JP7309907B2 - Actinic ray-sensitive or radiation-sensitive resin composition, pattern forming method, and electronic device manufacturing method - Google Patents

Description

TECHNICAL FIELD The present invention relates to an actinic ray-sensitive or radiation-sensitive resin composition, 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. Thereafter, development is performed using, for example, an alkaline developer. Thereby, a desired pattern can be obtained by removing the exposed portion.

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).

Resist compositions often contain an organic solvent. Various compounds are used as the organic solvent used in the resist composition, and one example thereof is propylene glycol monomethyl ether acetate (PGMEA). In addition, it is known that alkylene glycol monoalkyl ether acetate such as PGMEA has two isomers, α-type and β-type (see Patent Documents 1 and 2).

Japanese Patent Laid-Open No. 6-324483 Japanese Patent Application Laid-Open No. 2015-64605

A resist composition may be stored for a certain period of time after preparation, but in a conventional resist composition, when a pattern is formed after being stored for a certain period of time, development defects ("development defects after the passage of time ) may occur. Further, in recent years, due to further miniaturization of patterns to be formed, etc., the performance required of the resist composition is becoming higher. For example, excellent Line Width Roughness (LWR) performance is required. ing. Note that the LWR performance refers to the performance that can reduce the LWR of the pattern. In particular, there is a demand for excellent LWR performance (also referred to as “LWR performance after aging”) when pattern formation is performed after the resist composition has been stored for a certain period of time.

An object of the present invention is to provide an actinic ray-sensitive or radiation-sensitive resin composition that suppresses the occurrence of development defects after the passage of time and has excellent LWR performance after the passage of time, and the actinic ray- or radiation-sensitive resin composition. An object of the present invention is to provide a pattern forming method and an electronic device manufacturing method using the method.

式ＡＩ中、Ｘａ ^１ は、水素原子、フッ素原子以外のハロゲン原子、又は１価の有機基を表し、Ｔは、単結合又は２価の連結基を表し、Ｒｘ ^１ ～Ｒｘ ^３ は、それぞれ独立に、アルキル基、シクロアルキル基、アルケニル基、又はアリール基を表し、Ｒｘ ^１ ～Ｒｘ ^３ のいずれか２つが結合して環構造を形成してもよく、形成しなくてもよい。

式（ＡＩＩ）中、
Ｒ _６１ 、Ｒ _６２ 及びＲ _６３ は、各々独立に、水素原子、アルキル基、シクロアルキル基、ハロゲン原子、シアノ基、又はアルコキシカルボニル基を表す。但し、Ｒ _６２ はＡｒ _６ と結合して環を形成していてもよく、その場合のＲ _６２ は単結合又はアルキレン基を表す。
Ｘ _６ は、単結合、－ＣＯＯ－、又は－ＣＯＮＲ _６４ －を表す。Ｒ _６４ は、水素原子又はアルキル基を表す。
Ｌ _６ は、単結合又はアルキレン基を表す。
Ａｒ _６ は、（ｎ＋１）価の芳香族炭化水素基を表し、Ｒ _６２ と結合して環を形成する場合には（ｎ＋２）価の芳香族炭化水素基を表す。
Ｙ _２ は、ｎ≧２の場合には各々独立に、水素原子又は酸の作用により脱離する基を表す。但し、Ｙ _２ の少なくとも１つは、酸の作用により脱離する基を表す。
ｎは、１～４の整数を表す。

一般式（１）中、Ｒ _１ ～Ｒ _３ はメチル基を表す。
［２］
上記一般式（１）で表される化合物の含有量が、上記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、１質量ｐｐｍ以上である、［１］に記載の感活性光線性又は感放射線性樹脂組成物。
［３］
上記一般式（１）で表される化合物の含有量が、上記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、１００質量ｐｐｍ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］
下記一般式（２）で表される化合物を、上記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、０．１質量ｐｐｍ以上５００質量ｐｐｍ以下含有する、［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。

一般式（２）中、Ｒ _４ 及びＲ _５ は各々独立に炭素数１～５のアルキル基を表す。
［５］
上記一般式（２）で表される化合物の含有量が、上記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、１質量ｐｐｍ以上である、［４］に記載の感活性光線性又は感放射線性樹脂組成物。
［６］
上記一般式（２）で表される化合物の含有量が、上記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、２００質量ｐｐｍ以下である、［４］又は［５］に記載の感活性光線性又は感放射線性樹脂組成物。
［７］
水を、上記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、１質量ｐｐｍ以上１質量％以下含有する、［１］～［６］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。
［８］
上記水の含有量が、上記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、０．０１質量％以上である、［７］に記載の感活性光線性又は感放射線性樹脂組成物。
［９］
上記水の含有量が、上記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、０．５質量％以下である、［７］又は［８］に記載の感活性光線性又は感放射線性樹脂組成物。
［１０］
下記一般式（３）で表される化合物を含有し、上記一般式（３）で表される化合物に対する上記一般式（１）で表される化合物の含有量が、０．１質量ｐｐｍ以上０．０５質量％以下である、［１］～［９］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。

一般式（３）中、Ｒ _６ ～Ｒ _８ は各々独立に炭素数１～５のアルキル基を表す。
［１１］
上記一般式（３）で表される化合物に対する上記一般式（１）で表される化合物の含有量が、１質量ｐｐｍ以上０．００５質量％以下である、［１０］に記載の感活性光線性又は感放射線性樹脂組成物。
［１２］
支持体上に［１］～［１１］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を塗布した後に、７０℃～１００℃で加熱することにより感活性光線性又は感放射線性膜を形成する工程、上記感活性光線性又は感放射線性膜を露光する工程、及び、露光された上記感活性光線性又は感放射線性膜を、現像液を用いて現像する工程を含むパターン形成方法。
［１３］
［１２］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。
また、本明細書には参考のためその他の事項についても記載した。 Means for solving the above problems include the following aspects.
[1]
An actinic ray-sensitive or radiation-sensitive resin composition containing a resin whose polarity is increased by the action of an acid, a photoacid generator, and a compound represented by the following general formula (1),
The resin whose polarity is increased by the action of an acid has at least one repeating unit represented by the following formula AI and a repeating unit represented by the following formula (AII),
The photoacid generator is at least one of a sulfonium salt compound and an iodonium salt compound,
The content of the photoacid generator is 2% by mass or more based on the total solid content of the actinic ray-sensitive or radiation-sensitive resin composition,
The content of the compound represented by the general formula (1) is 0.1 mass ppm or more and 500 mass 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.

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, a cycloalkyl group, an alkenyl group, or an aryl group, and any two of Rx ¹ to Rx ³ may or may not combine to form a ring structure.

In 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.
n represents an integer of 1-4.

In general formula (1), R ₁ to R ₃ represent methyl groups.
[2]
The sensitizer according to [1], wherein the content of the compound represented by the general formula (1) is 1 ppm by mass or more with respect to the total mass of the actinic ray-sensitive or radiation-sensitive resin composition. Light sensitive or radiation sensitive resin composition.
[3]
[1] or [2], wherein the content of the compound represented by the general formula (1) is 100 ppm by mass 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 as described.
[4]
[1]-[ 3]. The actinic ray-sensitive or radiation-sensitive resin composition according to any one of 3].

In general formula (2), R ₄ and R ₅ each independently represent an alkyl group having 1 to 5 carbon atoms.
[5]
The sensitizer according to [4], wherein the content of the compound represented by the general formula (2) is 1 mass ppm or more with respect to the total mass of the actinic ray-sensitive or radiation-sensitive resin composition. Light sensitive or radiation sensitive resin composition.
[6]
[4] or [5], wherein the content of the compound represented by the general formula (2) is 200 mass 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 as described.
[7]
The sensitizer according to any one of [1] to [6], containing water in an amount of 1 ppm by mass or more and 1% by mass 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.
[8]
The actinic ray-sensitive or radiation-sensitive resin according to [7], wherein the water content is 0.01% by mass or more with respect to the total mass of the actinic ray-sensitive or radiation-sensitive resin composition. Composition.
[9]
The actinic ray-sensitive or according to [7] or [8], wherein the water content is 0.5% by mass or less with respect to the total mass of the actinic ray-sensitive or radiation-sensitive resin composition A radiation-sensitive resin composition.
[10]
It contains a compound represented by the following general formula (3), and the content of the compound represented by the general formula (1) with respect to the compound represented by the general formula (3) is 0.1 ppm by mass or more and 0 The actinic ray-sensitive or radiation-sensitive resin composition according to any one of [1] to [9], which is .05% by mass or less.

In general formula (3), R ₆ to R ₈ each independently represent an alkyl group having 1 to 5 carbon atoms.
[11]
The actinic ray-sensitive ray according to [10], wherein the content of the compound represented by the general formula (1) with respect to the compound represented by the general formula (3) is 1 ppm by mass or more and 0.005% by mass or less. sensitive or radiation sensitive resin composition.
[12]
After applying the actinic ray-sensitive or radiation-sensitive resin composition according to any one of [1] to [11] on a support, the actinic ray-sensitive or radiation-sensitive resin composition is heated at 70°C to 100°C. forming a radiation-sensitive film, exposing the actinic ray-sensitive or radiation-sensitive film, and developing the exposed actinic ray-sensitive or radiation-sensitive film with a developer. patterning methods including;
[13]
A method for manufacturing an electronic device, including the pattern forming method according to [12].
Other matters are also described herein for reference.

<1>
An actinic ray-sensitive or radiation-sensitive resin composition containing a resin whose polarity is increased by the action of an acid, a photoacid generator, and a compound represented by the following general formula (1),
The content of the compound represented by the general formula (1) is 0.1 mass ppm or more and 500 mass 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.

In general formula (1), R ₁ to R ₃ each independently represent an alkyl group having 1 to 5 carbon atoms.
<2>
The sensitizer according to <1>, wherein the content of the compound represented by the general formula (1) is 1 ppm by mass or more with respect to the total mass of the actinic ray-sensitive or radiation-sensitive resin composition. Light sensitive or radiation sensitive resin composition.
<3>
<1> or <2>, wherein the content of the compound represented by the general formula (1) is 100 ppm by mass 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 as described.
<4>
<1> to < containing a compound represented by the following general formula (2) at 0.1 mass ppm or more and 500 mass ppm or less with respect to the total mass of the actinic ray-sensitive or radiation-sensitive resin composition The actinic ray-sensitive or radiation-sensitive resin composition according to any one of 3>.

In general formula (2), R ₄ and R ₅ each independently represent an alkyl group having 1 to 5 carbon atoms.
<5>
The sensitizer according to <4>, wherein the content of the compound represented by the general formula (2) is 1 mass ppm or more with respect to the total mass of the actinic ray-sensitive or radiation-sensitive resin composition. Light sensitive or radiation sensitive resin composition.
<6>
<4> or <5>, wherein the content of the compound represented by the general formula (2) is 200 mass 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 as described.
<7>
The sensitizer according to any one of <1> to <6>, containing water in an amount of 1 ppm by mass or more and 1% by mass 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.
<8>
The actinic ray-sensitive or radiation-sensitive resin according to <7>, wherein the water content is 0.01% by mass or more with respect to the total mass of the actinic ray-sensitive or radiation-sensitive resin composition. Composition.
<9>
The actinic ray-sensitive or according to <7> or <8>, wherein the water content is 0.5% by mass or less with respect to the total mass of the actinic ray-sensitive or radiation-sensitive resin composition A radiation-sensitive resin composition.
<10>
It contains a compound represented by the following general formula (3), and the content of the compound represented by the general formula (1) with respect to the compound represented by the general formula (3) is 0.1 ppm by mass or more and 0 The actinic ray-sensitive or radiation-sensitive resin composition according to any one of <1> to <9>, which is .05% by mass or less.

In general formula (3), R ₆ to R ₈ each independently represent an alkyl group having 1 to 5 carbon atoms.
<11>
The actinic ray-sensitive light according to <10>, wherein the content of the compound represented by the general formula (1) with respect to the compound represented by the general formula (3) is 1 ppm by mass or more and 0.005% by mass or less. sensitive or radiation sensitive resin composition.
<12>
A step of forming an actinic ray-sensitive or radiation-sensitive film from the actinic ray-sensitive or radiation-sensitive resin composition according to any one of <1> to <11>, the actinic ray-sensitive or radiation-sensitive A pattern forming method comprising the steps of: exposing a film; and developing the exposed actinic ray-sensitive or radiation-sensitive film with a developer.
<13>
A method for manufacturing an electronic device, including the pattern forming method according to <12>.

According to the present invention, an actinic ray- or radiation-sensitive resin composition that suppresses the occurrence of development defects after the passage of time and has excellent LWR performance after the passage of time, and the actinic ray- or radiation-sensitive resin composition A pattern forming method and an electronic device manufacturing method using the method can be provided.

It is a schematic diagram which shows an example of a development defect. It is a schematic diagram which shows an example of a development defect.

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 rays" 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: 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 the emission line spectrum of a mercury lamp, far ultraviolet rays represented by excimer lasers, extreme ultraviolet rays, X-rays, and EUV exposure, but also electron beams and ion beams. It also includes exposure by particle beams such as 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 represents acrylate and methacrylate, and (meth)acryl represents 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.
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") of the present invention comprises a resin whose polarity is increased by the action of an acid, a photoacid generator, and the following general formula (1) An actinic ray-sensitive or radiation-sensitive resin composition containing a compound represented by
The content of the compound represented by the general formula (1) is 0.1 mass ppm or more and 500 mass ppm or less with respect to the total mass of the actinic ray-sensitive or radiation-sensitive resin composition. It is a light sensitive or radiation sensitive resin composition.

In general formula (1), R ₁ to R ₃ each independently represent an alkyl group having 1 to 5 carbon atoms.

The composition of the present invention can solve the problems of the present invention that the occurrence of development defects after the passage of time is suppressed and the LWR performance after the passage of time is excellent by adopting the above constitution.
Although the reason is not clear, the present inventors consider as follows.
The photoacid generator that can be contained in the actinic ray-sensitive or radiation-sensitive resin composition is usually an ionic compound or a highly polar compound, and is highly hydrophilic and therefore easily aggregates. In particular, after aging the actinic ray-sensitive or radiation-sensitive resin composition, photoacid when forming an actinic ray-sensitive or radiation-sensitive film (typically a resist film) using this composition Generating agent tends to aggregate. If the photoacid generator aggregates in the film after forming the actinic ray-sensitive or radiation-sensitive film, development defects tend to occur at the aggregated portions of the photoacid generator. For example, in the case of a positive resist film, the developability of the agglomerated portion of the photoacid generator is increased, so that disconnection defects are likely to occur. Also, in the case of a negative resist film, bridge defects tend to occur because the developability of the agglomerated portion of the photoacid generator is reduced.
The actinic ray-sensitive or radiation-sensitive resin composition of the present invention contains a compound represented by general formula (1). The compound represented by the general formula (1) is a β-type alkylene glycol monoalkyl ether acetate (e.g., β-type PGMEA, etc.), and an α-type alkylene glycol monoalkyl ether acetate (e.g., α-type PGMEA, etc.). ), it tends to remain in the film during actinic ray-sensitive or radiation-sensitive film formation. In addition, the compound represented by the general formula (1) has a high affinity with the photoacid generator, and can suppress aggregation of the photoacid generator during film formation. It is believed that this suppresses the occurrence of development defects after the aging of the actinic ray-sensitive or radiation-sensitive resin composition.

Further, in the actinic ray-sensitive or radiation-sensitive resin composition of the present invention, the compound represented by the general formula (1) is 0.1 mass ppm or more and 500 mass ppm or less with respect to the total mass of the composition. Contain within a specific range. As described above, the compound represented by the general formula (1) is a β-type alkylene glycol monoalkyl ether acetate (e.g., β-type PGMEA, etc.), and an α-type alkylene glycol monoalkyl ether acetate (e.g., α-type PGMEA, etc.), if contained in a large amount in the composition, the amount of residual solvent in the actinic ray-sensitive or radiation-sensitive film becomes excessive, resulting in deterioration of LWR performance after aging. Therefore, in the present invention, the compound represented by general formula (1) shall be contained within a specific range.

The actinic ray-sensitive or radiation-sensitive resin composition of 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.

Details of each component contained in the actinic ray-sensitive or radiation-sensitive resin composition of the present invention are described below.

<Compound Represented by Formula (1)>
The composition of the present invention contains a compound represented by general formula (1).

In general formula (1), R ₁ to R ₃ each independently represent an alkyl group having 1 to 5 carbon atoms.

The alkyl group having 1 to 5 carbon atoms represented by R ₁ to R ₃ may be linear or branched.
The alkyl group having 1 to 5 carbon atoms represented by R ₁ to R ₃ may have no substituent (unsubstituted alkyl group) or may have a substituent.
Each of R ₁ to R ₃ above preferably independently represents an alkyl group having 1 to 3 carbon atoms, more preferably independently represents a methyl group or an ethyl group, and still more preferably represents a methyl group. When R ₁ to R ₃ are methyl groups, the compound represented by general formula (1) represents β-type PGMEA (β-PGMEA).

The composition of the present invention may contain only one compound represented by formula (1), or may contain two or more compounds.

The content of the compound represented by formula (1) is 0.1 ppm by mass or more and 500 ppm by mass or less with respect to the total mass of the actinic ray-sensitive or radiation-sensitive resin composition. Note that "ppm" is an abbreviation for "parts per million". Moreover, "mass ppm" represents mass-based ppm.
When the compound represented by general formula (1) is only one compound, the content of the compound represented by general formula (1) is the content of that compound. Further, the content of the compound represented by the general formula (1) is the total (total amount) of the content of each compound when two or more kinds of the compounds represented by the general formula (1) are present.
When the content of the compound represented by the general formula (1) is less than 0.1 ppm by mass with respect to the total mass of the actinic ray-sensitive or radiation-sensitive resin composition, development defects occur after the passage of time. easier. Further, when the content of the compound represented by the general formula (1) is more than 500 ppm by mass with respect to the total mass of the actinic ray-sensitive or radiation-sensitive resin composition, the LWR performance after aging deteriorates. easier.

The content of the compound represented by the general formula (1) is 0.00, based on the total mass of the actinic ray-sensitive or radiation-sensitive resin composition, since the occurrence of development defects after the passage of time can be further suppressed. It is preferably 5 mass ppm or more, more preferably 1 mass ppm or more, still more preferably 10 mass ppm or more, and particularly preferably 15 mass ppm or more.
Further, since the occurrence of development defects over time can be suppressed more, the content of the compound represented by the general formula (1) is It is preferably 400 mass ppm or less, more preferably 300 mass ppm or less, still more preferably 200 mass ppm or less, particularly preferably 100 mass ppm or less, and 50 mass ppm or less. is most preferred.

The method for adjusting the content of the compound represented by formula (1) is not particularly limited. For example, when the compound represented by the general formula (1) is β-PGMEA, a method of adding isolated β-PGMEA to an actinic ray-sensitive or radiation-sensitive resin composition or a solvent used for its preparation. can be used. A commercially available product can also be used as the isolated β-PGMEA (cas number 70657-70-4). Alternatively, a mixture of α-PGMEA and β-PGMEA (for example, commercially available PGMEA, etc.) may be distilled to separate α-PGMEA and β-PGMEA. Furthermore, PGMEA can be produced using PGME as a raw material, but by producing PGMEA using PGME in which the production of β-isomers is controlled as a raw material, it is also possible to use one in which the content of β-PGMEA is adjusted.

The content of the compound represented by general formula (1) in the actinic ray-sensitive or radiation-sensitive resin composition can be quantified using gas chromatography/mass spectrometry (GC/MS).

<Compound Represented by Formula (2)>
The composition of the present invention preferably further contains a compound represented by the following general formula (2).
The composition of the present invention preferably contains 0.1 mass ppm or more and 500 mass ppm or less of the compound represented by the following general formula (2) with respect to the total mass of the composition of the present invention.

In general formula (2), R ₄ and R ₅ each independently represent an alkyl group having 1 to 5 carbon atoms.

The alkyl group having 1 to 5 carbon atoms represented by R ₄ and R ₅ may be linear or branched.
The alkyl group having 1 to 5 carbon atoms represented by R ₄ and R ₅ may have no substituent (unsubstituted alkyl group) or may have a substituent.
Each of R ₄ and R ₅ above preferably independently represents an alkyl group having 1 to 3 carbon atoms, more preferably independently represents a methyl group or an ethyl group, and still more preferably represents a methyl group. When R ₄ and R ₅ are methyl groups, the compound represented by general formula (2) represents β-type propylene glycol monomethyl ether (β-PGME). When R ₄ is a methyl group and R ₅ is an ethyl group, the compound represented by general formula (2) represents β-type propylene glycol monoethyl ether (β-PGEE).

The composition of the present invention may contain only one compound represented by formula (2), or may contain two or more compounds.

By containing 0.1 ppm by mass or more of the compound represented by the general formula (2) with respect to the total mass of the composition of the present invention, it is possible to further suppress the occurrence of development defects over time, which is preferable. This is because the compound represented by the general formula (2) (typically a primary alcohol) has less steric hindrance and has a high affinity with the photoacid generator, suppressing aggregation of the photoacid generator during film formation. This is considered to be because it is possible to
In addition, it is preferable that the compound represented by the general formula (2) is contained in an amount of 500 ppm by mass or less based on the total mass of the composition of the present invention, because the LWR performance after aging can be further improved. By setting this to 500 ppm by mass or less, the compound represented by the general formula (2) (typically a primary alcohol) is used in the composition of the present invention as a resin whose polarity increases due to the action of an acid. It is thought that it is because it can prevent reacting with other components.
The content of the compound represented by the general formula (2) is 0.5 mass ppm or more with respect to the total mass of the composition of the present invention, because it can further suppress the occurrence of development defects over time. is preferably 1 mass ppm or more, more preferably 10 mass ppm or more, and particularly preferably 15 mass ppm or more.
In addition, the content of the compound represented by the general formula (2) is 500 ppm by mass or less with respect to the total mass of the composition of the present invention, because the occurrence of development defects after the passage of time can be further suppressed. It is preferably 300 mass ppm or less, more preferably 200 mass ppm or less, particularly preferably 100 mass ppm or less, and most preferably 50 mass ppm or less.

The content of the compound represented by the general formula (2) is the content of that compound when the compound represented by the general formula (2) is only one compound. Moreover, when two or more kinds of compounds represented by the general formula (2) are present, the content of the compound represented by the general formula (2) is the total content (total amount) of the respective compounds.

The method for adjusting the content of the compound represented by formula (2) is not particularly limited. For example, when the compound represented by the general formula (2) is β-PGME, a method of adding isolated β-PGME to an actinic ray-sensitive or radiation-sensitive resin composition or a solvent used for its preparation. can be used. A commercially available product can also be used as the isolated β-PGME (cas number 1589-47-5). Alternatively, a mixture of α-PGME and β-PGME (for example, PGME generally available on the market) may be distilled to separate α-PGME and β-PGME. Furthermore, PGME in which the formation of the β-isomer is controlled during production can also be used.
Further, for example, when the compound represented by the general formula (2) is β-PGEE, the isolated β-PGEE is added to the actinic ray-sensitive or radiation-sensitive resin composition or the solvent used for its preparation. method can be used. A commercial product can also be used as the isolated β-PGEE (cas number 19089-47-5). Alternatively, a mixture of α-PGEE and β-PGEE (for example, commercially available PGEE) may be distilled to separate α-PGEE and β-PGEE. Furthermore, PGEE in which the formation of the β-isomer is controlled during production can also be used.

The content of the compound represented by general formula (2) in the actinic ray-sensitive or radiation-sensitive resin composition can be quantified using gas chromatography/mass spectrometry (GC/MS).

<Water>
The composition of the invention preferably further contains water.
Water has a high affinity with the compound represented by the general formula (1) or the compound represented by the general formula (2), and the composition of the present invention contains water. When forming an actinic ray-sensitive or radiation-sensitive film (typically a resist film) using a substance, the compound represented by the general formula (1) or the general formula (2) is added to the film together with water. ) tends to remain, and the above-mentioned effects of these compounds (suppression of development defects over time, etc.) are more likely to be exerted, which is preferable.

The composition of the present invention preferably contains water in an amount of 1 ppm by mass or more and 2% by mass or less, more preferably 1 ppm by mass or more and 1% by mass or less, relative to the total mass of the composition of the present invention. .

The content of water is preferably 1 ppm by mass or more, and 10 ppm by mass or more, based on the total mass of the composition of the present invention, because it can further suppress the occurrence of development defects after the passage of time. is more preferably 0.01 mass % (100 mass ppm) or more, and particularly preferably 0.1 mass % (1000 mass ppm) or more.
The water content is preferably 2% by mass (20000 ppm by mass) or less, more preferably 1% by mass (10000 ppm by mass) or less, relative to the total mass of the composition of the present invention. It is more preferably 0.5 mass % (5000 mass ppm) or less. When the water content is within the above range, the resin that increases in polarity due to the action of acid in the composition of the present invention does not become insoluble and precipitate in the liquid or during film formation, and as a result, the LWR after aging is improved. Excellent performance.

As water, for example, pure water, ultrapure water, or the like can be used.

A method for adjusting the water content is not particularly limited. For example, a method of using a solvent in which a predetermined amount of water is mixed in advance with a solvent used for preparing an actinic ray-sensitive or radiation-sensitive resin composition, or a method of using a water-containing actinic ray-sensitive or radiation-sensitive resin composition. On the other hand, for example, a method using a general dehydration method such as molecular sieves can be used.

The water content in the actinic ray-sensitive or radiation-sensitive resin composition can be measured using a Karl Fischer moisture meter.

<Compound Represented by Formula (3)>
The composition of the present invention preferably further contains a compound represented by the following general formula (3).
The composition of the present invention contains a compound represented by the following general formula (3), and the content of the compound represented by the above general formula (1) with respect to the compound represented by the following general formula (3) is It is preferably 0.1 mass ppm or more and 0.05 mass % or less, more preferably 1 mass ppm or more and 0.005 mass % or less.

In general formula (3), R ₆ to R ₈ each independently represent an alkyl group having 1 to 5 carbon atoms.

The alkyl group having 1 to 5 carbon atoms represented by R ₆ to R ₈ may be linear or branched.
The alkyl group having 1 to 5 carbon atoms represented by R ₆ to R ₈ may have no substituent (unsubstituted alkyl group) or may have a substituent.
Each of R ₆ to R ₈ above preferably independently represents an alkyl group having 1 to 3 carbon atoms, more preferably independently represents a methyl group or an ethyl group, and still more preferably represents a methyl group. When R ₆ to R ₈ are methyl groups, the compound represented by general formula (3) represents α-type PGMEA (α-PGMEA).

Since the compound represented by the general formula (3) has a structure similar to that of the compound represented by the general formula (1), it has a high affinity with the compound represented by the general formula (1). Further, when the compound represented by the general formula (1) and the compound represented by the general formula (3) coexist, the solubility of the photoacid generator increases, and the composition of the present invention can be used to sensitize actinic radiation. When forming a sensitive or radiation-sensitive film (typically a resist film), the aggregation of the photoacid generator is easily suppressed, and the above-mentioned effects (suppression of development defects after the passage of time, etc.) are more enhanced. It is preferable because it is easily exhibited.

When the composition of the present invention contains a compound represented by general formula (3) in addition to the compound represented by general formula (1), R ₆ in general formula (3) is represented by general formula (1) is preferably the same as R ₁ in general formula (3), R ₇ in general formula (3) is preferably the same as R ₂ in general formula (1), and R ₈ in general formula (3) is the same as general formula ( It is preferably the same as R ₃ in 1). As a result, the affinity between the compound represented by the general formula (3) and the compound represented by the general formula (1) becomes very high, and the above effects are more likely to be exhibited.

The composition of the present invention may contain only one compound represented by formula (3), or may contain two or more compounds.

The content of the compound represented by the general formula (3) is the content of that compound when the compound represented by the general formula (3) is only one compound. Moreover, when two or more kinds of compounds represented by the general formula (3) are present, the content of the compound represented by the general formula (3) is the sum (total amount) of the contents of the respective compounds.

The compound represented by general formula (3) may be used as a solvent, which will be described later, for example.
When the compound represented by the general formula (3) is used as a solvent, the solid content concentration of the composition of the present invention is such that the compound represented by the general formula (3) is 0.5% by mass to 60% by mass. It is preferable to use a solvent containing, more preferably a solvent containing a compound represented by the general formula (3) so as to be 1.0% by mass to 45% by mass, 1.0% by mass to 40% by mass %, it is more preferable to use a solvent containing the compound represented by the general formula (3).
When the compound represented by the general formula (3) is used as the solvent in the composition of the present invention, the mass of the compound represented by the general formula (3) with respect to the total mass of the solvent is 50% by mass or more and 100% by mass or less. is preferred.
The "solid content" in the composition of the present invention means a solvent, water, a compound represented by the general formula (1), and a compound represented by the general formula (2) from all the components contained in the composition of the present invention. , and the compound represented by the general formula (3), and may be solid or liquid at 25° C., for example.
Further, the "total solid content" in the composition of the present invention refers to the total composition of the composition, solvent, water, the compound represented by the general formula (1), the compound represented by the general formula (2), and general It refers to the total mass of components excluding the compound represented by formula (3).

The method for adjusting the content of the compound represented by formula (3) is not particularly limited. For example, when the compound represented by the general formula (3) is α-PGMEA, the isolated α-PGMEA may be added or used as a solvent in the preparation of the actinic ray-sensitive or radiation-sensitive resin composition. can do. A commercially available product can also be used as the isolated α-PGMEA (cas number 108-65-6). Alternatively, a mixture of α-PGMEA and β-PGMEA (for example, commercially available PGMEA, etc.) may be distilled to separate α-PGMEA and β-PGMEA.

The content of the compound represented by general formula (3) in the actinic ray-sensitive or radiation-sensitive resin composition can be quantified using gas chromatography/mass spectrometry (GC/MS).

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

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 of 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 formed. A mold 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, a cycloalkyl group, an alkenyl group, or an aryl 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 alkenyl groups of Rx ¹ , Rx ² and Rx ³ may be linear or branched. The number of carbon atoms in the alkenyl group is preferably 2-5, more preferably 2-3. A vinyl group is preferred as the alkenyl group.
The aryl groups of Rx ¹ , Rx ² and Rx ³ may be monocyclic or polycyclic. The number of carbon atoms in the aryl group is preferably 6-14, more preferably 6-10. As the aryl group, a phenyl group, a naphthyl group, an anthryl group and the like are preferable.

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), a cycloalkyl group (monocyclic or polycyclic), an alkenyl group (linear or branched), or an aryl 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.
The aryl group represented by Rx ₁ to Rx ₃ is preferably an aryl group having 6 to 14 carbon atoms, more preferably an aryl group having 6 to 10 carbon atoms. Examples of the aryl group for Rx ₁ to Rx ₃ include phenyl group, naphthyl group, anthryl group and the like.
The alkenyl groups represented by Rx ₁ to Rx ₃ are preferably alkenyl groups having 2 to 5 carbon atoms, more preferably alkenyl groups having 2 to 3 carbon atoms. A vinyl group is preferable as the alkenyl group for Rx ₁ to Rx ₃ .
For example, when the composition of the present invention is a resist composition for EUV exposure, an alkyl group, a cycloalkyl group, an alkenyl group, an aryl group represented by Rx ₁ to Rx ₃ , and 2 of Rx ₁ to Rx ₃ It is also preferred that the ring formed by combining two atoms further has a fluorine atom or an iodine atom as a substituent.

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.

Specific examples of the 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 are shown below, but are not limited to these specific examples.

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 in which two or more groups are combined, for example, a group in which an alkylene group and -COO- are combined, and a group in which -OCO- and an alkylene group are combined. 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 to 30 mol%, and 10 mol% to 25 mol% with respect to all structural units in the resin (A). 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 (a3)]
Resin (A) can further have the following repeating unit (a3).
The repeating unit (a3) is a repeating unit derived from a monomer (also referred to as “monomer a3”) having a glass transition temperature of 50° C. or lower when homopolymerized.
Also, the repeating unit (a3) is a non-acid-decomposable repeating unit. Therefore, the repeating unit (a3) 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 a3 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 a3 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 in the above range when the monomer a3 is a homopolymer, 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 (a3) 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 (a3) 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 (a3) 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 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-degradable alkyl group having a carboxy group or a hydroxyl group, which may contain a heteroatom in the chain, a non-acid-decomposable alkyl group which may contain a heteroatom in the chain, a ring member A group substituted by a non-acid-decomposable cycloalkyl group having a carboxy group or a hydroxyl group, which may contain a heteroatom, or a non-acid group having a carboxy group or a hydroxyl group, which may contain a heteroatom in a ring member represents a 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 , a non-acid-decomposable alkyl group which may contain a heteroatom in the chain, A group substituted by a non-acid-degradable cycloalkyl group having a carboxy group or a hydroxyl group, which may contain a heteroatom in a ring member, 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 a non-acid-decomposable alkyl group which may contain a heteroatom in the chain and a non-acid-decomposable cycloalkyl group which may contain a heteroatom in a ring member and which has a carboxy group or a hydroxyl group. A group substituted with an alkyl group or a non-acid-decomposable cycloalkyl group having a carboxy group or a hydroxyl group, which may contain a heteroatom in a ring member, is preferred. Examples of this aspect include repeating units having the following structures.

Examples of monomer a3 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 a3 is 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 (a3), or may contain two or more types of repeating units (a3).
In the resin (A), the content of the repeating unit (a3) (the total content of the repeating units (a3) when a plurality of repeating units (a3) are present) 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 (a3) in the resin (A) (the total when there are a plurality of repeating units (a3)) 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 Having Acid Group]
Resin (A) preferably has a repeating unit having an acid group.
As the acid group, an acid group having a pKa of 13 or less is preferable. The acid dissociation constant of the acid group is preferably 13 or less, more preferably 3-13, even more preferably 5-10.
When the resin (A) has an acid group with a pKa of 13 or less, the content of the acid group in the resin (A) is not particularly limited, but is usually 0.2 to 6.0 mmol/g. . The content of acid groups in the resin (A) is preferably 0.8 to 6.0 mmol/g, more preferably 1.2 to 5.0 mmol/g, even more preferably 1.6 to 4.0 mmol/g. . If the content of the acid group is within the above range, the development proceeds satisfactorily, the formed pattern shape is excellent, and the resolution is also excellent.
The acid group is preferably at least one selected from, for example, a carboxy group, a hydroxyl group, a phenolic hydroxyl group, a fluorinated alcohol group (preferably a hexafluoroisopropanol group), a sulfonic acid group, and a sulfonamide group.
In the above hexafluoroisopropanol group, a group in which one or more fluorine atoms (preferably 1 to 2) are substituted with a group other than a fluorine atom is also preferable as the acid group. Such groups include, for example, groups containing —C(CF ₃ )(OH)—CF ₂ —. The group containing -C(CF ₃ )(OH)-CF ₂ - may be a cyclic group containing -C(CF ₃ )(OH)-CF ₂ -.
The repeating unit having an acid group is a repeating unit different from the structural unit having an acid-decomposable group and the structural unit having at least one selected from the group consisting of a lactone structure, a sultone structure, and a carbonate structure. Units are preferred.

A repeating unit having an acid group may have a fluorine atom or an iodine atom.

[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 of the present invention is for fluorine argon (ArF) laser exposure, the resin (A) substantially has an aromatic group from the viewpoint of ArF permeability. preferably not. 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 of the present invention is for krypton fluoride (KrF) exposure, electron beam (EB) exposure or extreme ultraviolet (EUV) exposure, the resin (A) is aromatic It preferably contains a structural unit having a group 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 of 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 preferably has a structure protected by a leaving group (leaving group).
The content of the structural unit having an aromatic hydrocarbon group contained in the resin (A) is preferably 30 mol% to 100 mol%, preferably 40 mol% to 100 mol, based on the total structural units in the resin (A). %, more preferably 50 mol % to 100 mol %.

[Repeating Unit Having Photoacid-Generating Group]
The resin (A) may have, as a repeating unit other than the above, a repeating unit having a group that generates an acid upon exposure to actinic rays or radiation (also referred to as a "photoacid-generating group"). When the resin (A) has a repeating unit having a photoacid-generating group, it can be considered that the repeating unit having a photoacid-generating group corresponds to the photoacid generator. Examples of repeating units having a photoacid-generating group include repeating units represented by the following general formula (4).

^R41 represents a hydrogen atom or a methyl group. ^L41 represents a single bond or a divalent linking group. ^L42 represents a divalent linking group. ^R40 represents a structural site that is decomposed by exposure to actinic rays or radiation to generate an acid in the side chain.
Examples of repeating units having a photoacid-generating group are shown below.

In addition, specific examples of the repeating unit represented by the general formula (4) include, for example, repeating units described in paragraphs [0094] to [0105] of JP-A-2014-041327, and International Publication No. 2018/ Repeating units described in paragraph [0094] of 193954 are exemplified.

The resin (A) may not have a repeating unit having a photoacid-generating group, but when the resin (A) has a repeating unit having a photoacid-generating group, it contains a repeating unit having a photoacid-generating group. The amount is preferably 1 mol % or more, more preferably 2 mol % or more, based on all repeating units in the resin (A). Moreover, the upper limit of the content of the repeating unit having a photoacid-generating group is preferably 20 mol % or less, more preferably 10 mol % or less, and even more preferably 5 mol % or less.

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-16 and A-21 to A-36 used in 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 of the present invention. More preferably, 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 of the present invention contains a cross-linking agent (G) described later, the actinic ray-sensitive or radiation-sensitive resin composition of the present invention has an alkali-soluble It is preferable to contain a 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 of 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. At least a resin (C) other than a resin and a resin whose polarity is increased by the action of an acid may be included.
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 of the present invention is preferably 30% by mass or more, more preferably 40% by mass or more, It is 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. 2016/0282720 can be suitably used as the resin (C).

[Hydrophobic resin]
The actinic ray-sensitive or radiation-sensitive resin composition of the present invention preferably contains a hydrophobic resin (also referred to as "hydrophobic resin (E)").
The actinic ray-sensitive or radiation-sensitive resin composition of the present invention may contain 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. preferable.
By containing the hydrophobic resin (E) in the actinic ray-sensitive or radiation-sensitive resin composition of the present invention, the static/dynamic contact angle on the surface of the actinic ray-sensitive or radiation-sensitive film is controlled. can do. 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 preferable.

In formulas (F2) to (F4),
R ⁵⁷ to R ⁶⁸ each independently represent a hydrogen atom, a fluorine atom or an alkyl group (linear or branched). 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 from the viewpoint that the effects of the present invention are 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
Further, the actinic ray-sensitive or radiation-sensitive resin composition of the present invention has improved latitude in depth of focus, pattern linearity, development characteristics, suppression of outgassing, improvement in immersion liquid followability in immersion exposure, and From the viewpoint of reducing impregnation 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.

Further, 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.
Examples of the hydrophobic resin (E) include, but are not limited to, resins in which the following structural units are arbitrarily combined, or resins E-1 to E-15 used in Examples.

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, based on the total solid content of the actinic ray-sensitive or radiation-sensitive resin composition of the present invention. 05% by mass to 8% by mass is more preferable.

<(B) Photoacid generator>
The composition of the present invention 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.
The photoacid generator is preferably an ionic compound or a highly polar compound, preferably an ionic compound.
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 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 the photoacid generator, compounds PAG-1 to PAG-37 used in the examples are also preferable, but not limited to these.

The acid dissociation constant pKa of the acid generated from the photoacid generator by actinic rays or radiation irradiation is not particularly limited, but is preferably less than 1.1, more preferably less than -1.0. preferable.
The lower limit of the acid dissociation constant pKa of the acid generated from the photoacid generator by actinic rays or radiation irradiation is not particularly limited, but is usually -10.

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).

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.

The photoacid generator contained in the composition of the present invention may be at least one of compound (I) and compound (II) below. Compound (I) and compound (II) are also referred to as specific photoacid generators.

<Compound (I)>
Compound (I) is a compound having one or more structural moieties X shown below and one or more structural moieties Y shown below, wherein the first acidic It is a compound that generates an acid containing a site and a second acidic site described below derived from the structural site Y described below.
Structural site X: Structural site consisting of an anionic site A ₁ ⁻ and a cation site M ₁ ⁺ and forming a first acidic site represented by HA ₁ upon exposure to actinic rays or radiation Structural site Y: Anionic site A A structural moiety consisting of ₂ ⁻ and a cationic moiety M ₂ ⁺ and forming a second acidic site represented by HA ₂ upon exposure to actinic rays or radiation provided that compound (I) satisfies condition I below.

Condition I: A compound PI obtained by replacing the cation site M ₁ ⁺ in the structural site X and the cation site M ₂ ⁺ in the structural site Y in the compound (I) with H ⁺ in the structural site X and an acid dissociation constant a1 derived from the acidic site represented by HA ₁ obtained by replacing the cation site M 1 ⁺ with H ⁺ , and replacing the cation site M ₂ ⁺ in the structural site _Y with H ⁺ It has an acid dissociation constant a2 derived from the acidic site represented by _HA2 , and the acid dissociation constant a2 is greater than the acid dissociation constant a1.

Condition I will be described in more detail below.
When the compound (I) is, for example, an acid-generating compound having one first acidic site derived from the structural site X and one second acidic site derived from the structural site Y , compound PI corresponds to "a compound having HA ₁ and HA ₂ ".
More specifically, the acid dissociation constant a1 and the acid dissociation constant a2 of the compound PI are such that when the acid dissociation constant of the compound PI is determined, the compound PI is "a compound having A ₁ ^- and HA ₂ is the acid dissociation constant a1, and the pKa when the above "compound having A ₁ ^- and HA ₂ " becomes "the compound having A ₁ ^- and A ₂ ^- " is the acid dissociation constant a2 be.

Further, the compound (I) is, for example, a compound that generates an acid having two first acidic sites derived from the structural site X and one second acidic site derived from the structural site Y. In some cases, compound PI is a "compound with two HA ₁ and one HA ₂ ".
When the acid dissociation constant of such compound PI is obtained, the acid dissociation constant when compound PI becomes "a compound having one A ₁ ^- , one HA ₁ and one HA ₂ ", and "one The acid dissociation constant when the "compound having A ₁ ^- , one HA ₁ and one HA ₂ " becomes "the compound having two A ₁ ^- and one HA ₂ " is the acid dissociation constant a1 correspond to Also, the acid dissociation constant when "a compound having two A ₁ ^- and one HA _{2 -} " becomes "a compound having two A ₁ ^- and A ₂ ^- " corresponds to the acid dissociation constant a2. That is, in the case of such a compound PI, when it has a plurality of acid dissociation constants derived from the acidic site represented by HA ₁ obtained by replacing the cation site M ₁ ⁺ in the structural site X with H ⁺ , a plurality of The value of the acid dissociation constant a2 is larger than the largest value among the acid dissociation constants a1. The acid dissociation constant when the compound PI becomes "a compound having one A ₁ ^- , one HA ₁ and one HA ₂ " is aa, and "one A ₁ ^- and one HA ₁ and 1 The relationship ^between aa and ab satisfies aa<ab, where ab is the acid dissociation constant when a compound having two _HA2 's becomes _a compound having two A1- and one _HA2 . .

The acid dissociation constant a1 and the acid dissociation constant a2 are determined by the method for measuring the acid dissociation constant described above.
The above compound PI corresponds to an acid generated when compound (I) is irradiated with actinic rays or radiation.
When compound (I) has two or more structural moieties X, each structural moiety X may be the same or different. Two or more of A ₁ ⁻ and two or more of M ₁ ⁺ may be the same or different.
In compound (I), A ₁ ⁻ and A ₂ ⁻ , and M ₁ ⁺ and M ₂ ⁺ may be the same or different, but A 1 ⁻ and A ₂ − may be the same or different. Each A ₂ ^- is preferably different.

The difference between the acid dissociation constant a1 (the maximum value when there are multiple acid dissociation constants a1) and the acid dissociation constant a2 is 0.1 in the above compound PI in that the LWR performance of the formed pattern is superior. 0.5 or more is more preferable, and 1.0 or more is still more preferable. The upper limit of the difference between the acid dissociation constant a1 (the maximum value if there are a plurality of acid dissociation constants a1) and the acid dissociation constant a2 is not particularly limited, but is, for example, 16 or less.

In addition, in the compound PI, the acid dissociation constant a2 is, for example, 20 or less, preferably 15 or less, from the viewpoint that the LWR performance of the formed pattern is more excellent. The lower limit of the acid dissociation constant a2 is preferably -4.0 or more.

In addition, in the compound PI, the acid dissociation constant a1 is preferably 2.0 or less, more preferably 0 or less, from the viewpoint that the LWR performance of the pattern to be formed is more excellent. The lower limit of the acid dissociation constant a1 is preferably −20.0 or more.

The anion site A ₁ ^- and the anion site A ₂ ^- are structural sites containing negatively charged atoms or atomic groups, for example, formulas (AA-1) to (AA-3) and formula (BB -1) to (BB-6). The anion site A ₁ ^- is preferably one capable of forming an acidic site with a small acid dissociation constant, and among these, any one of formulas (AA-1) to (AA-3) is preferred. The anion site A ₂ ^- is preferably one capable of forming an acidic site having a larger acid dissociation constant than the anion site A ₁ ^- , and is selected from any of formulas (BB-1) to (BB-6). is preferred. In formulas (AA-1) to (AA-3) and formulas (BB-1) to (BB-6) below, * represents a bonding position. Each ^RA independently represents a monovalent organic group. The monovalent organic group represented by ^RA includes a cyano group, a trifluoromethyl group, a methanesulfonyl group, and the like.

Moreover, the cation site M ₁ ⁺ and the cation site M ₂ ⁺ are structural sites containing positively charged atoms or atomic groups, and examples thereof include monovalent organic cations. Although the organic cation is not particularly limited, cations represented by formulas ZI and ZII described above are preferably used.

The specific structure of compound (I) is not particularly limited, but examples thereof include compounds represented by formulas (Ia-1) to (Ia-5) described below.
First, the compound represented by Formula (Ia-1) will be described below. The compounds represented by formula (Ia-1) are as follows.

M ₁₁ ⁺ A ₁₁ ^- - L ₁ - A ₁₂ ^- M ₁₂ ⁺ (Ia-1)

Compound (Ia-1) generates an acid represented by HA ₁₁ -L ₁ -A ₁₂ H upon exposure to actinic rays or radiation.

In formula (Ia-1), M ₁₁ ⁺ and M ₁₂ ⁺ each independently represent an organic cation.
A ₁₁ ^- and A ₁₂ ^- each independently represent a monovalent anionic functional group.
L ₁ represents a divalent linking group.
Each of M ₁₁ ⁺ and M ₁₂ ⁺ may be the same or different.
A ₁₁ ^- and A ₁₂ ^- may be the same or different, but are preferably different from each other.
However, in the compound PIa (HA ₁₁ -L ₁ -A ₁₂ H) obtained by replacing the organic cations represented by M ₁₁ ⁺ and M ₁₂ ⁺ with H ⁺ in the above formula (Ia-1), A ₁₂ H The acid dissociation constant a2 derived from the acidic site represented is greater than the acid dissociation constant a1 derived from the acidic site represented by _HA11 . The preferred values of the acid dissociation constant a1 and the acid dissociation constant a2 are as described above. Further, the compound PIa and the acid generated from the compound represented by the formula (Ia-1) upon exposure to actinic rays or radiation are the same.
At least one of M ₁₁ ⁺ , M ₁₂ ⁺ , A ₁₁ ⁻ , A ₁₂ ⁻ , and L ₁ may have an acid-decomposable group as a substituent.

In formula (Ia-1), the organic cations represented by M ₁ ⁺ and M ₂ ⁺ are not particularly limited, but cations represented by formula ZI or ZII are preferably used.

The monovalent anionic functional group represented by A ₁₁ ^- intends a monovalent group containing the above-described anionic site A ₁ ^- . Further, the monovalent anionic functional group represented by A ₁₂ ^- is intended to be a monovalent group containing the above-described anion site A ₂ ^- .
The monovalent anionic functional groups represented by A ₁₁ ^- and A ₁₂ ^- include any of the above formulas (AA-1) to (AA-3) and formulas (BB-1) to (BB-6). It is preferably a monovalent anionic functional group containing an anion site, selected from the group consisting of formulas (AX-1) to (AX-3) and formulas (BX-1) to (BX-7) is more preferably a monovalent anionic functional group. Among the monovalent anionic functional groups represented by A ₁₁ ^- , monovalent anionic functional groups represented by any one of formulas (AX-1) to (AX-3) are preferred. preferable. Further, as the monovalent anionic functional group represented by A ₁₂ ^- , a monovalent anionic functional group represented by any one of the formulas (BX-1) to (BX-7) is preferable. , a monovalent anionic functional group represented by any one of the formulas (BX-1) to (BX-6) is more preferred.

In formulas (AX-2) to (AX-3), R ^A1 and R ^A2 each independently represent a monovalent organic group. In formulas (AX-1) to (AX-3), * represents a bonding position.

The monovalent organic group represented by R ^A1 includes a cyano group, a trifluoromethyl group, a methanesulfonyl group, and the like.

The monovalent organic group represented by ^RA2 is preferably a linear, branched or cyclic alkyl group or aryl group.
The number of carbon atoms in the alkyl group is preferably 1-15, more preferably 1-10, even more preferably 1-6.
The above alkyl group may have a substituent. The substituent is preferably a fluorine atom or a cyano group, more preferably a fluorine atom. When the alkyl group has a fluorine atom as a substituent, it may be a perfluoroalkyl group.

The aryl group is preferably a phenyl group or a naphthyl group, more preferably a phenyl group.
The aryl group may have a substituent. The substituent is preferably a fluorine atom, an iodine atom, a perfluoroalkyl group (eg, preferably having 1 to 10 carbon atoms, more preferably having 1 to 6 carbon atoms), or a cyano group, a fluorine atom, an iodine atom, or A perfluoroalkyl group is more preferred.

In formulas (BX-1) to (BX-4) and formula (BX-6), R 2 ^B represents a monovalent organic group. In formulas (BX-1) to (BX-7), * represents a bonding position.
The monovalent organic group represented by ^RB is preferably a linear, branched or cyclic alkyl group or aryl group.
The number of carbon atoms in the alkyl group is preferably 1-15, more preferably 1-10, even more preferably 1-6.
The above alkyl group may have a substituent. Although the substituent is not particularly limited, the substituent is preferably a fluorine atom or a cyano group, more preferably a fluorine atom. When the alkyl group has a fluorine atom as a substituent, it may be a perfluoroalkyl group.
In addition, the carbon atom that is the bonding position in the alkyl group (for example, in the case of formulas (BX-1) and (BX-4), the carbon atom directly bonded to -CO- indicated in the formula in the alkyl group is applicable. However, in the case of formulas (BX-2) and (BX-3), the carbon atom directly bonded to -SO ₂ - specified in the formula in the alkyl group corresponds, and in the case of formula (BX-6), In the alkyl group, the carbon atom directly bonded to ^N-- in the formula.) has a substituent, it is preferably a substituent other than a fluorine atom or a cyano group.
In the above alkyl group, at least one methylene group ( _--CH.sub.2-- ) constituting the alkyl group may be replaced with a carbonyl group (--C(=O)--).

The aryl group is preferably a phenyl group or a naphthyl group, more preferably a phenyl group.
The aryl group may have a substituent. Examples of substituents include a fluorine atom, an iodine atom, a perfluoroalkyl group (eg, preferably having 1 to 10 carbon atoms, more preferably 1 to 6 carbon atoms), a cyano group, an alkyl group (eg, 1 to 10 carbon atoms). is preferred, and more preferably 1 to 6 carbon atoms.), an alkoxy group (e.g., preferably 1 to 10 carbon atoms, more preferably 1 to 6 carbon atoms.), or an alkoxycarbonyl group (e.g., 2 to 10 carbon atoms are preferred, and those having 2 to 6 carbon atoms are more preferred.), and more preferred is a fluorine atom, an iodine atom, a perfluoroalkyl group, an alkyl group, an alkoxy group, or an alkoxycarbonyl group.

In formula (Ia-1), the divalent linking group represented by L ₁ is not particularly limited, and includes -CO-, -NR-, -CO-, -O-, -S-, -SO-, —SO ₂ —, an alkylene group (preferably having 1 to 6 carbon atoms, which may be linear or branched), a cycloalkylene group (preferably having 3 to 15 carbon atoms), an alkenylene group (preferably having 2 to 6 carbon atoms), ), a divalent aliphatic heterocyclic group (preferably a 5- to 10-membered ring having at least one N atom, O atom, S atom, or Se atom in the ring structure, more preferably a 5- to 7-membered ring, 5 ~ 6-membered ring is more preferable.), a divalent aromatic heterocyclic group (at least one N atom, O atom, S atom, or Se atom in the ring structure is preferably a 5- to 10-membered ring, 5- A 7-membered ring is more preferred, and a 5- to 6-membered ring is even more preferred.), a divalent aromatic hydrocarbon ring group (preferably a 6- to 10-membered ring, more preferably a 6-membered ring.), and a plurality of these A combined divalent linking group is included. The above R includes a hydrogen atom or a monovalent organic group. Although the monovalent organic group is not particularly limited, for example, an alkyl group (preferably having 1 to 6 carbon atoms) is preferable.
Further, the alkylene group, the cycloalkylene group, the alkenylene group, the divalent aliphatic heterocyclic group, the divalent aromatic heterocyclic group, and the divalent aromatic hydrocarbon ring group have a substituent. You may have Substituents include, for example, halogen atoms (preferably fluorine atoms).

Among them, the divalent linking group represented by _L1 is preferably a divalent linking group represented by formula (L1).

In formula (L1), L ₁₁₁ represents a single bond or a divalent linking group.
The divalent linking group represented by L ₁₁₁ is not particularly limited, and may be, for example, —CO—, —NH—, —O—, —SO—, —SO ₂ —, or have a substituent. An alkylene group (preferably having 1 to 6 carbon atoms, which may be linear or branched), an optionally substituted cycloalkylene group (preferably having 3 to 15 carbon atoms), having a substituent an aryl group (preferably having 6 to 10 carbon atoms) which may be substituted, and a divalent linking group combining a plurality of these groups. The substituent is not particularly limited, and examples thereof include halogen atoms.
p represents an integer of 0-3, preferably an integer of 1-3.
v represents an integer of 0 or 1;
Each Xf ₁ independently represents a fluorine atom or an alkyl group substituted with at least one fluorine atom. The number of carbon atoms in this alkyl group is preferably 1-10, more preferably 1-4. A perfluoroalkyl group is preferable as the alkyl group substituted with at least one fluorine atom.
Each _Xf2 independently represents a hydrogen atom, an alkyl group optionally having a fluorine atom as a substituent, or a fluorine atom. The number of carbon atoms in this alkyl group is preferably 1-10, more preferably 1-4. _Xf2 preferably represents a fluorine atom or an alkyl group substituted with at least one fluorine atom, more preferably a fluorine atom or a perfluoroalkyl group.
Among them, Xf ₁ and Xf ₂ are each independently preferably a fluorine atom or a perfluoroalkyl group having 1 to 4 carbon atoms, more preferably a fluorine atom or CF ₃ . In particular, both Xf ₁ and Xf ₂ are more preferably fluorine atoms.
* represents a binding position.
When L ₁ in formula (Ia-1) represents a divalent linking group represented by formula (L1), the bond (*) on the L ₁₁₁ side in formula (L1) is represented by formula (Ia-1 ) is preferred to bind to A ₁₂ ⁻ in

Next, Formulas (Ia-2) to (Ia-4) will be described.

In formula (Ia-2), A _21a ^- and A _21b ^- each independently represent a monovalent anionic functional group. Here, the monovalent anionic functional groups represented by A _21a ^- and A _21b ^- are meant to be monovalent groups containing the above-described anionic site A ₁ ^- . The monovalent anionic functional groups represented by A _21a ^- and A _21b ^- are not particularly limited. Examples include anionic functional groups.
A ₂₂ ^- represents a divalent anionic functional group. Here, the divalent anionic functional group represented by A ₂₂ ^- intends a divalent group containing the above-described anion site A ₂ ^- . Examples of the divalent anionic functional group represented by A ₂₂ ^- include divalent anionic functional groups represented by formulas (BX-8) to (BX-11) shown below. In formulas (BX-8) to (BX-11), * represents a bonding position

M _21a ⁺ , M _21b ⁺ , and M ₂₂ ⁺ each independently represent an organic cation. The organic cations represented by M _21a ⁺ , M _21b ⁺ , and M ₂₂ ⁺ are synonymous with M ₁ ⁺ described above, and the preferred embodiments are also the same.
_L21 and _L22 each independently represent a divalent organic group.

Further, in the compound PIa-2 obtained by replacing the organic cations represented by M _21a ⁺ , M _21b ⁺ _, and M ₂₂ ⁺ in the above formula (Ia-2) with H ⁺ , acidic The site-derived acid dissociation constant a2 is greater than the acid dissociation constant a1-1 derived from A _21a H and the acid dissociation constant a1-2 derived from the acidic site represented by A _21b H. The acid dissociation constant a1-1 and the acid dissociation constant a1-2 correspond to the acid dissociation constant a1 described above.
A _21a ^- and A _21b ^- may be the same or different. Moreover, M _21a ⁺ , M _21b ⁺ , and M ₂₂ ⁺ may be the same or different.
At least one of M _21a ⁺ , M _21b ⁺ , M ₂₂ ⁺ , A _21a ⁻ , A _21b ⁻ , L ₂₁ and L ₂₂ may have an acid-decomposable group as a substituent.

In formula (Ia-3), A _31a ^- and A ₃₂ ^- each independently represent a monovalent anionic functional group. The definition of the monovalent anionic functional group represented by A _31a ^- is synonymous with A _21a ^- and A _21b ^- in formula (Ia-2) described above, and the preferred embodiments are also the same.
The monovalent anionic functional group represented by A ₃₂ ^- intends a monovalent group containing the above-mentioned anion site A ₂ ^- . The monovalent anionic functional group represented by A ₃₂ ^- is not particularly limited, and is, for example, a monovalent anionic functional group selected from the group consisting of the above formulas (BX-1) to (BX-7). etc.
A _31b ^- represents a divalent anionic functional group. Here, the divalent anionic functional group represented by A _31b ^- intends a divalent group containing the above-mentioned anionic site A ₁ ^- . Examples of the divalent anionic functional group represented by A _31b ^- include divalent anionic functional groups represented by formula (AX-4) shown below.

M _31a ⁺ , M _31b ⁺ , and M ₃₂ ⁺ each independently represent a monovalent organic cation. M _31a ⁺ , M _31b ⁺ , and M ₃₂ ⁺ organic cations are synonymous with M ₁ ⁺ described above, and preferred embodiments are also the same.
L ₃₁ and L ₃₂ each independently represent a divalent organic group.

Further, in the compound PIa-3 obtained by replacing the organic cations represented by M _31a ⁺ , M _31b ⁺ , and M ₃₂ ⁺ in the above formula (Ia-3) with H ⁺ , an acidic compound represented by A ₃₂ H The acid dissociation constant a2 derived from the site is greater than the acid dissociation constant a1-3 derived from the acidic site represented by A _31a H and the acid dissociation constant a1-4 derived from the acidic site represented by A _31b H. . The acid dissociation constant a1-3 and the acid dissociation constant a1-4 correspond to the acid dissociation constant a1 described above.
A _31a ^- and A ₃₂ ^- may be the same or different. Moreover, M _31a ⁺ , M _31b ⁺ , and M ₃₂ ⁺ may be the same or different.
At least one of M _31a ⁺ , M _31b ⁺ , M ₃₂ ⁺ , A _31a ⁻ , A ₃₂ ⁻ , L ₃₁ and L ₃₂ may have an acid-decomposable group as a substituent.

In formula (Ia-4), A _41a ⁻ , A _41b ⁻ , and A ₄₂ ⁻ each independently represent a monovalent anionic functional group. The definitions of the monovalent anionic functional groups represented by A _41a ^- and A _41b ^- are the same as those of A _21a ^- and A _21b ^- in formula (Ia-2) described above. The definition of the monovalent anionic functional group represented by A ₄₂ ^- is the same as that of A ₃₂ ^- in formula (Ia-3) described above, and the preferred embodiments are also the same.
M _41a ⁺ , M _41b ⁺ , and M ₄₂ ⁺ each independently represent an organic cation.
_L41 represents a trivalent organic group.

Further, in the compound PIa-4 obtained by replacing the organic cations represented by M _41a ⁺ , M _41b ⁺ , and M ₄₂ ⁺ in the above formula (Ia-4) with H ⁺ , an acidic compound represented by A ₄₂ H The acid dissociation constant a2 derived from the site is greater than the acid dissociation constant a1-5 derived from the acidic site represented by A _41a H and the acid dissociation constant a1-6 derived from the acidic site represented by A _41b H. . The acid dissociation constant a1-5 and the acid dissociation constant a1-6 correspond to the acid dissociation constant a1 described above.
A _41a ⁻ , A _41b ⁻ , and A ₄₂ ⁻ may be the same or different. In addition, M _41a ⁺ , M _41b ⁺ , and M ₄₂ ⁺ may be the same or different.
At least one of M _41a ⁺ , M _41b ⁺ , M ₄₂ ⁺ , A _41a ⁻ , A _41b ⁻ , A ₄₂ ⁻ , and L ₄₁ may have an acid-decomposable group as a substituent.

The divalent organic groups represented by L ₂₁ and L ₂₂ in formula (Ia-2) and L ₃₁ and L ₃₂ in formula (Ia-3) are not particularly limited, for example, —CO— , —NR—, —O—, —S—, —SO—, —SO ₂ —, an alkylene group (preferably having 1 to 6 carbon atoms, which may be linear or branched), a cycloalkylene group (preferably 3 to 15 carbon atoms), alkenylene groups (preferably 2 to 6 carbon atoms), divalent aliphatic heterocyclic groups (at least one N atom, O atom, S atom, or Se atom in the ring structure 5 A to 10-membered ring is preferred, a 5- to 7-membered ring is more preferred, and a 5- to 6-membered ring is even more preferred.), a divalent aromatic heterocyclic group (at least one N atom, O atom, S atom, or Se A 5- to 10-membered ring having an atom in the ring structure is preferred, a 5- to 7-membered ring is more preferred, and a 5- to 6-membered ring is even more preferred.), a divalent aromatic hydrocarbon ring group (6- to 10-membered ring is preferred, and a 6-membered ring is more preferred.), and a divalent organic group combining a plurality of these. R above represents a hydrogen atom or a monovalent organic group. Although the monovalent organic group is not particularly limited, for example, an alkyl group (preferably having 1 to 6 carbon atoms) is preferable.
Further, the alkylene group, the cycloalkylene group, the alkenylene group, the divalent aliphatic heterocyclic group, the divalent aromatic heterocyclic group, and the divalent aromatic hydrocarbon ring group have a substituent. You may have Substituents include, for example, halogen atoms (preferably fluorine atoms).

Examples of divalent organic groups represented by L ₂₁ and L ₂₂ in formula (Ia-2) and L ₃₁ and L ₃₂ in formula (Ia-3) are represented by the following formula (L2): Divalent organic groups are also preferred.

In formula (L2), q represents an integer of 1-3. * represents a binding position.
Each Xf independently represents a fluorine atom or an alkyl group substituted with at least one fluorine atom. The number of carbon atoms in this alkyl group is preferably 1-10, more preferably 1-4. A perfluoroalkyl group is preferable as the alkyl group substituted with at least one fluorine atom.
Xf is preferably a fluorine atom or a C 1-4 perfluoroalkyl group, more preferably a fluorine atom or CF ₃ . In particular, it is more preferable that both Xf are fluorine atoms.

_LA represents a single bond or a divalent linking group.
The divalent linking group represented by L _A is not particularly limited, and examples thereof include -CO-, -O-, -SO-, -SO ₂ -, alkylene groups (preferably having 1 to 6 carbon atoms, straight-chain may be in the form of a branched chain), a cycloalkylene group (preferably having 3 to 15 carbon atoms), a divalent aromatic hydrocarbon ring group (preferably a 6- to 10-membered ring, more preferably a 6-membered ring), and Divalent linking groups in which a plurality of these are combined are included.
Moreover, the alkylene group, the cycloalkylene group, and the divalent aromatic hydrocarbon ring group may have a substituent. Substituents include, for example, halogen atoms (preferably fluorine atoms).

Examples of the divalent organic group represented by formula (L2) include *-CF ₂ -*, *-CF ₂ -CF ₂ -*, *-CF ₂ -CF ₂ -CF ₂ -*, *- Ph—O—SO ₂ —CF ₂ −*, *—Ph—O—SO ₂ —CF ₂ —CF ₂ —*, *—Ph—O—SO ₂ —CF ₂ —CF _{2 —CF 2} —*, * -Ph-OCO-CF ₂ -* and the like. Ph is an optionally substituted phenylene group, preferably a 1,4-phenylene group. Although the substituent is not particularly limited, an alkyl group (eg, preferably having 1 to 10 carbon atoms, more preferably 1 to 6 carbon atoms), an alkoxy group (eg, preferably having 1 to 10 carbon atoms, 1 to 1 carbon atoms, 6 is more preferable), or an alkoxycarbonyl group (eg, preferably having 2 to 10 carbon atoms, more preferably 2 to 6 carbon atoms).
When L ₂₁ and L ₂₂ in formula (Ia-2) represent a divalent organic group represented by formula (L2), the bond (*) on the L _A side in formula (L2) is represented by formula ( It preferably binds to A _21a ^- and A _21b ^- in Ia-2).
Further, when L ₃₁ and L ₃₂ in formula (Ia-3) represent a divalent organic group represented by formula (L2), the bond (*) on the L _A side in formula (L2) is Bonding with A _31a ^- and A ₃₂ ^- in formula (Ia-3) is preferred.

The trivalent organic group represented by L ₄₁ in formula (Ia-4) is not particularly limited, and examples thereof include trivalent organic groups represented by the following formula (L3).

In formula (L3), _LB represents a trivalent hydrocarbon ring group or a trivalent heterocyclic group. * represents a binding position.

The hydrocarbon ring group may be either an aromatic hydrocarbon ring group or an aliphatic hydrocarbon ring group. The number of carbon atoms contained in the hydrocarbon ring group is preferably 6-18, more preferably 6-14. The heterocyclic group may be either an aromatic heterocyclic group or an aliphatic heterocyclic group. The heterocyclic ring is preferably a 5- to 10-membered ring having at least one N atom, O atom, S atom, or Se atom in the ring structure, more preferably a 5- to 7-membered ring, and a 5- to 6-membered ring. A ring is more preferred.
Among them, _LB is preferably a trivalent hydrocarbon ring group, more preferably a benzene ring group or an adamantane ring group. The benzene ring group or adamantane ring group may have a substituent. Examples of substituents include, but are not limited to, halogen atoms (preferably fluorine atoms).

In formula (L3), L _B1 to L _B3 each independently represent a single bond or a divalent linking group. The divalent linking groups represented by L _B1 to L _B3 are not particularly limited, and examples thereof include —CO—, —NR—, —O—, —S—, —SO—, —SO ₂ —, and alkylene groups. (preferably having 1 to 6 carbon atoms, which may be linear or branched), cycloalkylene group (preferably having 3 to 15 carbon atoms), alkenylene group (preferably having 2 to 6 carbon atoms), divalent aliphatic Heterocyclic group (preferably a 5- to 10-membered ring having at least one N atom, O atom, S atom, or Se atom in the ring structure, more preferably a 5- to 7-membered ring, even more preferably a 5- to 6-membered ring ), a divalent aromatic heterocyclic group (preferably a 5- to 10-membered ring having at least one N atom, O atom, S atom, or Se atom in the ring structure, more preferably a 5- to 7-membered ring, A 5- to 6-membered ring is more preferred.), a divalent aromatic hydrocarbon ring group (preferably a 6- to 10-membered ring, more preferably a 6-membered ring.), and a divalent linking group combining a plurality of these. is mentioned. R above represents a hydrogen atom or a monovalent organic group. Although the monovalent organic group is not particularly limited, for example, an alkyl group (preferably having 1 to 6 carbon atoms) is preferable.
Further, the alkylene group, the cycloalkylene group, the alkenylene group, the divalent aliphatic heterocyclic group, the divalent aromatic heterocyclic group, and the divalent aromatic hydrocarbon ring group have a substituent. You may have Substituents include, for example, halogen atoms (preferably fluorine atoms).
As the divalent linking group represented by L _B1 to L _B3 , among the above, —CO—, —NR—, —O—, —S—, —SO—, —SO ₂ —, substituents An optional alkylene group and a divalent linking group combining a plurality of these groups are preferred.

Divalent linking groups represented by L _B1 to L _B3 are more preferably divalent linking groups represented by formula (L3-1).

In formula (L3-1), L _B11 represents a single bond or a divalent linking group.
The divalent linking group represented by L _B11 is not particularly limited, and examples thereof include —CO—, —O—, —SO—, —SO ₂ —, an optionally substituted alkylene group (preferably has 1 to 6 carbon atoms and may be linear or branched), and a divalent linking group combining a plurality of these. The substituent is not particularly limited, and examples thereof include halogen atoms.
r represents an integer of 1 to 3;
Xf has the same definition as Xf in formula (L2) described above, and the preferred embodiments are also the same.
* represents a binding position.

Examples of divalent linking groups represented by L _B1 to L _B3 include *-O-*, *-O-SO ₂ -CF ₂ -*, *-O-SO ₂ -CF ₂ -CF ₂ - *, *--O--SO ₂ --CF ₂ --CF ₂ --CF ₂ --*, *--COO--CH ₂ --CH ₂ --* and the like.
L ₄₁ in formula (Ia-4) contains a divalent organic group represented by formula (L3-1), and the divalent organic group represented by formula (L3-1) and A ₄₂ ⁻ is bound, the bond (*) on the carbon atom side specified in formula (L3-1) preferably binds to A ₄₂ ^- in formula (Ia-4).

Next, formula (Ia-5) will be described.

In formula (Ia-5), A _51a ⁻ , A _51b ⁻ , and A _51c ⁻ each independently represent a monovalent anionic functional group. Here, the monovalent anionic functional groups represented by A _51a ⁻ , A _51b ⁻ , and A _51c ⁻ are intended to be monovalent groups containing the above-described anionic site A ₁ ⁻ . The monovalent anionic functional groups represented by A _51a ⁻ , A _51b ⁻ , and A _51c ⁻ are not particularly limited, but are, for example, the group consisting of the above formulas (AX-1) to (AX-3) A selected monovalent anionic functional group and the like can be mentioned.
A _52a ^- and A _52b ^- represent divalent anionic functional groups. Here, the divalent anionic functional groups represented by A _52a ^- and A _52b ^- are intended to be divalent groups containing the above-described anion site A ₂ ^- . The divalent anionic functional group represented by A ₂₂ ^- includes, for example, a divalent anionic functional group selected from the group consisting of the above formulas (BX-8) to (BX-11). mentioned.

M _51a ⁺ , M _51b ⁺ , M _51c ⁺ , M _52a ⁺ , and M _52b ⁺ each independently represent an organic cation. The organic cations represented by M _51a ⁺ , M _51b ⁺ , M _51c ⁺ , M _52a ⁺ , and M _52b ⁺ are synonymous with M ₁ ⁺ described above, and the preferred embodiments are also the same.
_L51 and _L53 each independently represent a divalent organic group. The divalent organic groups represented by L ₅₁ and L ₅₃ have the same meanings as L ₂₁ and L ₂₂ in formula (Ia-2) above, and the preferred embodiments are also the same.
_L52 represents a trivalent organic group. The trivalent organic group represented by L ₅₂ has the same meaning as L ₄₁ in formula (Ia-4) above, and the preferred embodiments are also the same.

Further, in the compound PIa-5 obtained by replacing the organic cations represented by M _51a ⁺ , M _51b ⁺ , M _51c ⁺ , M _52a ⁺ , and M _52b ⁺ in the above formula (Ia-5) with H ⁺ , The acid dissociation constant a2-1 derived from the acidic site represented by A _52a H and the acid dissociation constant a2-2 derived from the acidic site represented by A _52b H are the acid dissociation constant a1- derived from A _51a H. 7, greater than the acid dissociation constant a1-8 derived from the acidic site represented by A _51b H and the acid dissociation constant a1-9 derived from the acidic site represented by A _51c H. The acid dissociation constants a1-7 to a1-9 correspond to the acid dissociation constant a1 described above, and the acid dissociation constants a2-1 and a2-2 correspond to the acid dissociation constant a2 described above.
A _51a ⁻ , A _51b ⁻ , and A _51c ⁻ may be the same or different. In addition, A _52a ^- and A _52b ^- may be the same or different. In addition, M _51a ⁺ , M _51b ⁺ , M _51c ⁺ , M _52a ⁺ , and M _52b ⁺ may be the same or different.
At least one of M _51b ⁺ , M _51c ⁺ , M _52a ⁺ , M _52b ⁺ , A _51a ⁻ , A _51b ⁻ , A _51c ⁻ , L ₅₁ , L ₅₂ and L ₅₃ is an acid-decomposable substituent You may have a group.

<Compound (II)>
Compound (II) is a compound having two or more of the above structural moieties X and one or more of the following structural moieties Z, wherein the first acidic It is an acid-generating compound containing two or more sites and an acid-generating compound containing the structural site Z described above.
Structural site Z: nonionic site capable of neutralizing acid

The definition of structural site X and the definitions of A ₁ ^- and M ₁ ⁺ in compound (II) are the same as the definitions of structural site X and the definitions of A ₁ ^- and M ₁ ⁺ in compound (I) above. is synonymous with and preferred embodiments are also the same.

HA ₁ obtained by replacing the cation site M ₁ ⁺ in the structural site X with H ⁺ in the compound PII, which is obtained by replacing the cation site M ₁ ⁺ in the structural site X with H ⁺ in the compound (II). The preferred range of the acid dissociation constant a1 derived from the acidic site represented by is the same as the acid dissociation constant a1 in the above compound PI.
In addition, for example, when the compound (II) is a compound that generates an acid having two of the first acidic sites derived from the structural site X and the structural site Z, the compound PII is "two HA ₁ It corresponds to "a compound having When the acid dissociation constant of this compound PII is determined, the acid dissociation constant when the compound PII is "a compound having one A ₁ ^- and one HA ₁ " and "one A ₁ ^- and one HA The acid dissociation constant when the "compound having ₁ " becomes the "compound having two A ₁ ^- " corresponds to the acid dissociation constant a1.

The acid dissociation constant a1 is obtained by the method for measuring the acid dissociation constant described above.
The above compound PII corresponds to an acid generated when compound (II) is irradiated with actinic rays or radiation.
The two or more structural sites X may be the same or different. Two or more of A ₁ ⁻ and two or more of M ₁ ⁺ may be the same or different.

The acid-neutralizing nonionic site in the structural site Z is not particularly limited, and for example, a site containing a group capable of electrostatically interacting with protons or a functional group having electrons is preferable. .
As a group capable of electrostatically interacting with protons or a functional group having electrons, a functional group having a macrocyclic structure such as a cyclic polyether, or a nitrogen atom having a lone pair of electrons that does not contribute to π conjugation is used. a functional group having a 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.

Partial structures of functional groups having electrons or groups capable of electrostatically interacting with protons include, for example, a crown ether structure, an azacrown ether structure, a primary to tertiary amine structure, a pyridine structure, an imidazole structure, and a pyrazine structure. etc., among which primary to tertiary amine structures are preferred.

Compound (II) is not particularly limited, and examples thereof include compounds represented by the following formulas (IIa-1) and (IIa-2).

In formula (IIa-1) above, A _61a ^- and A _61b ^- have the same meanings as A ₁₁ ^- in formula (Ia-1) above, and preferred embodiments are also the same. M _61a ⁺ and M _61b ⁺ have the same meaning as M ₁₁ ⁺ in formula (Ia-1) above, and the preferred embodiments are also the same.
In formula (IIa-1) above, L ₆₁ and L ₆₂ have the same meanings as L ₁ in formula (Ia-1) above, and preferred embodiments are also the same.

In formula (IIa-1), R _2X represents a monovalent organic group. _The monovalent organic group represented by R _2X is not particularly limited _. - which may be substituted with one or a combination of two or more selected from the group consisting of an alkyl group (preferably having 1 to 10 carbon atoms, which may be linear or branched), a cycloalkyl group (preferably 3 to 15 carbon atoms), alkenyl groups (preferably 2 to 6 carbon atoms), and the like.
Moreover, the alkylene group, the cycloalkylene group, and the alkenylene group may have a substituent. Examples of substituents include, but are not particularly limited to, halogen atoms (preferably fluorine atoms).

Further, in the compound PIIa-1 obtained by replacing the organic cations represented by M _61a ⁺ and M _61b ⁺ with H ⁺ in the above formula (IIa-1), the acid derived from the acidic site represented by A _61a H The dissociation constant a1-10 and the acid dissociation constant a1-11 derived from the acidic site represented by A _61b H correspond to the acid dissociation constant a1 described above.
The compound PIIa-1 obtained by replacing the cation sites M _61a ⁺ and M _61b ⁺ in the structural site X in the structural site X in the compound (IIa-1) with H ⁺ is HA _61a -L ₆₁ -N(R _2X ) -L ₆₂ -A _61b H. In addition, compound PIIa-1 is the same as the acid generated from the compound represented by formula (IIa-1) upon exposure to actinic rays or radiation.
At least one of M _61a ⁺ , M _61b ⁺ , A _61a ⁻ , A _61b ⁻ , L ₆₁ , L ₆₂ and R _2X may have an acid-decomposable group as a substituent.

In formula (IIa-2) above, A _71a ⁻ , A _71b ⁻ , and A _71c ⁻ have the same meanings as A ₁₁ ⁻ in formula (Ia-1) above, and preferred embodiments are also the same. M _71a ⁺ , M _71b ⁺ , and M _71c ⁺ each have the same meaning as M ₁₁ ⁺ in formula (Ia-1) described above, and preferred embodiments are also the same.
In formula (IIa-2), L ₇₁ , L ₇₂ , and L ₇₃ have the same meanings as L ₁ in formula (Ia-1) above, and preferred embodiments are also the same.

Further, in the compound PIIa-2 obtained by replacing the organic cations represented by M _71a ⁺ , M _71b ⁺ , and M _71c ⁺ in the above formula (IIa-2) with H ⁺ , the acidic site represented by A _71a H The acid dissociation constant a1-12 derived from, the acid dissociation constant a1-13 derived from the acidic site represented by A _71b H, and the acid dissociation constant a1-14 derived from the acidic site represented by A _71c H are It corresponds to the acid dissociation constant a1 described above.
A compound PIIa-2 obtained by replacing the cation sites M _71a ⁺ , M _71b ⁺ , and M _71c ⁺ in the structural site X of the compound (IIa-1) with H ⁺ is HA _71a -L ₇₁ -N (L ₇₃ -A _71c H)-L ₇₂ -A _71b H is applicable. In addition, compound PIIa-2 is the same as the acid generated from the compound represented by formula (IIa-2) upon exposure to actinic rays or radiation.
At least one of M _71a ⁺ , M _71b ⁺ , M _71c ⁺ , A _71a ⁻ , A _71b ⁻ , A _71c ⁻ , L ₇₁ , L ₇₂ and L ₇₃ has an acid-decomposable group as a substituent. may be

Next, the sites other than the organic cation that the specific photoacid generator may have are exemplified.

Although the molecular weight of the specific photoacid generator is not particularly limited, it is preferably from 100 to 10,000, more preferably from 100 to 2,500, and even more preferably from 100 to 1,500.

When the composition of the present invention contains a specific photoacid generator, its content (total content of compounds (I) and (II)) is 10% by mass or more relative to the total solid content of the composition. Preferably, 20% by mass or more is more preferable. Moreover, the upper limit thereof is preferably 80% by mass or less, more preferably 70% by mass or less, and even more preferably 60% by mass or less.
The specific photoacid generator may be used singly or in combination of two or more. When two or more are used, the total content is preferably within the range of the preferred content.

The composition of the present invention may contain the following compound (III) as a photoacid generator.

<Compound (III)>
Compound (III) is a compound having two or more structural moieties X below, and is a compound that generates two acidic moieties derived from the structural moieties X below upon exposure to actinic rays or radiation.
Structural site X: a structural site consisting of an anion site A ₁ ⁻ and a cation site M ₁ ⁺ and forming an acidic site represented by HA ₁ upon exposure to actinic rays or radiation

Two or more structural moieties X contained in compound (III) may be the same or different. Two or more of A ₁ ⁻ and two or more of M ₁ ⁺ may be the same or different.

The definition of structural site X and the definitions of A ₁ ^- and M ₁ ⁺ in compound (III) are the same as the definitions of structural site X and the definitions of A ₁ ^- and M ₁ ⁺ in compound (I) above. is synonymous with and preferred embodiments are also the same.

<Acid diffusion control agent>
The actinic ray-sensitive or radiation-sensitive resin composition of 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 of 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 the passage of time. It is more preferable to include
Known acid diffusion control agents can be appropriately used in the actinic ray-sensitive or radiation-sensitive resin composition of 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 represents 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 the 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.

[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 of the present invention, an onium salt (DC), which is a relatively weak acid relative to the photoacid generator, can be used as an acid diffusion controller.
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 of 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. It 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.
^L1 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 under 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 protective 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, but are not limited to these. In addition, acid diffusion controllers D-1 to D-17 used in Examples are also included.

In the actinic ray-sensitive or radiation-sensitive resin composition of the present invention, the acid diffusion controller 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 20% by mass, preferably 0.1% by mass, based on the total solid content of the composition. ~10% by mass is more preferable, and 0.1% by mass to 5% by mass is even more preferable.

<Solvent>
The actinic ray-sensitive or radiation-sensitive resin composition of the present invention preferably contains a solvent (also referred to as "solvent (F)"), more preferably an organic solvent.
Known resist solvents can be appropriately used in the actinic ray-sensitive or radiation-sensitive resin composition of 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 carboxylate, alkylene glycol monoalkyl ether, alkyl lactate, alkyl alkoxypropionate, cyclic lactone (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. (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 (1-methoxy-2-acetoxypropane), ethyl ethoxypropionate, 2-heptanone, γ-butyrolactone, cyclohexanone, cyclopentanone or butyl acetate are more preferred, propylene glycol monomethyl ether acetate, γ-butyrolactone, ethyl More preferred are ethoxypropionate, cyclohexanone, cyclopentanone or 2-heptanone. 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 of the present invention is not particularly limited, but it is preferably 0.5% by mass to 60% by mass, and 1.0% by mass to 45% by mass. is more preferable, and 1.0% by mass to 40% by mass is even more preferable.
When exposing a film formed from the actinic ray-sensitive or radiation-sensitive resin composition of the present invention with a KrF excimer laser, the solid content concentration of the actinic ray-sensitive or radiation-sensitive resin composition is 10% by mass. or more, preferably 15% by mass or more, and preferably 20% by mass or more.
The solid content concentration refers to the solvent, water, the compound represented by the general formula (1), the compound represented by the general formula (2), and the compound represented by the general formula (3) relative to the total mass of the composition. is the mass percentage of the mass of other resist components excluding

<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 of 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.

<Crosslinking agent>
The actinic ray-sensitive or radiation-sensitive resin composition of 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 of 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.

By containing a surfactant, the actinic ray-sensitive or radiation-sensitive resin composition of the present invention has good sensitivity and resolution when using an exposure light source with a wavelength of 250 nm or less, particularly 220 nm or less, and has good adhesion. And a resist pattern with few development defects can be obtained.
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 of 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. is preferred, and 0.0005% by mass to 1% by mass is more preferred.
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 of 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 of the present invention is prepared by dissolving the above-described components in a predetermined organic solvent, preferably in the above-described mixed solvent, and filtering the solution through a filter. It is preferable to use it by applying it on top.
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 filtration, 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 of 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- or radiation-sensitive resin composition of the present invention is an actinic ray- or radiation-sensitive resin composition that reacts with irradiation of light to change its properties. More specifically, the actinic ray-sensitive or radiation-sensitive resin composition of the present invention can be used in semiconductor manufacturing processes such as ICs (Integrated Circuits), manufacturing circuit boards such as liquid crystals or thermal heads, and manufacturing imprint mold structures. , other photofabrication processes, or actinic ray- or radiation-sensitive resin compositions used in the manufacture of lithographic printing plates or acid-curable compositions. The resist pattern formed by the actinic ray-sensitive or radiation-sensitive resin composition of the present invention can be formed through an etching process, an ion implantation process, a bump electrode forming process, a rewiring forming process, MEMS (Micro Electro Mechanical Systems), and the like. can be used in

The resist composition of the present invention is also suitably used as a photosensitive composition for EUV light.
EUV light has a wavelength of 13.5 nm, which is shorter than ArF (wavelength 193 nm) light and the like, so the number of incident photons is smaller when exposed with the same sensitivity. Therefore, the influence of "photon shot noise", in which the number of photons stochastically varies, is large, leading to deterioration of LER (Line Edge Roughness) and bridging defects. To reduce the photon shot noise, there is a method of increasing the number of incident photons by increasing the amount of exposure, but this is a trade-off with the demand for higher sensitivity.

When the A value obtained by the following formula (1) is high, the EUV light and electron beam absorption efficiency of the resist film formed from the resist composition increases, which is effective in reducing photon shot noise. The A value represents the absorption efficiency of the EUV light and the electron beam relative to the mass ratio of the resist film. Formula (1): A = ([H] x 0.04 + [C] x 1.0 + [N] x 2.1 + [O] x 3.6 + [F] x 5.6 + [S] x 1.5 + [I] × 39.5) / ([H] × 1 + [C] × 12 + [N] × 14 + [O] × 16 + [F] × 19 + [S] × 32 + [I] × 127)
The A value is preferably 0.120 or more. The upper limit is not particularly limited, but if the A value is too large, the EUV light and electron beam transmittance of the resist film will decrease, the optical image profile in the resist film will deteriorate, and as a result, it will be difficult to obtain a good pattern shape. Therefore, 0.240 or less is preferable, and 0.220 or less is more preferable.

In the formula (1), [H] represents the molar ratio of hydrogen atoms derived from the total solid content to the total atoms of the total solid content in the actinic ray-sensitive or radiation-sensitive resin composition, and [C] represents the molar ratio of carbon atoms derived from the total solid content to the total atoms of the total solid content in the actinic ray-sensitive or radiation-sensitive resin composition, [N] is the actinic ray-sensitive or radiation-sensitive resin Represents the molar ratio of nitrogen atoms derived from the total solid content with respect to the total atoms of the total solid content in the composition, [O] is the total atoms of the total solid content in the actinic ray-sensitive or radiation-sensitive resin composition , represents the molar ratio of oxygen atoms derived from the total solid content, and [F] represents the molar ratio of fluorine atoms derived from the total solid content to the total atoms of the total solid content in the actinic ray-sensitive or radiation-sensitive resin composition. represents, [S] represents the molar ratio of sulfur atoms derived from the total solid content to the total atoms of the total solid content in the actinic ray-sensitive or radiation-sensitive resin composition, [I] is the actinic ray-sensitive represents the molar ratio of iodine atoms derived from the total solid content to the total atoms of the total solid content in the curable or radiation-sensitive resin composition.
For example, when the resist composition contains a resin whose polarity increases under the action of acid (acid-decomposable resin), a photoacid generator, an acid diffusion controller, and a solvent, the resin, the photoacid generator, and the acid A diffusion control agent corresponds to solid content. That is, the total atoms of the total solid content correspond to the sum of all atoms derived from the resin, all atoms derived from the photoacid generator, and all atoms derived from the acid diffusion control agent. For example, [H] represents the molar ratio of hydrogen atoms derived from the total solid content to the total atoms of the total solid content. The ratio of hydrogen atoms derived from the resin, hydrogen atoms derived from the photo-acid generator, and hydrogen atoms derived from the acid diffusion controller to the sum of all atoms derived from the acid generator and all atoms derived from the acid diffusion controller It will represent the total molar ratio.

The A value can be calculated by calculating the atomic number ratios contained when the structures and contents of the constituent components of the total solid content in the resist composition are known. Further, even if the constituent components are unknown, the constituent atomic number ratio can be calculated by analytical methods such as elemental analysis for the resist film obtained by evaporating the solvent component of the resist composition. .

(Actinic ray-sensitive or radiation-sensitive film)
The actinic ray-sensitive or radiation-sensitive film (preferably, resist film) in the present invention is a film formed from the actinic ray-sensitive or radiation-sensitive resin composition of the present invention. The actinic ray-sensitive or radiation-sensitive film in the present invention is a solidified product of the actinic ray-sensitive or radiation-sensitive resin composition of 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 actinic ray-sensitive or radiation-sensitive film in the present invention is dried after coating the actinic ray-sensitive or radiation-sensitive resin composition of the present invention on a support such as a substrate. obtained by
The drying means removing at least part of the solvent contained in the actinic ray-sensitive or radiation-sensitive resin composition of 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 actinic ray-sensitive or radiation-sensitive film of the present invention are the same as the components contained in the actinic ray-sensitive or radiation-sensitive resin composition of the present invention, excluding the solvent, and are preferred. Aspects are also the same.
The content of each component contained in the actinic ray-sensitive or radiation-sensitive film in the present invention refers to the content of each component other than the solvent in the actinic ray-sensitive or radiation-sensitive resin composition of the present invention. "solid content" is read as "total mass of actinic ray-sensitive or radiation-sensitive film".

The thickness of the actinic ray-sensitive or radiation-sensitive film in the present invention is not particularly limited, but is preferably 1 nm to 700 nm, more preferably 30 nm to 500 nm, even more preferably 50 nm to 150 nm. , 80 nm to 130 nm.
In addition, when it is desired to form a thick actinic ray-sensitive or radiation-sensitive 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. More preferably, the thickness is 20 μm or more.

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

<Film formation process>
The pattern formation method of the present invention may include a film formation step. As a method for forming an actinic ray-sensitive or radiation-sensitive film in the film formation step, for example, the actinic ray-sensitive or radiation-sensitive film is formed by drying as described in the item of the actinic ray-sensitive or radiation-sensitive film above. method.

[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 other lithography processes for photofabrication. A substrate can be used. Specific examples of the support include inorganic substrates such as silicon, SiO ₂ , and SiN.

<Exposure process>
The exposure step is a step of exposing the actinic ray-sensitive or radiation-sensitive film to light.
The exposure method may be liquid immersion exposure.
The pattern forming method of 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 having 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.
Specifically, the light used is KrF excimer laser (248 nm), ArF excimer laser (193 nm), _F2 excimer laser (157 nm), X-ray, EUV (13 nm), electron beam, etc. ArF excimer laser , EUV or electron beam are preferred.
Among them, the exposure in the exposing step is preferably performed by liquid immersion exposure using an argon fluoride laser.
The exposure amount is preferably 5 mJ/cm ² to 200 mJ/cm ² , 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 above acid diffusion control agent.

[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 it 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 step, post-exposure heating step>
The pattern forming method of the present invention preferably includes a pre-heating (PB: PreBake) step before the exposure step.
The pattern formation method of the present invention may include the preheating step multiple times.
The pattern forming method of the present invention preferably includes a post exposure bake (PEB) step after the exposure step and before the development step.
The pattern forming method of 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 of the present invention may further include a step of forming a resist underlayer film (resist underlayer film forming step) before the film formation 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 of 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 of 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 that the cleaning treatment is performed by a spin coating method, and after cleaning, the substrate is rotated at a rotation speed of 2,000 to 4,000 rpm (rotations per minute) to remove the rinsing liquid from the substrate. It is also preferable to include a heating step (Post Bake) after the rinsing step. This heating process removes the developer and rinse remaining between the patterns and inside the patterns. In the heating step after the rinsing step, the heating temperature is 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 of 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 of the present invention includes the pattern forming method of the present invention. The electronic device manufactured by the method for manufacturing an electronic device of the present invention is suitably mounted in electrical and electronic equipment (for example, home appliances, OA (Office Automation) related equipment, media related equipment, optical equipment, communication equipment, etc.). be done.

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.

(Purification of β-PGMEA and α-PGMEA)
Propylene glycol monomethyl ether acetate (PGMEA) (manufactured by Kanto Kagaku Co., Ltd.) was placed in a flask equipped with a distillation apparatus, and the pressure was reduced to 100 mmHg and the mixture was gradually heated. After removing the fraction (1-methoxy-2-propyl acetate (α-PGMEA)) (solvent F-1) obtained at around 80°C, the fraction (2-methoxy-1 -propanol acetate (β-PGMEA)) was recovered.
Thus, α-PGMEA and β-PGMEA were obtained.
It was confirmed by ¹ H-NMR (Nuclear Magnetic Resonance) that the obtained distillates were α-PGMEA and β-PGMEA.

1-Methoxy-2-propanol (α-PGME) (solvent F-2) and 2-methoxy-1-propanol (β-PGME) were prepared from commercially available propylene glycol monomethyl ether (PGME) in the same manner as above. Obtained.
Also, in the same manner as described above, from commercially available propylene glycol monoethyl ether (PGEE), 1-ethoxy-2-propanol (α-PGEE) (solvent F-3) and 2-ethoxy-1-propanol (β- PGEE) was obtained.

<Resin (A)>
The resins (A-1 to A-16, A-21 to A-36) used have the structural units (repeating units) shown in Tables 1 and 2 below, respectively, at the molar ratios shown in Tables 1 and 2. is. Each structural unit is indicated by the structure of the corresponding monomer.
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 composition ratio (molar ratio) of the resin was measured by ¹³ C-NMR (Nuclear Magnetic Resonance).

When a homopolymer of a monomer a3 corresponding to a repeating unit (a3) derived from a monomer (monomer a3) 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 (WO2018/212079A1).

<Photoacid generator>
The structures of the photoacid generators (PAG-1 to PAG-37) used are shown below.

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

<Hydrophobic resin>
The hydrophobic resins (E-1 to E-15) used each have the structural units (repeating units) shown in Table 3 below in the molar ratio shown in Table 3. Each structural unit is indicated by the structure of the corresponding monomer. 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).

<Surfactant>
The surfactants used are shown below.
H-1: Megafac F176 (manufactured by DIC Corporation, fluorine-based surfactant)
H-2: Megafac R08 (manufactured by DIC Corporation, fluorine and silicone surfactant)
H-3: PF656 (manufactured by OMNOVA, fluorine-based surfactant)
H-4: PF6320 (manufactured by OMNOVA, fluorine-based surfactant)
H-5: FC-4430 (manufactured by Sumitomo 3M, fluorosurfactant)

<Solvent>
The solvents used are shown below.
F-1: 1-methoxy-2-propyl acetate (α-PGMEA)
F-2: 1-methoxy-2-propanol (α-PGME)
F-3: 1-ethoxy-2-propanol (α-PGEE)
F-4: cyclohexanone F-5: cyclopentanone F-6: 2-heptanone F-7: ethyl lactate F-8: γ-butyrolactone F-9: propylene carbonate

<Additive>
The structures of the additives used are shown below.

(Examples 1 to 90 and Comparative Examples 1 to 11)
<Preparation of resist composition>
Each component shown in Tables 4 to 8 below was used in the amount (parts by mass) shown in Tables 4 to 8 and mixed so that the solid content concentration was 4.0% by mass to obtain a solution. However, the contents of β-PGMEA, β-PGME, β-PGEE, and water were adjusted to the values shown in Tables 9 to 13 below. Then, the resulting solution was filtered through a polyethylene filter having a pore size of 0.03 μm to prepare a resist composition (actinic ray-sensitive or radiation-sensitive resin composition).
The contents of β-PGMEA, β-PGME, and β-PGEE are obtained by adding β-PGMEA, β-PGME, and β-PGEE obtained by the method described above to the solvent used for preparing the resist composition. adjusted by
The water content was adjusted by adding pure water to α-PGMEA (F-1) used in the resist composition, or by performing dehydration.
In addition, the solid content in the resist composition means from the components contained in the resist composition, the solvent, water, the compound represented by the general formula (1), the compound represented by the general formula (2), and the compound represented by the general formula (3 ) means all components except for the compounds represented by The resulting resist compositions were used in Examples and Comparative Examples.

Although the resist composition Re-79 does not contain the above PAG-1 to PAG-37 shown as photoacid generators, MC-, which is a repeating unit having a photoacid-generating group in resin A-35, 17 can be considered to correspond to a photoacid generator.

<Measurement of β-PGMEA content in resist composition>
The content of β-PGMEA in the resist composition was measured as follows.
Using a heating adsorption device μ-CTE250 manufactured by MARKES, the solvent component in the sample was heated and vaporized at a heating temperature of 170° C. and adsorbed in a dedicated sample tube. After that, using a thermal desorption device HandyTD TD265 manufactured by GL Sciences Co., Ltd., the solvent component adsorbed on the sample tube was desorbed at a heating temperature of 170 ° C., and then quantitatively analyzed with a gas chromatograph mass spectrometer JMS-Q1500GC manufactured by JEOL Ltd. did

<Measurement of β-PGME content in resist composition>
The content of β-PGME in the resist composition was also measured in the same manner as in "Measurement of the content of β-PGMEA in the resist composition".

<Measurement of β-PGEE content in resist composition>
The content of β-PGEE in the resist composition was also measured in the same manner as in "Measurement of the content of β-PGMEA in the resist composition".

<Measurement of Water Content in Resist Composition>
The content of water in the resist composition was measured using a Karl Fischer moisture meter MKC-510N manufactured by Kyoto Electronics Industry Co., Ltd. Hydronal Chromat AK (manufactured by Honeywell Co.) was used as the anolyte and Hydronal Chromat CG (manufactured by Honeywell Co.) was used as the catholyte.

<Pattern formation method (1): ArF immersion exposure, alkaline aqueous solution development>
Examples 1 to 10, Example 16, Example 17, Example 19, Example 20, Example 23, Example 26, Example 27, Example 36, Example 37, Example 40, Example 41, Example 42, Example 43, Example 46, Example 48, Example 49, Example 51, Example 52, Example 53, Example 55, Example 56, Example 58, Example 60, Comparative Example In Comparative Example 1 and Comparative Example 3, patterns were formed by the following pattern forming method (1) using the resist compositions shown in Tables 9 to 11, respectively.
An organic antireflection film forming composition ARC29SR (manufactured by Brewer Science) was applied onto a silicon wafer and baked at 205° C. for 60 seconds to form an antireflection film with a thickness of 98 nm. A resist composition shown in Tables 9 to 11 was applied thereon and baked at 100° C. for 60 seconds to form a resist film having a thickness of 90 nm. The resist composition used was stored in a constant temperature bath at 35° C. for 6 months after preparation.
An ArF excimer laser immersion scanner (manufactured by ASML; XT1950i, NA 1.35, C-Quad, outer sigma 0.930, inner sigma 0.730, XY deflection) was used to scan the resist film with a line width of 45 nm. Exposure was through a 6% halftone mask with a 1:1 line and space pattern. Ultrapure water was used as the immersion liquid.
The exposed resist film was baked at 100° C. for 60 seconds, developed with a 2.38 mass % tetramethylammonium hydroxide (TMAH) aqueous solution for 30 seconds, and then rinsed with pure water for 30 seconds. After that, it was spin-dried to obtain a positive pattern.

<Pattern formation method (2): ArF immersion exposure, organic solvent development>
Examples 11-15, Example 18, Example 21, Example 22, Example 24, Example 25, Example 28-35, Example 38, Example 39, Example 44, Example 45, Example 47, Example 50, Example 54, Example 57, Example 59, Example 61, and Comparative Example 2, the following pattern forming method (2 ) to form a pattern.
An organic antireflection film forming composition ARC29SR (manufactured by Brewer Science) was applied onto a silicon wafer and baked at 205° C. for 60 seconds to form an antireflection film with a thickness of 98 nm. A resist composition shown in Tables 9 to 11 was applied thereon and baked at 100° C. for 60 seconds to form a resist film having a thickness of 90 nm. The resist composition used was stored in a constant temperature bath at 35° C. for 6 months after preparation.
An ArF excimer laser immersion scanner (manufactured by ASML; XT1950i, NA 1.35, C-Quad, outer sigma 0.930, inner sigma 0.730, XY deflection) was used to scan the resist film with a line width of 45 nm. Exposure was through a 6% halftone mask with a 1:1 line and space pattern. Ultrapure water was used as the immersion liquid.
The exposed resist film was baked at 100° C. for 60 seconds, developed with n-butyl acetate for 30 seconds, and then rinsed with 4-methyl-2-pentanol for 30 seconds. After that, it was spin-dried to obtain a negative pattern.

<Pattern formation method (3): EUV exposure, alkaline aqueous solution development>
In Examples 62 to 74 and Comparative Examples 4 to 6, patterns were formed by the following pattern forming method (3) using the resist compositions shown in Table 12, respectively.
An underlayer film forming composition AL412 (manufactured by Brewer Science) was applied onto a silicon wafer and baked at 205° C. for 60 seconds to form an underlayer film having a thickness of 20 nm. A resist composition shown in Table 12 was applied thereon and baked at 100° C. for 60 seconds to form a resist film having a thickness of 40 nm. The resist composition used was stored in a constant temperature bath at 35° C. for 6 months after preparation.
Using an EUV exposure machine (model "NXE3300", manufactured by ASML, NA = 0.33, Dipole, outer sigma 0.9, inner sigma 0.7) on the resist film, a 1: 1 line with a line width of 20 nm It was exposed through an And-space pattern mask.
The exposed resist film was baked at 100° C. for 60 seconds, developed with a 2.38 mass % tetramethylammonium hydroxide (TMAH) aqueous solution for 30 seconds, and then rinsed with pure water for 30 seconds. After that, it was spin-dried to obtain a positive pattern.

<Pattern formation method (4): EUV exposure, organic solvent development>
In Examples 75 to 77 and Comparative Example 7, patterns were formed by the following pattern forming method (4) using the resist compositions shown in Table 12, respectively.
An underlayer film forming composition AL412 (manufactured by Brewer Science) was applied onto a silicon wafer and baked at 205° C. for 60 seconds to form an underlayer film having a thickness of 20 nm. A resist composition shown in Table 12 was applied thereon and baked at 100° C. for 60 seconds to form a resist film having a thickness of 40 nm. The resist composition used was stored in a constant temperature bath at 35° C. for 6 months after preparation.
Using an EUV exposure machine (model "NXE3300", manufactured by ASML, NA = 0.33, Dipole, outer sigma 0.9, inner sigma 0.7) on the resist film, a 1: 1 line with a line width of 20 nm It was exposed through an And-space pattern mask.
The exposed resist film was baked at 100° C. for 60 seconds, developed with n-butyl acetate for 30 seconds, and spin-dried to obtain a negative pattern.

<Pattern formation method (5): EB exposure, alkaline aqueous solution development>
In Examples 78 to 90 and Comparative Examples 8 to 11, patterns were formed by the following pattern forming method (5) using the resist compositions shown in Table 13, respectively.
An underlayer film forming composition AL412 (manufactured by Brewer Science) was applied onto a silicon wafer and baked at 205° C. for 60 seconds to form an underlayer film having a thickness of 20 nm. A resist composition shown in Table 13 was applied thereon and baked at 100° C. for 60 seconds to form a resist film having a thickness of 40 nm. The resist composition used was stored in a constant temperature bath at 35° C. for 6 months after preparation.
The resist film was subjected to pattern irradiation using an electron beam exposure apparatus (EBM-7000 manufactured by NuFlare Technology Co., Ltd., acceleration voltage of 50 kV). At this time, drawing was performed so as to form a 1:1 line and space of 20 nm.
The exposed resist film was baked at 100° C. for 60 seconds, developed with a 2.38 mass % tetramethylammonium hydroxide (TMAH) aqueous solution for 30 seconds, and then rinsed with pure water for 30 seconds. After that, it was spin-dried to obtain a positive pattern.

<Performance evaluation>
[Development defect after aging]
In the case of ArF immersion exposure experiments (Examples 1 to 61, Comparative Examples 1 to 3), after forming a 1:1 line and space pattern with a line width of 45 nm, UVision 5 (manufactured by AMAT) was used to detect defects on a silicon wafer. The distribution was detected, and the shape of the defect was observed using SEMVision G4 (manufactured by AMAT). Defects occurring in the pattern wafer are observed as images shown in FIGS. 1 and 2, for example. Evaluation was made by counting the number of defects per silicon wafer. A smaller number of defects indicates a better result.
A: The number of defects per wafer is 10 or less B: The number of defects per wafer is 11 to 50 C: The number of defects per wafer is 51 to 100 D: The number of defects per wafer is 101 or more

In the case of EUV exposure and EB exposure experiments (Examples 62 to 90, Comparative Examples 4 to 11), after forming a 1:1 line and space pattern with a line width of 20 nm, UVision 5 (manufactured by AMAT) was used on a silicon wafer. The defect distribution was detected, and the defect shape was observed using SEMVision G4 (manufactured by AMAT). Defects occurring in the pattern wafer are observed as images shown in FIGS. 1 and 2, for example. Evaluation was made by counting the number of defects per silicon wafer. A smaller number of defects indicates a better result.
A: The number of defects per wafer is 10 or less B: The number of defects per wafer is 11 to 50 C: The number of defects per wafer is 51 to 100 D: The number of defects per wafer is 101 or more

[LWR performance after aging]
In the case of ArF immersion exposure experiments (Examples 1 to 61, Comparative Examples 1 to 3), a 45 nm (1:1) line-and-space resist pattern resolved at the optimum exposure dose was subjected to a length measurement scanning type When observing from above the pattern using an electron microscope (SEM, CG-4100 manufactured by Hitachi, Ltd.), the line width was observed at an arbitrary point, and the measurement variation was evaluated by 3σ. A smaller value indicates better performance. The optimum exposure dose is the irradiation energy for resolving a 1:1 line-and-space pattern with a line width of 45 nm.
A: 3σ is 4.0 nm or less B: 3σ is over 4.0 nm and 5.0 nm or less C: 3σ is over 5.0 nm

In the case of EUV exposure and EB exposure experiments (Examples 62 to 90, Comparative Examples 4 to 11), length measurement scanning was performed on a 20 nm (1:1) line and space resist pattern resolved at the optimum exposure dose. When observed from above the pattern using a type electron microscope (SEM, CG-4100 manufactured by Hitachi, Ltd.), the line width was observed at an arbitrary point, and the measurement variation was evaluated by 3σ. A smaller value indicates better performance. The optimum exposure amount is the irradiation energy for resolving a 1:1 line-and-space pattern with a line width of 20 nm.
A: 3σ is 2.0 nm or less B: 3σ is more than 2.0 nm and 3.0 nm or less C: 3σ is more than 3.0 nm

The obtained evaluation results are shown in Tables 9 to 13.
The "β-PGMEA content" shown in Tables 9 to 13 is the content of β-PGMEA with respect to the total mass of the resist composition.
The "β-PGME content" shown in Tables 9 to 13 is the content of β-PGME with respect to the total mass of the resist composition.
The "β-PGEE content" shown in Tables 9 to 13 is the β-PGEE content relative to the total mass of the resist composition.
The "water content" shown in Tables 9 to 13 is the water content relative to the total mass of the resist composition.
"Ratio of β-PGMEA to α-PGMEA" shown in Tables 9 to 13 is the ratio (% by mass) of the content of β-PGMEA to α-PGMEA in the resist composition.
In Tables 9 to 13, "the content of β-PGMEA" is "undetected" means that the content of β-PGMEA is less than 0.1 mass ppm with respect to the total mass of the resist composition. .
In Tables 9 to 13, "-" for "content of β-PGME" indicates that the content of β-PGME is less than 0.1 ppm by mass relative to the total mass of the resist composition.
In Tables 9 to 13, "-" for "content of β-PGEE" indicates that the content of β-PGEE is less than 0.1 ppm by mass relative to the total mass of the resist composition.
In Tables 9 to 13, "water content" of "not detected" means that the water content is less than 0.1 ppm by mass relative to the total mass of the resist composition.

From the results in Tables 9 to 13, it can be seen that the compositions of the present invention suppress the occurrence of development defects after aging and are excellent in LWR performance after aging.

According to the present invention, an actinic ray- or radiation-sensitive resin composition that suppresses the occurrence of development defects after the passage of time and has excellent LWR performance after the passage of time, and the actinic ray- or radiation-sensitive resin composition A pattern forming method and an electronic device manufacturing method using the method can be provided.

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 a Japanese patent application filed on November 29, 2019 (Japanese patent application 2019-217606), a Japanese patent application filed on March 25, 2020 (Japanese patent application 2020-54955), filed on June 22, 2020 It is based on Japanese patent application (Japanese Patent Application No. 2020-107200) and Japanese Patent Application (Japanese Patent Application No. 2020-145919) filed on August 31, 2020, the contents of which are incorporated herein by reference.

Claims (13)

An actinic ray-sensitive or radiation-sensitive resin composition containing a resin whose polarity is increased by the action of an acid, a photoacid generator, and a compound represented by the following general formula (1),
The resin whose polarity is increased by the action of an acid has at least one repeating unit represented by the following formula AI and a repeating unit represented by the following formula (AII),
The photoacid generator is at least one of a sulfonium salt compound and an iodonium salt compound,
The content of the photoacid generator is 2% by mass or more based on the total solid content of the actinic ray-sensitive or radiation-sensitive resin composition,
The content of the compound represented by the general formula (1) is 0.1 mass ppm or more and 500 mass 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.

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, a cycloalkyl group, an alkenyl group, or an aryl group, and any two of Rx ¹ to Rx ³ may or may not combine to form a ring structure.

In 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.
n represents an integer of 1-4.

In general formula (1), R ₁ to R ₃ represent methyl groups. The activity sensitivity according to claim 1, wherein the content of the compound represented by the general formula (1) is 1 ppm by mass or more with respect to the total mass of the actinic ray-sensitive or radiation-sensitive resin composition. Light sensitive or radiation sensitive resin composition. 3. The content of the compound represented by the general formula (1) is 100 mass ppm or less with respect to the total mass of the actinic ray-sensitive or radiation-sensitive resin composition, according to claim 1 or 2. Actinic ray-sensitive or radiation-sensitive resin composition. Claims 1 to 3, wherein a compound represented by the following general formula (2) is contained in an amount of 0.1 ppm by mass or more and 500 ppm by mass 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 according to any one of the above.

In general formula (2), R ₄ and R ₅ each independently represent an alkyl group having 1 to 5 carbon atoms. The activity sensitivity according to claim 4, wherein the content of the compound represented by the general formula (2) is 1 ppm by mass or more with respect to the total mass of the actinic ray-sensitive or radiation-sensitive resin composition. Light sensitive or radiation sensitive resin composition. 6. The content of the compound represented by the general formula (2) is 200 mass ppm or less with respect to the total mass of the actinic ray-sensitive or radiation-sensitive resin composition, according to claim 4 or 5. Actinic ray-sensitive or radiation-sensitive resin composition. The actinic ray-sensitive or radiation-sensitive resin composition according to any one of claims 1 to 6, containing 1 mass ppm or more and 1 mass% or less of water with respect to the total mass of the actinic ray-sensitive or radiation-sensitive resin composition. Or a radiation-sensitive resin composition. The actinic ray-sensitive or radiation-sensitive resin according to claim 7, wherein the water content is 0.01% by mass or more 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 7 or 8, wherein the content of said water is 0.5% by mass or less with respect to the total mass of said actinic ray-sensitive or radiation-sensitive resin composition. elastic resin composition. It contains a compound represented by the following general formula (3), and the content of the compound represented by the general formula (1) with respect to the compound represented by the general formula (3) is 0.1 ppm by mass or more and 0 The actinic ray-sensitive or radiation-sensitive resin composition according to any one of claims 1 to 9, which is 0.05% by mass or less.

In general formula (3), R ₆ to R ₈ each independently represent an alkyl group having 1 to 5 carbon atoms. The actinic ray according to claim 10, wherein the content of the compound represented by the general formula (1) with respect to the compound represented by the general formula (3) is 1 ppm by mass or more and 0.005% by mass or less. sensitive or radiation sensitive resin composition. After applying the actinic ray-sensitive or radiation-sensitive resin composition according to any one of claims 1 to 11 on a support , the active ray-sensitive or radiation-sensitive resin composition is heated at 70°C to 100°C. a pattern comprising the steps of: forming an active ray-sensitive or radiation-sensitive film; exposing the actinic ray-sensitive or radiation-sensitive film; and developing the exposed actinic ray-sensitive or radiation-sensitive film with a developer. Forming method. A method for manufacturing an electronic device, comprising the pattern forming method according to claim 12 .

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