as memory devices become three-dimensional, for example, the thickness is preferably 2 μm or more, more preferably 2 μm or more and 50 μm or less, and 2 μm or more and 20 μm or less. More preferred.

(Pattern formation method)
The pattern forming method according to the present invention comprises:
A step of exposing the resist film according to the present invention to actinic rays or radiation (exposure step), and
A step of developing the resist film after the step of exposing with a developing solution (developing step).
Further, the pattern forming method according to the present invention includes a step of forming a resist film on a support using 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 step of exposing with a developer (developing step).

<Film formation process>
The pattern forming method according to the present invention may include a film forming process. As a method of forming the resist film in the film forming step, for example, the method of forming the resist film by drying described in the item of the resist film described above can be used.

[Support]
The support is not particularly limited, and is generally used in the manufacturing process of semiconductors such as ICs, the manufacturing process of circuit boards such as liquid crystals or thermal heads, and the lithography process of other photofabrications. 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 to light.
The exposure method may be liquid immersion exposure.
The pattern forming method according to the present invention may include the exposure step multiple times.
The type of light (actinic ray or radiation) used for exposure may be selected in consideration of the characteristics of the photoacid generator and the desired pattern shape. , extreme ultraviolet light (EUV), X-rays, and electron beams, and far ultraviolet light is preferred.
For example, actinic rays with a wavelength of 250 nm or less are preferable, 220 nm or less is more preferable, and 1 to 200 nm is even more preferable.
Specific examples of the light used include KrF excimer laser (248 nm), ArF excimer laser (193 nm), _F2 excimer laser (157 nm), X-rays, EUV (13 nm), electron beams, and the like. , EUV or electron beam are preferred.
Among them, exposure in the exposing step is preferably performed by liquid immersion exposure using an argon fluoride laser.
The exposure dose is preferably 5 mJ/cm ² to 200 mJ/cm ² , more preferably 10 mJ/cm ² to 100 mJ/cm ² .

<Development process>
The developer used in the development step may be an alkaline developer or a developer containing an organic solvent (hereinafter also referred to as an organic developer), and is preferably an aqueous alkaline solution.

[Alkaline developer]
As the alkaline developer, quaternary ammonium salts typified by tetramethylammonium hydroxide are preferably used. Aqueous alkaline solutions can also be used.
Furthermore, 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 developer 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 ketone solvents, ester solvents, alcohol solvents, amide solvents, ether solvents, and hydrocarbon solvents. Preferably.

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

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

-Other solvents-
As alcohol-based solvents, amide-based solvents, ether-based solvents, and hydrocarbon-based solvents, 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 may be mixed with a solvent other than the above or water. The water content of the developer as a whole is preferably less than 50% by mass, more preferably less than 20% by mass, even more preferably less than 10% by mass, and particularly preferably substantially free of water.
The content of the organic solvent in the organic developer is preferably 50% 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 developer. The following are more preferable, and 95% by mass or more and 100% by mass or less are particularly preferable.

-Surfactant-
The organic developer can contain a suitable amount of a known surfactant as required.
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 more preferably 0.01% by mass to 0.01% by mass, based on the total mass of the developer. 5% by mass is more preferred.

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

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

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

<Pre-heating process, post-exposure heating process>
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 multiple times.
The pattern forming method according to the present invention preferably includes a post exposure bake (PEB) 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 multiple times.
The heating temperature is preferably 70° C. to 130° C., more preferably 80° C. to 120° C. in both the preheating step and the post-exposure heating step.
The heating time is preferably 30 seconds to 300 seconds, more preferably 30 seconds to 180 seconds, even more preferably 30 seconds to 90 seconds, in both the preheating step and the post-exposure heating step.
Heating can be performed by means provided in the exposure device and the development device, and may be performed using a hot plate or the like.

<Resist Underlayer 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. As the resist underlayer film, a known organic or inorganic material can be appropriately used.

<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 (topcoat) on the upper layer of the resist film. A known material can be used as appropriate for the protective film. For example, US2007/0178407, US2008/0085466, US2007/0275326, US2016/0299432, The composition for forming a protective film disclosed in US Patent Application Publication No. 2013/0244438 and International Publication No. 2016/157988 can be preferably used. As the composition for forming a protective film, a composition containing the acid diffusion control agent described above is preferable.
A protective film may be formed on the above resist film containing the hydrophobic resin.

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

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

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

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

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

The rinse liquid may contain an appropriate amount of surfactant.
In the rinsing step, the substrate developed with the organic developer is washed with a rinse containing an organic solvent. The method of the cleaning treatment is not particularly limited, but for example, a method of continuously discharging the rinse solution onto the substrate rotating at a constant speed (rotation coating method), or a method of immersing the substrate in a tank filled with the rinse solution for a certain period of time. A method (dip method), a method of spraying a rinse liquid onto the substrate surface (spray method), or the like can be applied. Among them, it is preferable to perform the cleaning treatment by a spin coating method, rotate the substrate at a rotation speed of 2,000 to 4,000 rpm (revolutions/minute) after cleaning, and remove the rinse liquid from the substrate. It is also preferable to include a heating step (Post Bake) after the rinsing step. This heating process removes the developer and rinse remaining between the patterns and inside the patterns. In the heating step after the rinsing step, the heating temperature is 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 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, there is a method of treating the resist pattern with hydrogen-containing gas plasma, disclosed in US Patent Application Publication No. 2015/0104957. In addition, Japanese Patent Application Laid-Open No. 2004-235468, US Patent Application Publication No. 2010/0020297, Proc. of SPIE Vol. 8328 83280N-1 “EUV Resist Curing Technique for LWR Reduction and Etch Selectivity Enhancement” may be applied.
Also, the resist pattern formed by the above method can be used as a 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 for manufacturing electronic device)
A 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.). to be installed.

EXAMPLES The embodiments of the present invention will be described more specifically with reference to examples below. Materials, usage amounts, proportions, processing details, processing procedures, and the like shown in the following examples can be changed as appropriate without departing from the gist of the embodiments of the present invention. Accordingly, the scope of embodiments of the present invention is not limited to the specific examples shown below. "Parts" 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 degree of dispersion (Mw/Mn) of the resin were measured by GPC (carrier: tetrahydrofuran (THF)) as described above (in terms of polystyrene). Also, the resin composition ratio (mol% ratio) was measured by ¹³ C-NMR (Nuclear Magnetic Resonance).

In addition, the unit of the content ratio of each repeating unit of the resin is mol %.

A homopolymer of a monomer a1 corresponding to a repeating unit (a1) derived from a monomer (monomer a1) having a glass transition temperature (Tg) of 50° C. or lower when converted to a homopolymer in the present specification and examples The value of the glass transition temperature (Tg) of can refer to the description of PCT/JP2018/018239.

<Photoacid generator>
The structures of the photoacid 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 structures of the cross-linking agents used are shown below.

The structures of the hydrophobic resins used are shown below. The weight average molecular weight (Mw), number average molecular weight (Mn), and degree of dispersion (Mw/Mn) of the hydrophobic resin were measured by GPC (carrier: tetrahydrofuran (THF)) as described above (in terms of polystyrene). ). Also, the resin composition ratio (mol% ratio) 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 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: Megaface R-41 (manufactured by DIC Corporation)
E-3: KF-53 (manufactured by Shin-Etsu Chemical Co., Ltd.)
E-4: Megaface F176 (manufactured by DIC Corporation)
E-5: Megaface R08 (manufactured by DIC Corporation)
E-6: Troysol S366 (manufactured by Troy Corporation)

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

The solvents used are 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 1-7, 15-18, 23-29, 36, 127-246, Comparative Examples 1, 2, 5-10)
Each component shown in Tables 3 and 4 was mixed so as to have the solid content concentration (% by mass) shown in Tables 3 and 4 to obtain a solution. 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 addition, in the resist composition, in this embodiment, the solid content means all components other than the solvent and specific additives. The resulting resist compositions were 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. In addition, the content ratio (% by mass) of the solvent used with respect to the total solvent is shown in the table.

<Measurement of content of specific additive in 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 in the amounts shown in Tables 3 and 4.
The contents of specific additives were measured as follows.
(Compound represented by general formula (1))
A 10% by mass acetonitrile solution of the resist solution was prepared and filtered through a PTFE filter (DISMIC-25JP, manufactured by ADVANTEC) with a pore size of 0.20 μm. (Agilent-6890A, manufactured by Agilent Technologies) using a GC (gas chromatograph) device (Agilent-6890A, manufactured by Agilent Technologies) using 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 standard reagents for each compound.
The standard reagent is a mixture of the compound represented by the general formula (1) with a known concentration to be quantified and acetonitrile with a known concentration. A commercial item can be used as said acetonitrile.
The contents of compounds (AEC-1 to AEC-4) similar to the compound represented by general formula (1) shown in Comparative Examples were also measured in the same manner.

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

<Pattern formation method (1): KrF exposure, alkaline aqueous solution development>
Using Tokyo Electron's spin coater "ACT-8", hexamethyldisilazane-treated 8-inch Si substrate (manufactured by Advanced Materials Technology (hereinafter also referred to as "substrate")), an antireflection layer , the resist compositions described in Tables 3 and 4 prepared above were dropped while the substrate was stationary. After the dropping, the substrate was rotated, and the rotation speed was maintained at 500 rpm for 3 seconds, then at 100 rpm for 2 seconds, at 500 rpm for further 3 seconds, and again at 100 rpm for 2 seconds, after which the film thickness setting rotation was performed. (1200 rpm) and maintained for 60 seconds. Then, it was dried by heating on a hot plate at 130° C. for 60 seconds to form a positive resist film with a thickness of 12 μm.
This resist film is scanned with a KrF excimer laser scanner (ASML) through a mask having a line-and-space pattern such that the pattern formed after reduction projection exposure and development has a space width of 4.5 μm and a pitch width of 25 μm. PAS5500/850C wavelength 248 nm) was used to perform 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, dried, and heated to 110°C. An isolated space pattern with a space width of 4.5 μm and a pitch width of 25 μm was formed.
The above 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. The optimum exposure dose (sensitivity) (mJ/cm ² ) for forming an isolated space pattern with a pitch width of 25 μm was set to 5 μm. In determining the sensitivity, the space width of the pattern was measured using a scanning electron microscope (SEM: 9380II manufactured by Hitachi High-Technologies Corporation).
By the above procedure, a patterned wafer for evaluation having a substrate and a pattern formed on the surface of the substrate 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 resulting isolated space pattern was determined in the same manner as described above, and the sensitivity of the isolated space pattern formed using the resist composition before storage over time and the resist composition after storage over time (at 40°C for 4 weeks) were compared. The difference from the sensitivity of the isolated space pattern formed using , that is, the degree of sensitivity fluctuation was evaluated according to the following criteria.
(criterion)
A: The observed sensitivity variation is less than 1 mJ/cm ² B: The observed sensitivity variation is 1 mJ/cm ² or more and less than 2 mJ/cm ^{2 C: The observed sensitivity variation is 2 mJ/cm 2 or} more and less than 3 mJ/cm ² D : Observed sensitivity fluctuation is 3 mJ/cm ² or more

[Rectangularity]
Observe the cross-sectional shape of a line-and-space pattern with a line width of 20.5 μm and a film thickness of 12 μm, and use a length measurement scanning electron microscope (SEM, Hitachi Ltd. S-9380II) to determine the line width Lb at the bottom of the resist pattern. and the line width La at the upper part of the resist pattern is measured, and if 0.95 ≤ (La/Lb) ≤ 1.05, "A" and 0.90 ≤ (La/Lb) < 0.95 or "B" if 1.05<(La/Lb)≤1.10 and 0.85≤(La/Lb)<0.90 or 1.10<(La/Lb) When ≦1.15, it was evaluated as "C", and when it was out of the range in the above "A", "B", and "C", it was evaluated as "D".

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

<Pattern formation method (2): ArF immersion exposure, alkaline aqueous solution development (positive)>
The composition SOC9110D for forming an organic antireflection film and the composition HM9825 for forming a Si-containing antireflection film were applied onto a silicon wafer to form an antireflection film. A resist composition was applied onto the obtained antireflection film and baked (PB: Prebake) at 100° C. for 60 seconds to form a resist film with a thickness of 100 nm.
The resulting wafer was scanned with an ArF excimer laser immersion scanner (manufactured by ASML; XT1700i, NA 0.85, Annular, outer sigma 0.9, inner sigma 0.6) to form a 1:1 line and space pattern with a line width of 100 nm. was exposed through a 6% halftone mask. Ultrapure water was used as the immersion liquid. After that, it was baked at 90° C. for 60 seconds (PEB: Post Exposure Bake). Next, development was performed by puddling with an aqueous solution of tetramethylammonium hydroxide (2.38% by mass) for 30 seconds as a developer, followed by rinsing with pure water to form a 1:1 line and space (LS) pattern with a line width of 100 nm. formed.
The optimum exposure dose (sensitivity) (mJ/cm ² ) for forming a 1:1 line-and-space (LS) pattern with a line width of 100 nm was used. In determining the sensitivity, the space width of the pattern was measured using a scanning electron microscope (SEM: 9380II manufactured by Hitachi High-Technologies Corporation).
By the above procedure, a pattern wafer for evaluation having a substrate and a pattern formed on the surface of the substrate was obtained.
<Pattern Forming Method (3): ArF Immersion Exposure, Organic Solvent Development (Negative)>
The composition SOC9110D for forming an organic antireflection film and the composition HM9825 for forming a Si-containing antireflection film were applied onto a silicon wafer to form an antireflection film. A resist composition was applied onto the obtained antireflection film and baked (PB: Prebake) at 100° C. for 60 seconds to form a resist film with a thickness of 100 nm.
The resulting wafer was scanned with an ArF excimer laser immersion scanner (manufactured by ASML; XT1700i, NA 0.85, Annular, outer sigma 0.9, inner sigma 0.6) to form a 1:1 line and space pattern with a line width of 100 nm. was exposed through a 6% halftone mask. Ultrapure water was used as the immersion liquid. After that, it was baked at 90° C. for 60 seconds (PEB: Post Exposure Bake). Then, the film was developed by puddling with butyl acetate as a developer for 30 seconds and rinsed with methyl isobutyl carbinol (MIBC) to form a 1:1 line and space (LS) pattern with a line width of 100 nm.
The optimum exposure dose (sensitivity) (mJ/cm ² ) for forming a 1:1 line-and-space (LS) pattern with a line width of 100 nm was used. In determining the sensitivity, the space width of the pattern was measured using a scanning electron microscope (SEM: 9380II manufactured by Hitachi High-Technologies Corporation).
By the above procedure, a pattern wafer for evaluation having a substrate and a pattern formed on the surface of the substrate 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. In the resulting line-and-space pattern, the sensitivity was determined in the same manner as above, and the sensitivity of the line-and-space pattern formed using the resist composition before storage over time and the resist after storage over time (at 40 ° C. for 4 weeks). The difference from the sensitivity of the line-and-space pattern formed using the composition, that is, the degree of sensitivity fluctuation, was evaluated according to the following criteria.
(criterion)
A: The observed sensitivity variation is less than 1 mJ/cm ² B: The observed sensitivity variation is 1 mJ/cm ² or more and less than 2 mJ/cm ^{2 C: The observed sensitivity variation is 2 mJ/cm 2 or} more and less than 3 mJ/cm ² D : Observed sensitivity fluctuation is 3 mJ/cm ² or more

[Rectangularity]
Observing the cross-sectional shape of a line and space pattern with a line width of 100 nm / film thickness of 100 nm, using a length measurement scanning electron microscope (SEM Co., Ltd. Hitachi Ltd. S-9380II), the line width Lb at the bottom of the resist pattern, The line width La at the top of the resist pattern is measured, and "A" if 0.95 ≤ (La/Lb) ≤ 1.05, 0.90 ≤ (La/Lb) < 0.95, or , “B” if 1.05<(La/Lb)≦1.10, and 0.85≦(La/Lb)<0.90, or 1.10<(La/Lb)≦1 0.15 was rated as "C", and if outside the ranges of "A", "B" and "C" above, it was rated as "D".

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

<Pattern Forming Method (4): EUV Exposure, Alkaline Development (Positive)>
A silicon wafer was coated with AL412 (manufactured by Brewer Science) and baked at 205° C. for 60 seconds to form a 30 nm-thick underlayer film. A resist composition was applied thereon and baked (PB) at 120° C. for 60 seconds to form a resist film with a thickness of 30 nm.
This resist film was subjected to pattern irradiation using an EUV exposure apparatus (Exitech, Micro Exposure Tool, NA 0.3, Quadrupol, outer sigma 0.68, inner sigma 0.36). As the reticle, a mask having a line size of 40 nm and a line:space ratio of 1:1 was used.
The exposed resist film 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. A line-and-space pattern with a pitch of 80 nm and a line width of 40 nm (space width of 40 nm) was obtained by rotating the silicon wafer at a rotation speed of 4000 rpm for 30 seconds and baking it at 90° C. for 60 seconds.
The optimum exposure dose (sensitivity) (mJ/cm ² ) for forming a line-and-space (LS) pattern with a line width of 40 nm was used. In determining the sensitivity, the space width of the pattern was measured using a scanning electron microscope (SEM: 9380II manufactured by Hitachi High-Technologies Corporation).
By the above procedure, a patterned wafer for evaluation having a substrate and a pattern formed on the surface of the substrate was obtained.

<Pattern Forming Method (5): EUV Exposure, Organic Solvent Development (Negative)>
A silicon wafer was coated with AL412 (manufactured by Brewer Science) and baked at 205° C. for 60 seconds to form a 30 nm-thick underlayer film. A 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 thickness of 30 nm.
This resist film was subjected to pattern irradiation using an EUV exposure apparatus (Exitech, Micro Exposure Tool, NA 0.3, Quadrupol, outer sigma 0.68, inner sigma 0.36). As the reticle, a mask having a line size of 40 nm and a line:space ratio of 1:1 was used.
After the exposed resist film was baked (PEB) at 120° C. for 60 seconds, it was developed with butyl acetate for 30 seconds. A line-and-space pattern with a pitch of 80 nm and a line width of 40 nm (space width of 40 nm) was obtained by rotating the silicon wafer at a rotation speed of 4000 rpm for 30 seconds and baking it at 90° C. for 60 seconds.
The optimum exposure dose (sensitivity) (mJ/cm ² ) for forming a line-and-space (LS) pattern with a line width of 40 nm was used. In determining the sensitivity, the space width of the pattern was measured using a scanning electron microscope (SEM: 9380II manufactured by Hitachi High-Technologies Corporation).
By the above procedure, a patterned wafer for evaluation having a substrate and a pattern formed on the surface of the substrate 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. In the resulting line-and-space pattern, the sensitivity was determined in the same manner as above, and the sensitivity of the line-and-space pattern formed using the resist composition before storage over time and the resist after storage over time (at 40 ° C. for 4 weeks). The difference from the sensitivity of the line-and-space pattern formed using the composition, that is, the degree of sensitivity fluctuation, was evaluated according to the following criteria.
(criterion)
A: The observed sensitivity variation is less than 1 mJ/cm ² B: The observed sensitivity variation is 1 mJ/cm ² or more and less than 2 mJ/cm ^{2 C: The observed sensitivity variation is 2 mJ/cm 2 or} more and less than 3 mJ/cm ² D : Observed sensitivity fluctuation is 3 mJ/cm ² or more

[Rectangularity]
Observing the cross-sectional shape of a line-and-space pattern with a line width of 40 nm and a film thickness of 30 nm, a line width Lb at the bottom of the resist pattern and a length measurement scanning electron microscope (SEM, Hitachi Ltd. S-9380II) were measured. The line width La at the top of the resist pattern is measured, and "A" if 0.95 ≤ (La/Lb) ≤ 1.05, 0.90 ≤ (La/Lb) < 0.95, or , “B” if 1.05<(La/Lb)≦1.10, and 0.85≦(La/Lb)<0.90, or 1.10<(La/Lb)≦1 0.15 was rated as "C", and if outside the ranges of "A", "B" and "C" above, it was rated as "D".

<Preparation of actinic ray-sensitive or radiation-sensitive resin composition> (EB exposure)
(Examples 13, 14, 22, 34, 35, 37-126)
Various components shown in Tables 3 and 4 were mixed and mixed so that the solid content concentration (% by mass) shown in Tables 3 and 4 was obtained to obtain a solution. The obtained liquid 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 addition, in the resist composition, in this embodiment, the solid content means all components other than the solvent and specific additives.
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. In addition, the content ratio (% by mass) of the solvent used with respect to the total solvent is shown in the table.
Contents of specific additives were measured in the same manner as above.

<Pattern Forming Method (6): EB Exposure, Alkaline Development (Positive)>
A resist composition shown in Tables 3 and 4 was applied using a spin coater Mark 8 manufactured by Tokyo Electron Co., Ltd. on a 6-inch wafer, and baked (PB) on a hot plate at 110 ° C. for 90 seconds to obtain a film thickness of 80 nm. of the resist film was obtained.
This resist film was subjected to pattern irradiation using an electron beam lithography system (ELS-7500 manufactured by Elionix Co., Ltd.; acceleration voltage: 50 KeV). As the reticle, a mask having a line size of 100 nm and a line:space ratio of 1:1 was used. After irradiation, it is baked (PEB) on a hot plate at 110° C. for 90 seconds, immersed in a 2.38% by mass tetramethylammonium hydroxide aqueous solution as a developer for 60 seconds, and then rinsed with pure water for 30 seconds. By drying, a line-and-space pattern with a pitch of 200 nm and a line width of 100 nm (space width of 100 nm) was obtained.
The optimum exposure dose (sensitivity) (μC/cm ² ) for forming a line-and-space (LS) pattern with a line width of 100 nm was used. In determining the sensitivity, the space width of the pattern was measured using a scanning electron microscope (SEM: 9380II manufactured by Hitachi High-Technologies Corporation).
By the above procedure, a patterned wafer for evaluation having a substrate and a pattern formed on the surface of the substrate 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. In the resulting line-and-space pattern, the sensitivity was determined in the same manner as above, and the sensitivity of the line-and-space pattern formed using the resist composition before storage over time and the resist after storage over time (at 40 ° C. for 4 weeks). The difference from the sensitivity of the line-and-space pattern formed using the composition, that is, the degree of sensitivity fluctuation, was evaluated according to the following criteria.
(criterion)
A: The observed sensitivity variation is less than 1 μC/cm ² B: The observed sensitivity variation is 1 μC/cm ² or more and less than 2 μC/cm ^{2 C: The observed sensitivity variation is 2 μC/cm 2 or} more and less than 3 μC/cm ² D : Observed sensitivity fluctuation of 3 μC/cm ² or more

[Rectangularity]
Observe the cross-sectional shape of a line-and-space pattern with a line width of 100 nm and a film thickness of 80 nm, and use a length measurement scanning electron microscope (SEM Co., Ltd. Hitachi Ltd. S-9380II) to determine the line width Lb at the bottom of the resist pattern, The line width La at the top of the resist pattern is measured, and "A" if 0.95 ≤ (La/Lb) ≤ 1.05, 0.90 ≤ (La/Lb) < 0.95, or , “B” if 1.05<(La/Lb)≦1.10, and 0.85≦(La/Lb)<0.90, or 1.10<(La/Lb)≦1 0.15 was rated as "C", and if outside the ranges of "A", "B" and "C" above, it was rated as "D".

Table 5 shows the obtained evaluation results.

The results in Table 5 show 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.
In addition, Examples 23-33, 36, 59-69, 72, 95-105, 108, 131-141, 144, 167-177, 180, 203-213, 216, 239-249, 252, 275-285, 288, 311-318 are Reference Examples 23-33, 36, 59-69, 72, 95-105, 108, 131-141, 144, 167-177, 180, 203-213, 216, 239-249, 252, 275 to 285, 288, and 311 to 318.

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

Although the present invention has been described in detail and with reference to specific 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 a Japanese patent application (Japanese patent application 2018-248645) filed on December 28, 2018 and a Japanese patent application (Japanese patent application 2019-138319) filed on July 26, 2019, and the content is Incorporated here as a reference.

Claims (7)

a resin (A) whose polarity increases under the action of an acid;
An actinic ray-sensitive or radiation-sensitive resin composition containing a compound (B) that generates an acid upon exposure to actinic rays or radiation, and a compound (P) that is a compound represented by any of the following,
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 composition further contains an acid diffusion control agent, and the acid diffusion control agent is a basic compound.

The actinic ray-sensitive or radiation-sensitive resin according to claim 1 , wherein the content of the compound (P) is 1 ppm or more and 500 ppm or less with respect to the total mass of the actinic ray-sensitive or radiation-sensitive resin composition. Composition. The actinic ray-sensitive or radiation-sensitive according to claim 1 or 2 , wherein 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. elastic resin composition. The sensitizer according to any one of claims 1 to 3 , wherein 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. Light sensitive or radiation sensitive resin composition. A resist film formed from the actinic ray-sensitive or radiation-sensitive resin composition according to any one of claims 1 to 4 . 6. A pattern forming method, comprising the steps of: exposing the resist film according to claim 5 ; and developing the exposed resist film using a developer. A method for manufacturing an electronic device, comprising the pattern forming method according to claim 6 .